Indian Institute of Metals Series

A. K. Tyagi
Raghumani S. Ningthoujam Editors

Handbook
on Synthesis
Strategies
for Advanced
Materials
Volume-II: Processing and
Functionalization of Materials
Metallurgy
Materials Engineering
Indian Institute of Metals Series
About the Book Series:
The study of metallurgy and materials science is vital for developing advanced
materials for diverse applications. In the last decade, the progress in this field has
been rapid and extensive, giving us a new array of materials, with a wide range of
applications, and a variety of possibilities for processing and characterizing the
materials. In order to make this growing volume of knowledge available, an
initiative to publish a series of books in Metallurgy and Materials Science was taken
during the Diamond Jubilee year of the Indian Institute of Metals (IIM) in the year
2006. Ten years later the series is now published in partnership with Springer.
This book series publishes different categories of publications: textbooks to
satisfy the requirements of students and beginners in the field, monographs on
select topics by experts in the field, professional books to cater to the needs of
practicing engineers, and proceedings of select international conferences organized
by IIM after mandatory peer review. The series publishes across all areas of
materials sciences and metallurgy. An eminent panel of international and national
experts acts as the advisory body in overseeing the selection of topics, important
areas to be covered, and the selection of contributing authors.

More information about this series at https://link.springer.com/bookseries/15453

A. K. Tyagi · Raghumani S. Ningthoujam
Editors

Handbook on Synthesis
Strategies for Advanced
Materials
Volume-II: Processing and Functionalization
of Materials

Metallurgy
Materials Engineering
Editors
A. K. Tyagi Raghumani S. Ningthoujam
Chemistry Division Chemistry Division
Bhabha Atomic Research Centre Bhabha Atomic Research Centre
Mumbai, Maharashtra, India Mumbai, Maharashtra, India
Homi Bhabha National Institute Homi Bhabha National Institute
Mumbai, Maharashtra, India Mumbai, Maharashtra, India

ISSN 2509-6400 ISSN 2509-6419 (electronic)

Indian Institute of Metals Series
ISBN 978-981-16-1802-4 ISBN 978-981-16-1803-1 (eBook)
https://doi.org/10.1007/978-981-16-1803-1

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature
Singapore Pte Ltd. 2022
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Singapore
Series Editor’s Preface

The Indian Institute of Metals Series is an institutional partnership series focusing

on metallurgy and materials science and engineering.

About the Indian Institute of Metals

The Indian Institute of Metals (IIM) is a premier professional body (since 1947)
representing an eminent and dynamic group of metallurgists and materials scientists
and engineers from R&D institutions, academia, and industry, mostly from India.
It is a registered professional institute with the primary objective of promoting and
advancing the study and practice of the science and technology of metals, alloys, and
novel materials. The institute is actively engaged in promoting academia–research
and institute–industry interactions.

Genesis and History of the Series

The study of metallurgy and materials science and engineering is vital for developing
advanced materials for diverse applications. In the last decade, the progress in this
field has been rapid and extensive, giving us a new array of materials, with a wide
range of applications and a variety of possibilities for processing and characterizing
the materials. In order to make this growing volume of knowledge available, an
initiative to publish a series of books in metallurgy and materials science and engi-
neering was taken during the Diamond Jubilee year of the Indian Institute of Metals
(IIM) in the year 2006. IIM entered into a partnership with Universities Press, Hyder-
abad, and, as part of the IIM book series, 11 books were published, and a number
of these have been co-published by CRC Press, USA. The books were authored by
eminent professionals in academia, industry, and R&D with outstanding background
in their respective domains, thus generating unique resources of validated expertise

v
vi Series Editor’s Preface

of interest in metallurgy. The international character of the authors’ and editors has
enabled the books to command national and global readership. This book series
includes different categories of publications: textbooks to satisfy the requirements of
undergraduates and beginners in the field, monographs on selected topics by experts
in the field, and proceedings of selected international conferences organized by IIM,
after mandatory peer review. An eminent panel of international and national experts
constitutes the advisory body in overseeing the selection of topics, important areas
to be covered, in the books and the selection of contributing authors.

Current Series Information

To increase the readership and to ensure wide dissemination among global readers,
this new chapter of the series has been initiated with Springer in the year 2016.
The goal is to continue publishing high-value content on metallurgy and materials
science and engineering, focusing on current trends and applications. So far, four
important books on state of the art in metallurgy and materials science and engi-
neering have been published and, during this year, three more books are released
during IIM-ATM 2021. Readers who are interested in writing books for the Series
may contact the Series Editor-in-Chief, Dr. U. Kamachi Mudali, Former President
of IIM and Vice Chancellor of VIT Bhopal University at [email protected],
[email protected] or the Springer Editorial Director, Ms. Swati Meherishi at
[email protected].

About the Three Volumes of Handbook on Synthesis

Strategies for Advanced Materials

The Handbook on “Synthesis Strategies for Advanced Materials” is aimed to provide

information on (i) Variety of synthetic methods to prepare advanced materials
(stable and metastable hitherto unknown materials, chemically and crystallograph-
ically designed materials and assemblies) and their structure, micro-structure, and
morphology; and (ii) Functional properties like soft to hard, insulators to supercon-
ductors, crystalline to amorphous like glass or polymeric, nano- to thin films to bulk
single crystals. Keeping in mind the interests of students and young researchers, and
senior faculty members, the basic concepts of synthesis, processing and materials
aspects, and their recent developments are covered in three volumes.
The Editors Dr. A.K. Tyagi, Director, Chemistry Group, and Dr. S.R. Ningth-
oujam, Scientific Officer-F, Chemistry Group, from Bhabha Atomic Research Centre
have meticulously edited the three volumes with 20 each chapters for Vols. I and II,
and 18 chapters for Vol. III. These chapters have been prepared by the editors as well
as well-experienced authors from academia, R&D, and industry. This handbook will
Series Editor’s Preface vii

be a treasure for those who are interested in learning everything about advanced mate-
rials and pursue a career and study in the area of advanced materials. The editors
and authors are gratefully acknowledged for their excellent chapters covering wide
range of information on the subject matter.
Dr. U. Kamachi Mudali
Editor-in-Chief
Series in Metallurgy and Materials Engineering
Preface

The ever-developing human civilization thrives on materials which may be of tech-

nological, health, environmental, or geological relevance. The development of mate-
rials has, thus, been a constantly evolving process both in nature as well as by human
efforts. Over the time immemorial, a continuous evolution of materials for fulfillment
of needs of healthy living or advanced lifestyle has been witnessed and that makes
the twenty-first century a century of materials. This is recognized by the surge in
advanced materials in engineering, electronics, and communications as well as in
healthcare, medicine, and societal sectors. The fascinating and ever-growing world
of materials extends from soft materials to super-hard materials, insulators to super-
conductors, extended solids to molecular solids, self-assembled materials, catalysts,
materials with tailored thermal expansion, composites and hybrid materials, materials
with multifunctionality, ceramics and glasses, metals–alloys–intermetallics, drugs
and drugs delivery systems, polymers, bio-materials, nuclear materials, optical mate-
rials, fast ionic conductors, soft and hard magnets, etc. Still the quest of humanity for
developing better and more efficient materials remains never ending. The develop-
ment of materials depends on the ability to synthesize them, or to find a more cost- and
energy-efficient synthesis methodology or design newer materials with appropriate
constituents and functionalities to make them usable. Thus, the synthesis methods
play a pivotal role in the materials research. Although the synthesis or synthetic
materials chemistry originated just after the Stone Age, the understanding of chem-
istry and physics of materials with the progress of time only could lead to discovery
of newer materials as well as the targeted materials for desired purposes. This in
turn resulted in the development of state-of-art synthesis procedures. Further, new
functional materials are also being designed by interplay of synthesis methodologies,
crystallographic structures, morphologies, and dimensionality for desired functional
properties. Many a times, thermodynamics and kinetic parameters are controlled
to overcome the barriers to achieve the desired materials. Thus, the methodologies
for synthesis of materials became multidisciplinary which include the approaches
from chemists, biologists, physicists, metallurgists, and engineers. This has been
witnessed as the development of several unconventional synthetic routes that involve

ix
x Preface

parameters such as extremely high temperature, high pressure, radiation, mechan-

ical attrition and unusually reactive intermediates. Some non-traditional synthesis
routes have also been developed that follow a gentle chemical reaction favoring an
intermediate or alternate pathway to bypass hindrance to reach the targeted material
or utilizing the memory of the materials to introduce functionalities. The unconven-
tional synthesis methodologies play important roles in the direction of many new
and metastable materials which otherwise were not possible to prepare. Similarly,
the multifunctional materials, i.e., the materials which can perform two or more
synergistic or antagonistic functionalities are being achieved by judicious adoption
of synthesis methods. In addition, varieties of soft chemical methods have emerged
that play important roles in the field of functional materials, in particular medicine
and healthcare products to design materials for desired technological applications.
Thus, the material synthesis assumes an unprecedented role in this endeavor and
remains as a challenge as well as an opportunity to chemists and materials scien-
tists. The synthesis methods and their scopes have been discussed in varieties of
monographs as well as compilations and proceedings from time to time. Usage for
various synthetic methods for preparation of newer and exotic materials as well as
recent modifications and their potentials as handy information is essentially a need
for researchers in today’s times and that has been achieved in this present compilation
Handbook on Synthesis Strategies for Advanced Materials, Volumes I, II, and III.
This handbook series on Synthesis Strategies for Advanced Materials is aimed to
provide information on varieties of synthetic methods being adopted by researchers
to prepare different kinds of advanced materials covering from the viewpoints of
structure, micro-structure and morphology of materials, stable and metastable hith-
erto unknown materials, chemically and crystallographically designed materials and
assemblies, as well as from the viewpoints of functional properties like soft to hard,
insulators to superconductors, crystalline to amorphous like glass or polymeric, nano-
to thin films to bulk single crystal. These have been achieved by adoption, alter-
ation, or judicious selection of synthesis methods. Keeping in mind the interests
of students and young researchers, and senior faculty members, the basic concepts
of synthesis, processing, and materials aspects and their recent developments are
covered in three volumes, namely Volume-I: Techniques and Fundamentals, Volume-
II: Processing and Functionalization of Materials, and Volume-III: Materials Specific
Synthesis Strategies. Each volume is made independent by taking care of minimal
overlap of the topics. Volume-I is primarily focused on the principles and proce-
dures of various synthesis methods. The basic principles and scope/limitations of
various synthetic methods, like solid-state reaction to gentle molecular aggregation
methods and chimie douce, synthesis under high temperature, hot-injection method,
polyol method, metal-organic frameworks, electrochemical method, mechanochem-
istry, hydro/solvothermal reaction, high-pressure and high-temperature reactions, arc
melting, induction heating, melt-quench method, ion-exchange process, microwave
and visible to gamma radiations, green methods of synthesis, thermolysis, bio-
inspired synthesis, etc., are discussed along with the inputs from authors’ hands on
experience and expertise. In Volume-II, various processing methodologies for prepa-
ration of various types of functional materials or functionalization of materials by
Preface xi

chemical, structural, or microstructural alterations are presented. This volume covers

the processing of nanomaterials, porous or sintered materials, composite materials,
low-dimensional like 1D to 2D materials, thin films, single crystals, template method,
self-assembly, biomaterials, inkjet printing, 3D printing, size and shape engineering,
etc., in a lucid manner. Volume-III is focused on the synthesis aspects of materials
like hybrid inorganic–organic, metal oxide frameworks, intermetallics, hydrides,
borides, carbides, nitrides, phosphides, silicide, selenides, fluorides, various bio-
materials, materials for sensors and detectors, optical materials, carbon-based mate-
rials, colloids, noble gas compounds, lithium based ceramics, materials with unusual
oxidation state, organo-selenium and platinum compounds, silicon-based materials,
and lithium-based ceramics. The evolution and state-of-the-art synthesis methods for
practical requirements as well as new concepts with most recent literatures dealing
with their synthesis are presented in this volume. These volumes are expected to
serve as handy guides for synthesis and processing of advanced materials of wide
range and category.
The editors are immensely thankful to all the authors for their rich contributions
toward this book. Although due efforts have been taken to make the book as error-free
as possible, some may have crept in as unnoticed. We shall be thankful to the readers
for bringing such unintentional errors to our notice. Finally, we sincerely hope that
our efforts will be of use to both new and experienced researchers in the field.

Mumbai, India A. K. Tyagi

November, 2021 Raghumani. S. Ningthoujam
Contents

1 Shape Forming and Sintering of Ceramics . . . . . . . . . . . . . . . . . . . . . . . 1

R. K. Lenka, P. K. Patro, and T. Mahata
2 Growth of Single Crystals for Nuclear Radiation Detection . . . . . . . . 55
Mohit Tyagi and S. C. Gadkari
3 Techniques for Thin Films of Advanced Materials . . . . . . . . . . . . . . . . 81
K. R. Sinju, A. K. Debnath, and Niranjan S. Ramgir
4 Inkjet Printing of Nanomaterials and Nanoinks . . . . . . . . . . . . . . . . . . 119
O. D. Jayakumar and A. K. Tyagi
5 Particle Size and Shape Engineering for Advanced Materials . . . . . . 133
R. S. Ningthoujam and A. K. Tyagi
6 Synthesis of Porous Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
Deepak Tyagi and K. Bhattacharyya
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium
Oxide Templates and Template-Based Nanomaterials . . . . . . . . . . . . . 229
S. Boominatha sellarajan and Subir Kumar Ghosh
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional
Thin Film Architecture Photoelectrodes for Artificial
Photosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
Rajini P. Antony
9 Synthesis Strategies and Applications of Metallic Foams
and Hollow Structured Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Ashis Kumar Satpati
10 Exfoliation Routes to the Production of Nanoflakes
of Graphene Analogous 2D Materials and Their Applications . . . . . 377
N. Padma

xiii
xiv Contents

11 Drying of Tiny Colloidal Droplets: A Novel Synthesis Strategy

for Nano-structured Micro-granules . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Debasis Sen, Jitendra Bahadur, and Avik Das
12 Amphiphilic Self-Assembly in the Synthesis and Processing
of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
Bijaideep Dutta, K. C. Barick, Gunjan Verma, Sipra Choudhury,
R. Ganguly, and P. A. Hassan
13 Synthesis of Functionalized Noble Metal Nanoparticles . . . . . . . . . . . 515
Abhishek Das and Nandita Maiti
14 Synthesis and Surface Functionalization of Nanostructured
Biomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
Santosh L. Gawali, Bijaideep Dutta, Jagriti Gupta, P. A. Hassan,
and K. C. Barick
15 Implications of Synthesis Methodology on Physicochemical
and Biological Properties of Hydroxyapatite . . . . . . . . . . . . . . . . . . . . . 617
Mural Quadros, Munira Momin, and Gunjan Verma
16 Synthesis and Processing of Magnetic-Based Nanomaterials
for Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
Arunima Rajan, R. K. Chandunika, Femy Raju, Rashmi Joshi,
Niroj Kumar Sahu, and Raghumani Singh Ningthoujam
17 Role of Synthesis in Evolution of Catalyst: Bulk, Dispersed
to Single Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
Mrinal R. Pai, Sushma. A. Rawool, Rajendra V. Singh,
Atindra Mohan Banerjee, and A. K. Tripathi
18 Synthesis—Activity Correlations Established for TiO2 Based
Photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 753
Sushma A. Rawool, Mrinal R. Pai, Rajendra V. Singh,
Atindra Mohan Banerjee, and Arvind K. Tripathi
19 Lasers in Materials Processing and Synthesis . . . . . . . . . . . . . . . . . . . . 791
Sisir K. Sarkar
20 Ultra Fast Electrically Exploding Wire Method for Production
of Raw Material for Additive Manufacturing Based 3D
Printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
Rohit Shukla and Archana Sharma
About the Editors

Dr. A. K. Tyagi obtained his M.Sc. (Chemistry)

degree in 1985 from Meerut University, Meerut, Uttar
Pradesh, India and joined 29th batch of BARC Training
School, Mumbai in the same year. After completing one
year orientation course, he joined Chemistry Division,
Bhabha Atomic Research Centre (BARC), Mumbai
in 1986. Presently, he is Director, Chemistry Group,
BARC, Mumbai, and a Senior Professor of Chemistry
at Homi Bhabha National Institute (HBNI), Mumbai.
His research interests are in the field chemistry of mate-
rials, which includes functional materials, nanomate-
rials, nuclear materials, energy materials, metastable
materials, hybrid materials and structure-property corre-
lation. He has published more than 600 papers in
journals, several books and has supervised 30 Ph.D.
students.
He was awarded Ph.D. by Mumbai University,
Mumbai in 1992. He did postdoctoral research at
Max-Planck Institute for Solid State Research (MPI-
FKF), Stuttgart, Germany during 1995–1996 on a Max-
Planck Fellowship. Subsequently, he regularly visited
MPI-FKF, Stuttgart as a visiting scientist. In addi-
tion, he has also visited Institute of Superior Tech-
nology, Portugal; Institute for Chemical Process and
Environmental Technology, Ottawa, Canada; Dalhousie
University, Halifax, Canada; Moscow State University,
Moscow, Russia; Institute for Materials, Nantes, France;
University of Malay, Malaysia; National Institute of
Materials Science, Tsukuba, Japan; National University
of Singapore, Singapore; Royal Institute of Technology,
Stockholm, Sweden; Rice University, Houston, USA;

xv
xvi About the Editors

Shanghai, China; University of Valencia, Valencia,

Spain; Weizmann Institute of Science, Israel; Univer-
sity of Queensland, Brisbane, Australia; US-Air Force
Research Lab, Dayton, USA, Institute for Studies of
Nanostructured Materials, Palermo, Italy and iThemba
Labs, Cape Town, South Africa.
In recognition of his significant contributions to the
field of chemistry of materials, he has been conferred
with many prestigious awards, such as Dr. Lakshmi
award by the Indian Association of Solid State Chemists
and Allied Scientists (2001); Rheometric Scientific-
Indian Thermal Analysis Society Award (2002); Gold
Medal of Indian Nuclear Society (2003); Materials
Research Society of India’s Medal (2005); Chemical
Research Society of India’s Bronze Medal (2006); DAE-
Homi Bhabha Science and Technology Award (2006);
IANCAS-Dr. Tarun Datta Memorial Award (2007);
Rajib Goyal Prize in Chemical Sciences (2007); RD
Desai Memorial Award from Indian Chemical Society
(2008) and DAE-SRC Outstanding Research Investi-
gator Award (2010); CRSI-Prof. CNR Rao National
Prize in Chemical Sciences (2012); ISCB Award for
Excellence in Chemical Sciences (2013); MRSI-ICSC
Materials Science Senior Award (2014); Coastal Chem-
ical Research Society’s Award (2014); Platinum Jubilee
Lecture Award in Materials Science from Indian Science
Congress Association (2015); Metallurgist of the Year
Award (2017), from Ministry of Steel, Government
of India; Chemical Research Society of India’s Silver
Medal (2018); Materials Research Society of India’s
Prof. CNR Rao Prize in Advanced Materials (2018);
JNCASR’s National Prize in Solid State and Mate-
rials Chemistry (2018) and Acharya PC Ray Memo-
rial Award from Indian Science Congress Association
(2020).
He is an elected Fellow of the Indian Academy of
Sciences (FASc); National Academy of Sciences, India
(FNASc); Maharashtra Academy of Sciences (FMASc);
Royal Society of Chemistry, UK (FRSC) and Asia
Pacific Academy of Materials.
About the Editors xvii

Dr. Raghumani S. Ningthoujam obtained M.Sc. in

Chemistry from Manipur University, Imphal, Manipur,
India in 1994. He was awarded Ph.D. in Chemistry
from IIT Kanpur in area of superconductivity, elec-
tron transport and magnetic properties of nanostruc-
tured transition metal nitrides in 2004. He joined BARC
(Bhabha Atomic Research Centre), Mumbai as Scien-
tific Officer (D) in 2006 after completion of Dr. K. S.
Krishnan Research Associate Fellowship. Presently, he
is working in area of Luminescent and Magnetic Nano-
materials and their applications in sensors, imaging,
diagnosis and therapy. He did Post-Doctoral Fellow-
ship at University of Victoria, Canada in the area of
quantum dots. Presently, he is Scientific Officer (F)
at Chemistry Division, BARC, Mumbai. He is recog-
nized for Guideship of Ph.D. at Homi Bhabha National
Institute (HBNI), Mumbai and Mumbai University,
Mumbai. Many research scholars and students finished
their projects under his guidance. He has published
about 150 papers in the refereed journals, five review
articles and four book chapters. In recognition of his
significant contributions to the chemical science, he
has been awarded DAE-Scientific & Technical Excel-
lence Award in 2012 and Young Achiever Award, SSPS
2010. He has been elected as a Fellow, The National
Academy of Sciences, India (FNASc) in 2016 and
Fellow, Maharashtra Academy of Sciences (FMASc) in
2013.
Chapter 1
Shape Forming and Sintering
of Ceramics

R. K. Lenka, P. K. Patro, and T. Mahata

Abstract Ceramic materials at large are inorganic compounds (oxides, borides,

carbides, and nitrides) having high melting temperature and inherent brittleness.
Because of these properties the state-of-the-art melting and casting methodologies
are not applicable for shape forming of ceramic materials. Further, conventional
machining of ceramics is also difficult due to their brittle nature. Therefore, powder
metallurgy route is usually adopted for making ceramic body of near net shape.
Initially green shapes are formed and subsequently sintered to get the product of
desired density and microstructure. The packing of ceramic powders need to be
uniform throughout the green shape in order to avoid warping or cracking of the
shape during sintering. For achieving uniform packing, the powder particles must
flow significantly to fill every space and contours. Different ceramic shape forming
techniques have been evolved based on convenience, reproducibility, and state of
feed material. Dry powder pressing is the most common among these. Various addi-
tives are mixed with powders to make the feed material in paste form or suspension
form which shows good plasticity and flowability. In the green shapes, powder parti-
cles are in physical contact without any bonding. Upon firing the green compact, a
coherent, predominantly a solid structure is formed due to mass transfer through a
process called sintering. Decrease in surface free energy is the driving force for the
process. Mass transfer is the basis to fill the pores and a resultant dense coherent
mass with definite microstructure is obtained. Mass transfer takes place due to the
difference in chemical potential between two regions. There are different pathways
through which mass transfer takes place. Sintering techniques are generally classified
based on diffusion pathway and type of applied field/heating to assist in sintering.
This chapter deals with the various techniques of ceramic shape forming, sintering
techniques, mechanism of sintering, and factors affecting sintering. At the end the
future directions of ceramic shape forming and sintering have been discussed.

R. K. Lenka (B) · P. K. Patro · T. Mahata

Powder Metallurgy Division, Bhabha Atomic Research Centre, Vashi Complex, Navi Mumbai
400703, India
e-mail: [email protected]
P. K. Patro · T. Mahata
Homi Bhabha National Institute, Mumbai 400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 1
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_1
2 R. K. Lenka et al.

Keywords Consolidation techniques · Shape forming · Sintering phenomena ·

Sintering mechanism · Assisted sintering

1.1 Introduction

Ceramic materials are being used since ancient times for different applications due to
its higher strength and non-corrosive nature. In date to day life traditional ceramics
like potteries, porcelains, cement, glass, etc. are being used. Advance ceramics or
engineering ceramics are being explored in recent times to mitigate the challenges
offered to develop materials of enhanced functional properties. These ceramics are
being used for electrical, optical, magnetic, nuclear, thermal, chemical, and biolog-
ical applications [1–4]. Among these advanced ceramics which finds its technolog-
ical application needs stringiest compositional control, processing condition, shape
forming methodology, and sintering conditions to meet the functional requirement.
This needs expertise in the field of advanced ceramic fabrication technology with
a combination of a good understanding of solid-state chemistry and physics. Based
on the end applications, one particular ceramic material may have to go through
several processing conditions. Material availability, specific properties, and fabrica-
tion technique are three corners of the product triangle. However, availability of the
material or synthesis of the material in desired phase is a matter of concern. Once
the phase pure material is developed, the role of fabrication technique is to prepare
desired shape and size for the intended application. Here, processing of ceramics is
required to get a near net structure which need to be sintered for further densifica-
tion. During sintering, dimension of the green shape decreases appreciably leading
to stress and defects in the material. Raw material quality and pre-processing are
required to minimize the dimensional change and defect annihilation.
Ceramic materials due to its higher melting temperature cannot be shaped like
metals via melting and casting methods. Hence powder metallurgy route is adopted
for shape forming of ceramics followed by sintering. Shape forming in ceramics
is undoubtedly the key stage in the manufacturing of any ceramic component; this
not only determines its geometry but also its functional requirement. The functional
properties are in turn influenced by the properties of the raw materials [5]. Broadly
ceramics show mixed bonding behavior, a combination of covalent and ionic bonds.
This determines the type and selections of consolidation techniques which will be
more appropriate to arrive at a component with desired properties. Before finalizing
a consolidation technique, physical and chemical characterization of powder parti-
cles are carried out first followed by the selection of additives required for powder
processing and shape forming technique.
Shaping alone does not circumvent the purpose. The desired functional proper-
ties like mechanical property, electrical property, optical property, magnetic property,
catalytic property are prominent in the dense structure. Intrinsic properties such as
thermal expansion, elastic modulus, and melting temperature do not depend on the
1 Shape Forming and Sintering of Ceramics 3

microstructure of the sintered body. However, electrical properties, magnetic proper-

ties, dielectric properties, mechanical properties depend on the microstructure [6]. In
a sintering process, coherent and preferentially a solid structure is achieved on heating
the green compact at high temperatures. Strong inter particle bonding is developed
with decrease in the inter particle space by diffusional mass transport. With progress
of sintering temperature and time different microstructure is developed. Based on
the microstructural development, different stages of sintering are assigned and mech-
anism for the same has been evolved. The factors that influence sintering process
are sintering temperature, heating rate, atmosphere, pressure, composition, and non-
stoichiometry; hence influence the product quality [7, 8]. All these aspects will be
covered in this chapter.

1.2 Important Characteristics of Ceramic Feed Material

for Shape Forming

The starting powder characteristics (physical and chemical) have significant influence
on the consolidation and sintering processes. The most important characteristics are
phase purity, particle shape, size, and distribution. For achieving a good sintered
product it is desirable to have a uniform and more closed powder packing in the
green compact which is guided by the powder quality. Chemical composition and
purity are of utmost importance in processing advance ceramics. A small change in
the chemical composition or presence of impurity largely influences the functional
property of the ceramic products. For example, transparency in magnesium aluminate
ceramics decreases drastically with the incorporation of a small amount of impurity
[9]. LiF addition to the magnesium aluminate spinel increases the transparency as it
helps in removing the impurities at the grain boundaries. Apart from impurity, phase
purity of the starting powder is also ensured to achieve desired properties.
Surface area of the powder is an important parameter which influences the sinter-
ability and densification. Particle agglomeration is a phenomenon which retards
sinterability. As the particles obtained from various processes are generally submi-
cron in size there is a tendency to agglomerate during preparation steps. This agglom-
eration can be avoided in the wet chemical synthesis route by adding suitable disper-
sant. In a powder mass the particles can be a primary particles or particle agglom-
erate. Primary particle is the smallest unit with definite boundary/surface. It cannot
be further broken down by forces like ultrasonication, grinding etc. Primary particles
are bonded together by weak forces and form agglomerates. Hence, interconnected
porosities remain there within an agglomerate. Based on the strength of the agglom-
erates, it can be soft or hard. The soft agglomerates are likely to be broken down into
primary particles by repeated milling or pressing. Particle is in general the smallest
unit that moves in a medium or the smallest unit that is transferred. Schematic diagram
of primary particle, porosity, and agglomerates is shown in Fig. 1.1. From the picture,
it can be seen that isolated pores do exist in the primary particle and continuous pores
4 R. K. Lenka et al.

Fig. 1.1 Schematic diagram

of agglomerate showing
particles and porosity

in the inter particle space. Another term commonly used is aggregate, which is a large
size (1–50 μm) hard agglomerate. Aggregates are difficult to break by ultrasonica-
tion and even by ball milling, hence avoided in the powder metallurgical processes.
Non-uniform and preferential sintering takes place at certain regions in the aggregate
which leads to non-uniform densification.
Ceramics are divided into two categories, namely, crystalline materials and amor-
phous materials. In crystalline materials, there is a long range repeated rearrangement
of atoms in three dimensions. The smallest unit of the crystalline material is called
crystallite or grain. When the primary particle is a single crystallite, it is called a
single crystal. When a primary particle constitutes lots of crystallites separated by
boundaries called grain boundaries, this particle is called a polycrystalline material.
This grain boundary region is a highly disordered area where there is a random
arrangement of atoms. Grain size may vary from nanometer range to micron range.
In polycrystalline materials when the grains are in nanometer range, these are called
nanocrystalline materials. These nanocrystalline materials show distinct advantages
due to finer grains, and higher grain boundary area to grain area. For example, super-
plasticity of Ni3 Al alloys decreases from 1050 to 650 °C when the grain size changes
from 6 μm to 50 nm [10]. Many of the properties like hardness, strength, ductility,
thermal conductivity, electrical conductivity are influenced by the nanocrystalline
nature of the materials [11]. Amorphous materials like glasses and cements do not
have either long range repeated arrangement of atoms or they have distinct grain
boundaries. Hence, they offer different kinds of mechanical, thermal, and electrical
properties.
In many of the shape forming methods, powders are often granulated to increase
the flowability which in turn gives uniform green density, reproducible property, and
improved productivity. Within a granule, a high packing density is obtained. The need
of granulation is experienced while compacting nano-powders. Low flowability of
nano-powders in the die filling step leads to inhomogeneous powder packing. There-
fore, nano-powders need to be granulated before going for any shape forming process.
Some of the defects in the pressing of nano-powder are end capping, chipping, non-
uniform densification along the uniaxial pressure direction. For ceramics, both dry
and wet granulation methodologies are adopted depending on the nature of powder.
1 Shape Forming and Sintering of Ceramics 5

As the starting powder has significant influence on the shape forming methods, its
physical and chemical characterization is done first. Based on the properties, further
processing method is decided.

1.2.1 Physical Characteristics

Measurement of particle size and distribution: Different methods have been used to
measure the particle size of the powders. Microscopy is being used to see the particle
size and shape. If the particle size is more than ~1 μm optical microscope is used
to observe the size. For lower size particles down to ~1 nm, electron microscope is
used. Due to higher resolution, degree of agglomeration is also observed from the
electron micrographs. For measuring the average particle size and distribution, the
image analysis tools are used where a large number of image files can be processed
in a small-time scale.
Sedimentation method is also used for size measurement. Principle of particle
size measurement using sedimentation of powder particle through a liquid medium
is based on Stokes law. When a powder is falling in a viscous medium, it attains
a constant velocity called terminal velocity defined by the weight of the particle
and viscosity of the medium. In this method powder is put on a liquid surface and
concentration of particles at a particular height is measured with time. This gives
information about the size and particle fraction. Sedimentation method has its own
limitation. When the size of the particle comes down to nanometer range, the particle
follows Brownian motion, and erroneous sedimentation result is obtained.
The most common method used for particle size measurement is based on light
scattering. The principle of particle size measurement based on light scattering is
based on Raleigh scattering theory, Mie theory and Fraunhofer diffraction theory.
When light falls on a particle dispersed in a medium, the scattering angle is inversely
proportional to the size of the particle. One to two monochromatic light sources are
used for scattering experiment and the intensity of light are measured at different
angles. Measurement of scattered light at a certain angle defines the particle size
and intensity of light defines the population. Particle sizes from 0.1 to 1000 μm can
be measured by light scattering method. Brownian motion of smaller particle lower
than 0.1 μm when dispersed in a liquid limits the use of most intensively used light
scattering method for measuring the size. For nano particles, intensity of the scattered
light at a particular angle changes with time. This change in intensity of the scattered
light is monitored and particle size information is calculated from Stokes-Einstein
equation. This is the basis of particle size measurement of nano particles via dynamic
light scattering.
6 R. K. Lenka et al.

Particle size can also be measured from the broadening of the x-ray diffraction
peak pattern.
This broadening is calculated from the full width at half maximum (FWHM).
Instrument broadening and residual stress in the sample also contribute to the broad-
ening phenomena. Suitable methods are utilized to calculate the broadening due to
sample only and the other factors are subtracted from the measurement. It can be
mentioned here that the size measured by x-ray line broadening is the crystallite size.
Hence, the value measured here will be always lowest compared to size measured
by other methods. For most of the nano-materials, crystallite size is equal to particle
size when there is no agglomeration between the particles.
Surface area: Measurement of surface area is based on the principle of nitrogen
adsorption on the particle surface. Powder sample is degassed at 200–300 °C and
equilibrated with nitrogen gas at different pressure keeping sample at liquid nitrogen
temperature. Adsorption-desorption isotherm from the surface area measurement
gives an idea of pores inside the particles. Results from particle size analysis, surface
area measurement, and X-ray line broadening can be correlated to get information
about primary particles, agglomerates, and extent of agglomeration.

1.2.2 Chemical Characteristics

Chemical characterization of powders before shape forming includes compositional

characterization, phase characterization, and surface characterization. Compositional
characterization of the powder includes the determination of chemical composition
and the impurity analysis in the sample. Phase characterization includes the phase
formation and crystal structure determination. Surface characterization includes the
determination of composition at the surface and oxidation state of the element on the
powder surface.

1.2.2.1 Chemical Characterization

Powder composition has been analyzed by atomic absorption spectroscopy (AAS)

and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The
sample is dissolved in suitable acid or alkali medium and the elemental composition
is measured from the absorption or emission spectra. Many ceramics are not soluble
with any of the solvents. Hence it is difficult to analyze the samples by these above
methods. X-ray fluorescence spectroscopy is often used to analyze the elemental
composition of ceramics. Solid samples can be analyzed directly without dissolving
in a medium. As the analysis is very fast, it is widely used for compositional analysis
at the first site. Detection limit of this method is poor compared to AAS, hence impu-
rity analysis is more preferred in AAS. Another method of analyzing composition is
by DC arc method. DC arc is being used to excite the sample from solid state to vapor
1 Shape Forming and Sintering of Ceramics 7

form. Once the sample is vaporized, its absorption spectra are recorded for elemental
analysis. Apart from these, techniques like neutron activation analysis (NAA), energy
dispersive spectra (EDS), and electron energy loss spectroscopy (EELS) are used for
impurity analysis.

1.2.2.2 Phase Characterization

The phase purity of the material is confirmed by analyzing the X-ray diffraction
pattern of the sample at room temperature. Phase evolution of the sample at high
temperatures is analyzed by heating the sample at high temperature and simultane-
ously taking the diffraction data. Apart from the phase information, the lattice struc-
ture can be refined from the diffraction data. Similar to x-ray diffraction, neutron
diffraction experiments are used for phase and structural characterizations of mate-
rials. As neutrons interact more with low Z elements, polymer samples are extensively
studied via neutron diffraction experiments. Due to coupling of magnetic field with
neutrons, magnetic domains are well characterized by neutrons. However, due to less
availability of neutron source, this method is limited to laboratory experiments only.

1.2.2.3 Surface Characterization (Compositional)

As decrease in surface free energy is the driving force for sintering, surface charac-
terization has immense influence in the sintering process. Surface compositions and
defect concentration on the surface are important. Techniques like auger electron
spectroscopy, x-ray photo electron spectroscopy, Fourier-transform infrared spec-
troscopy (FTIR), Raman spectroscopy are used to know the surface composition and
oxidation state of different elements. Combined with surface area data, this surface
information has vital role in defining surface diffusion mechanism and hence the
sintering mechanism.

1.3 Role of Additives in Ceramic Green Shape Formation

There are four categories of ceramic shape forming processes, which are largely
classified based on the quantity of water/solvent in the ceramic bodies and pressure
applied for shape forming. These are (i) dry shaping (ii) semi dry pressing (iii)
plastic forming and (iv) semi-liquid shaping as shown in Fig. 1.2. In dry pressing, no
water/solvent is mixed with the powder and very high pressure is required. As water
content increases, pressure required for shape forming decreases [12, 13]. Table 1.1
compares the details about three major shape forming methods, namely, dry pressing,
extrusion and slip casting. Comparison is made with respect to complexity of shaping,
cost of production, production rate, industrial adoption of the process, etc.
8 R. K. Lenka et al.

Fig. 1.2 Water content

versus required pressure in
different shape forming
process

Table 1.1 Comparisons of

Dry pressing Extruding Slip casting
three major shape forming
methods Average 5 wt% 17 wt% 28 wt%
moisture
content
Green density High Medium-high Low
Green Low Medium High
deformability
Mold/die Rigid or Elastic Rigid Rigid
material
Mold/die No No Yes
porosity
Shrinkage Low Medium High
after sintering
Drying ability High Low Low
Geometry of Simple Quite complex Complex
shaped article
Productivity High High Low
Automation High High Low
level
Specific Medium Low High
production
cost

Powder packing density in the green shape should be uniform in order to achieve
sintered body with uniform density and microstructure. Depending on the shape
forming method ceramic powder is mixed with essential additives in a definite ratio.
The common additives include solvent, binder, plasticizer, dispersant, and lubricant.
1 Shape Forming and Sintering of Ceramics 9

The combination of additives that are to be used depends on the shape forming
methodology. Each additive has specific roles in green shape forming as described
below.
Binders: Binders are long chain polymer molecules either soluble in water or in
organic liquid. Binder when added with powder in small concentration creates bridges
between the particles and provides handling strength in the green body formed by
pressing dry powders. Binders are also added in the powder granulation step. The
granules are often used as feed material for powder compaction. Binders are used
in high concentration to provide flexibility in the feed material for shape forming
through processes like extrusion and injection molding. When used in high concen-
tration, binder burn out (BBO) step becomes critical in subsequent processing.
Temperature, holding time, heating rate, and atmosphere are judiciously chosen in
the binder burn out step. Some of the water soluble binders are polyvinyl alcohol
(PVA), polyvinylpyrrolidone, poly acrylic acid, polyethylene glycol, methyl cellu-
lose, starch, and dextrins. Binders commonly used in organic medium are polyvinyl
butyral (PVB), poly methyl methacrylate (PMMA), ethyl cellulose, etc.
Plasticizers: Plasticizers are usually of low molecular weight organic substances and
used to soften the binder in the dry or near dry state. Plasticizer is most commonly
used in tape casting process and the role is to increase the flexibility of the green
body. Plasticizers must be soluble in the same liquid which dissolves the binder. The
plasticizer molecules interact with the polymer chains of the binder softens the chain
alignment and reduce the Van der Waals bonding. Some commonly used plasticizers
are ethylene glycol, polyethylene glycol (PEG), glycerol, dimethyl phthalate, and
di-butyl phthalate.
Dispersant/De-flocculent: This is essentially used in slurry-based shape forming
methods such as slip casting and tape casting. Dispersants are used to stabilize the
slurry by increasing the repulsion between the particles. The viscosity of slurry is
strongly influenced by the addition of small concentration of dispersant. Addition of
dispersant helps in getting a slurry with high solid content. In aqueous-based slurry,
some of the dispersants are sodium silicate, sodium carbonate, calcium carbonate,
and magnesium sulphate. The most commonly used commercial dispersant in organic
solvents are menhaden fish oil, glyceryl trioleate, oleic acid, sodium polyacrylate,
ammonium polyacrylate, sodium succinate, and sodium citrate. Sometimes these
dispersants leave impurity in the ceramic body, however, their quantity is so small
that it does not affect the functional properties.
Lubricants: It reduces the friction between the powder and the die during compaction
or shaping. This not only increases the life of the die but also gives a smooth surface
to the compact. A dilute lubricant solution is applied over the die surface which
are exposed to the powder. These lubricants are removed at higher temperatures.
Lubricants play important role in die compaction, extrusion, and injection molding
process. Commonly used lubricants are stearic acid, stearates, waxy substances, and
carboxymethyl cellulose.
10 R. K. Lenka et al.

Solvents: The primary role of the solvent lies in the dissolution of the additives and
formation of a homogenous distribution of powder in it. This gives fluidity to the
slurry. Choice of additives depends on the solvent or vice versa. Aqueous medium
is mostly used for making slurry for slip casting and extrusion. The commonly used
organic solvents are methanol, ethanol, isopropanol, acetone, methyl ethyl ketone
(MEK), chlorinated hydrocarbons (tri-chloroethylene), toluene, and xylene. Based
on the cost of organic solvents and associated health issues, aqueous solvent is most
preferred.

1.4 Green Shape Forming Techniques

1.4.1 Shape Forming Processes Staring with Dry Powders

There are two types of dry powder-based shaping methods (a) Uniaxial die pressing
(Hydraulic Pressing) and (b) Isostatic Pressing. Homogenous powder filling in the die
cavity is essential to get a uniform green density. In both types of pressing methods
granulated powder (or spray dried powder) is usually used. As solvent is not used, no
dimensional change is expected in the green compact. A better dimensional control
can be achieved by this dry powder pressing methodology.

1.4.1.1 Uniaxial Die Pressing

In this process granulated powder is allowed to flow into a hardened steel die/mold
followed by uniaxial pressing. Powder inside the die is pressurized and kept at desired
pressure for some time before releasing the pressure. The same press is being used
for ejecting the compact from the die. Normally the die materials used are either
hardened steel or tungsten carbide. Pressing action can be done by movement of
either single punch (top or bottom) or both punches. Accordingly, these are called
as single acting or double acting uniaxial pressing. Schematic of single acting and
double acting die pressing is shown in Fig. 1.3. Double action press is better than the
single action press in getting a fairly uniform density product. This becomes more
significant when the desired shape has large length to diameter ratio.
Sometimes binder is added during dry pressing of the powder which helps in
retaining its shape after the compaction and gives handling strength to the compact.
The binder is chosen in such a way that it leaves the system upon heating without
any traces. Binder is removed at a temperature around 300–500 °C. Binder burnout
schedule and sintering atmosphere are defined accordingly. This method of shape
forming is normally automated to a large extent for mass production of the compo-
nents in industries. A simple grinding or polishing of the compact may result in a
ready to use product. However, this technique is not used for complicated shapes.
1 Shape Forming and Sintering of Ceramics 11

Fig. 1.3 Single and double

action die pressing

After compaction, the green body must be ejected from the die. During die ejection
the green body is released from compression at high pressure to very low pressure
gradually and then pushed out of the mold. The primary force to be overcome during
die ejection is that of wall friction which depends on the roughness of the die wall
and lubrication applied. For walls with a scale of roughness larger than the diameter
of the powder, the wall friction is essentially the same as the internal friction of
the powder. If the wall has a scale of roughness smaller than the diameter of the
powder, the wall friction is controlled by particle-wall friction [14]. Wall friction can
be decreased by lubricants applied to the wall prior to pressing. Common lubricants
like steric acids, stearates, and various waxy substances can be used to minimize the
particle-die wall friction [15].
The common defects observed in this process are delaminations, end capping,
or ring capping. However, use of proper die tooling, selection of pressure, powder
granulation, proper lubrication, and powder filling reduces these common defects. For
example, making a pellet using fine/nano-powder directly may cause end capping and
sometimes cracks. Here, pre-compaction of the powder and granulation annihilates
these defects.

1.4.1.2 Cold Isostatic Pressing (CIP)

In cold isostatic pressing method of shape forming, powders are filled in a flexible
mold (e.g., a rubber membrane or a metallic can) that is subjected to isostatic, external
pressure. The rubber mold is filled with powder and is then submerged in a pressure
12 R. K. Lenka et al.

vessel filled with oil. The fluid is pressurized and the fluid pressure is isostatically
transmitted to the powder.
Normally cold isostatic pressing is of two types (a) Wet bag CIP and (b) Dry bag
CIP as shown in Fig. 1.4a and b. In Wet bag CIP, the rubber mold is filled with powder
and is then submerged in the pressure vessel. This type of CIP is used for shaping
complicated shapes and large jobs with extremely high applied pressure (104 –105
psi). The disadvantage of a wet bag CIP is the possible contamination of the job
with the pressurizing fluid. A leak during compaction or removal of job in the rubber
mold will lead to contamination of the compact with the oil. It is not suitable for near
net shaping, labor intensive, and has low production rate. Hence usually this type of
CIP is limited to R&D laboratories and academic institutes. In dry bag CIP the mold
is fixed in the pressure vessel; powder filling and compacting takes place within the
pressure vessel. The advantages of this type of CIPs are high production rate in an
automatic to semi-automatic systems, free from fluid contamination, capability of
pressing near net-shaped compacts, and less labor intensive. The disadvantages of
dry bag CIP systems are smaller size of compact formation capability and have a
lower pressure capability compared to wet CIP systems [16]. These systems are very
much suited for industries with larger production cycle.
Compression, holding, and decompression cycle is followed precisely to achieve
sound green compact. As the pressure is isostatic the compact achieves uniform
density. The advantages of isostatic pressing over die compaction are uniform hydro-
static pressure, no friction with die wall, and complex shape formation with uniform
density.

1.4.2 Shape Forming Using Ceramic Paste

1.4.2.1 Extrusion

In extrusion, a powder is mixed with solvent, binder, and lubricant to make stiff
dough. Green shapes are formed by pushing the pastes continuously through a die.
Due to higher hardness of ceramics, erosion of the die walls decreases the die life.
Hence, it is a general practice to use lubricating agent while preparing the dough.
Die is typically made of hardened steel or tungsten carbide.
Industrially, the process is usually carried out by a screw-fed extruder connected
to an electric motor. This process can be used to produce long extrudates. Because
of the high shear rates imposed upon the ceramic paste it flows through the die and
upon leaving the die it solidifies into the desired shape as the paste is no longer under
shear. Before it completely solidifies, the extrudate is cut periodically to give green
bodies of definite length [17]. The schematic of extrusion process is shown in Fig. 1.5.
Extrusion is a continuous process with high production rate and low production cost.
However, the products have limited complexity in shape and have uniform cross-
sectional area. Ram driven by hydraulic press is also used for extrusion press. But
these are semi-continuous processes, dough is filled in the die periodically. Solvent
1 Shape Forming and Sintering of Ceramics 13

Fig. 1.4 Schematic of cold

isostatic pressing a Wet bag
CIP. b Dry bag CIP

(a) Wet-bag CIP

(b) Dry-bag CIP

14 R. K. Lenka et al.

Fig. 1.5 Schematic of an extruder machine

drying and binder burn out is a critical step before firing the components. Therefore,
binders and additives are judiciously chosen in an extrusion process.

1.4.2.2 Injection Molding

Ceramic injection molding is the most versatile technique in which the ceramic
powders are converted into a green shape through an organic vehicle. This technique
is similar to polymer processing where a thermoplastic polymer which softens upon
heating and hardens on cooling is used. This thermoplastic polymer is used as binder
in injection molding process. In ceramic injection molding normally the ceramic
powder is added to the thermoplastic polymer (binder) along with other organic
materials to achieve the desired rheological properties. The total organic component
may be as high as 40% of the total mix. Here the plastic mass is first heated and then
forced into a cavity when the desired softening of the mass is achieved. It was then
allowed to cool in the mold so that the organic component hardens. In this process a
typical shrinkage of 15–20% makes it difficult in achieving the desired dimensions
unless vigorous optimization in powder processing, polymer type, quantity of organic
polymer, and molding conditions are carried out [18].
Binder burnout is a crucial step in injection molding technology. Decomposition
or evaporation behavior of binder, decomposition temperature, and impurity content
affect the product quality. When this binder leaves the molded product, rearrangement
of particles takes place. Hence removal rate or kinetics of decomposition essentially
affects the product quality. A schematic of the ceramic injection molding is shown in
Fig. 1.6. Split mold is used for shape forming through injection molding as compli-
cated shapes are difficult to come out of the mold. Proper joining of the two splits of
the mold is essential to hold the powder with the thermoplast at high temperature and
high pressure. This technique has the capability of manufacturing complex shapes
with dimensional accuracy. The limiting factors are a high capital and tooling cost.
Non-uniform solidification and removal of organic matter prior to the initiation of
sintering are also the limitations of this method [12].
1 Shape Forming and Sintering of Ceramics 15

Fig. 1.6 Schematics of an injection molding machine

1.4.3 Shape Forming Using Ceramic Slurry

In this type of shape forming processes, ceramic powders are dispersed in a solvent
for the preparation of the slurry. The slurry formation involves (a) wetting the
solid particle surface with the liquid (i.e., replacing solid-vapor interracial area with
solid-liquid interfaces), (b) breaking down agglomerates, and (c) controlling particle
surface charge to prevent flocculation or re-agglomeration. To optimize dispersion
and stability, dispersants, also known as deflocculants are often added to the slurries
[19]. Deflocculants prevent dispersed particles from re-agglomerating in the slurry
by keeping particle-particle separation distances sufficiently large such that the short
range Van der Waals attractive forces that hold particles together are negligible.
Particle stabilization in a slurry is achieved by steric effect of the dispersant or the
electrostatic effect of the dispersant with respect to the charge of the particles. The
preferential adsorption of large deflocculant molecules on the particle surfaces sepa-
rates the particles by steric effect. Electrostatic stabilization is achieved by forming
electrical double layer around the particles that results in repulsion between particles
of similar surface charges [20].
Two major types of slurry-based shape forming processes are
(a) Slip casting/pressure casting
(b) Tape casting.

1.4.3.1 Slip Casting

Slip casting is an old and well-established technique which uses precisely shaped
porous molds for casting. It normally utilizes relatively cheap plaster of Paris molds.
This process is extensively used in white-ware and lab-ware ceramic fabrication
industries. This technique is usually selected for production of complicated shapes
that cannot be achieved by simple pressing. In slip casting the slurry is poured into a
porous mold that removes the liquid by capillary force through the pores and leaves
16 R. K. Lenka et al.

Fig. 1.7 Schematic of slip casting process using a plaster of Paris mold

a powder compact in the mold. Once a sufficient thickness is achieved, the remaining
slip is poured out and the cast is allowed to dry. Once the cast is sufficiently dried it
shrinks and easily comes out of the mold. The schematic of slip casting process is
shown in Fig. 1.7. Another variation of slip casting is filter-pressing. Here, pressure
is applied on the slurry to enhance the fluid flow through the pores of the filter.
Instead of a plaster of Paris mold a durable resin mold is used. Both the capillary
action of the porous mold and pressure applied to the slurry accelerate the casting
process [21]. Figure 1.8 shows the schematic of the pressure slip casting process.
In slip casting and filter-pressing homogeneous distribution of particles in the slurry
plays an important role to ensure high green density. Slurry rheology becomes an
important parameter in determining the quantity of additives (dispersant, solvents,
etc.) in order to ensure good repeatability in different slip batches [22].
The solvents used in slip casting are usually classified into two major groups: (i)
aqueous and (ii) organic. Most traditional ceramic industries are aqueous based.
When there is a possibility of reaction between powder particles with aqueous
medium, organic solvents are preferred. As there is higher cost attached to the organic
solvents, its use is restricted to the casting of high-performance ceramics in industries.

1.4.3.2 Tape Casting

Tape casting is a process in which slurry consisting of ceramic powder, binder,

plasticizer, and solvent is poured onto a flat substrate and then evenly spread using
casting knife alternatively known as doctor-blade. The solvent subsequently evap-
orates resulting in a ceramic tape which can be peeled off from the flat substrate
(glass/polished granite/silicone-coated mylar film) for further processing. Figure 1.9
shows the schematic of tape casting process. The equipment used for casting the
1 Shape Forming and Sintering of Ceramics 17

Fig. 1.8 Schematic of

Pressure slip casting

Fig. 1.9 Schematic of tape

casting process

tape is called doctor-blade tape caster. It can be a moving blade type or moving bed
type. For lab scale fabrication process moving blade type systems are used where
normally the tape is casted on a fixed glass or granite surface. In a moving bed
type tape casting system which is normally employed for regular production in an
industry, the bed (silicone-coated mylar film) is moved at certain speed keeping the
doctor-blade constant. These systems are usually accompanied with an in-situ dryer
so that the casted tape can be stored in a film roll immediately.
The tape thickness can be controlled by adjusting the gap between the substrate
and blade. Both water and organic-based slurry formulation can be done and powder
can have moderate to high packing factor. Some solvents or other constituents might
be carcinogenic and care must be taken during drying and debinding steps. Quality
18 R. K. Lenka et al.

of tape is very sensitive to slurry composition and ambient conditions (temperature

and humidity) of the lab [23].
In a tape casting slurry normally both binder and plasticizer are added to the
solvent. The solvents can be either water or organics like alcohols, ketones etc. In
some cases an azeotropic mixture of solvents is used and the commonly azeotropic
mixture used is ethanol-methyl ethyl ketone [24]. In the azeotropic mixture the drying
rate of the solvent is controlled. When the amount of binder is less it generates crack
in the tape and excess binder may result in tapes with many voids. With increase in
binder, the green tape strength increases but this leads to a decrease in green tape
density. Most commonly used binders are ethyl cellulose, poly vinyl alcohol (PVA)
and poly vinyl-butaral (PVB). Glycerine, diethyl oxalate, poly ethylene glycol (PEG),
and di-butyl pthalate (DBP) are the most commonly used plasticizer in the process
of tape casting. It is difficult to handle either nano-powders or large micron size
particles (>50 μ) for tape casting. Slurry rheology will be difficult to adjust for these
types of powders. Tape-casted products find applications mainly in capacitors and
piezo actuators (either in manolayer or multilayer forms) porous substrate for filter
applications, solid oxide fuel cell, etc.

1.5 Sintering Phenomenon

Sintering is a process in which a green compact is heat treated at high temperatures

to give a coherent and preferentially solid structure as a result of strong bonding
between the particles [6]. Coherent bonding between the particles leads to decrease
in porosity in the green compact. These strongly bonded structures generate different
microstructures. Some of the properties that depend on microstructure are mechan-
ical strength, dielectric strength, electrical conductivity, etc. which improves upon
sintering. All pre-compaction technologies discussed earlier generate near net shape.
This only offers handling strength in the compact and deprives of required functional
properties which depends on density. Hence sintering not only gives strength but also
influences some of the microstructural and density dependant properties. The driving
force for sintering process is the decrease in surface free energy of the system. There
is a large change in the surface area of the particles which leads to decrease in
surface free energy of the system. Particles lose its identity in sintering and inter
particle pores are closed by the mass transfer from particles to pores. Chemical
potential at a point depends on surface free energy and chemical composition. Mass
transfer takes place due to the chemical potential difference between two points
[25]. There are different pathways through which mass transfer takes place. The
various mass transport phenomena are surface diffusion, viscous flow, plastic flow,
vapor transport, volume diffusion, and grain boundary diffusion [26]. Mass transfer
takes place through the solid state diffusion process primarily. Sintering is predom-
inately discussed for solid state sintering of crystalline materials. Other two types
of sintering are liquid phase sintering and reaction sintering where an added liquid
phase or reactive phase enhances the mass transport process.
1 Shape Forming and Sintering of Ceramics 19

In the sintering processes, intra particle and inter particle pores close and bonding
between particles take place. Therefore, change in dimension occurs during sintering
of ceramics. Precise dimensional control in sintering is essential. If highly compress-
ible powder is used as initial powder, a large dimensional change is expected. The ulti-
mate goal in sintering lies in densification with limited shrinkage and free of defects.
However, impurity from binders, plasticizers, dispersants, and additives generate
defects in the dense structure. As sintering is an irreversible process, defects remain
to the end. Similarly, in-homogeneity in the green compact is reflected in the final
structure as a defect. Hence in getting a finished product with precise dimension free
of defects, a lot of parameters have to be taken care.
Sintering takes place in stages and transport of mass is the phenomena that guides
sintering. If spherical model of sintering is considered, first the particles come in
contact followed by neck formation. Neck growth is the next step in sintering where
separation between particles comes down. With increase in neck size, interconnected
porosity decreases and at certain stage only isolated pores are formed. In the final
stage, these isolated pores are closed. This whole process is pictorially represented
in Fig. 1.10.

Fig. 1.10 Inter particle bonding during sintering

20 R. K. Lenka et al.

1.5.1 Different Energy Terms in Sintering

In the solid-state sintering of polycrystalline materials grain and grain boundaries are
developed upon densification. Scanning electron micrograph of a sintered material
is shown in Fig. 1.11 reflecting distinct grains separated by grain boundaries. The
grains can be considered as single crystals within which the atomic arrangements
are regular in three dimensions. At the grain boundaries there is discontinuity in the
repeated pattern. Atomic positions at the grains and grain boundaries are schemat-
ically presented in Fig. 1.12. These atomic positions can be visualized through a
high resolution transmission microscope (TEM). It can be observed that the misfits
between two grains are not constant. This misfit is measured in terms of misfit angle
as shown in Fig. 1.13. Based on the misfit angle grain boundaries are assigned as
small angle and large angle grain boundaries. A lot of mechanical properties depend
upon this orientation of the grain and grain boundaries. The deviation of atomic posi-
tion from the perfect lattice leads to a higher energy-state. This is the origin of grain
boundary energy. Grain boundary energy is correlated with excess volume of an inter-
face which can be calculated from the knowledge of grain boundary crystallography.
Anisotropy in the grain boundary energy is measured from the dihedral angle at triple
lines and using Herring equation at triple junctions. Grain boundary energy dictates
the distribution and population of grain boundary [27]. Grain boundary energy is
related to the energy of two surfaces that make up the boundary.
Surface energy (γ) is the energy required to create a new surface and defined by

γ = dG dA

dG is the change in free energy of the surface due a small change in area dA.
Surface free energy is similar to surface tension. Surface tension is the force
per unit length in all directions on the surface. Whereas surface energy is the

Fig. 1.11 SEM picture of

sintered ytterbium iron
garnet showing grain and
grain boundary
1 Shape Forming and Sintering of Ceramics 21

Fig. 1.12 Pictorial presentation of atomic arrangements in a grain and grain boundary

Fig. 1.13 Representation of the dihedral angle and energy balance at the triple point
22 R. K. Lenka et al.

energy required to create a new surface. Assume a molecule inside a liquid droplet.
It is homogenously surrounded by other molecules by cohesive forces. However,
molecules at the surface are attached to the molecules inside the bulk by cohesive
forces from inside. But have unbalanced forces on the top. This creates stress on the
surface [28].

1.5.2 Sintering and De-Sintering Phenomena

During sintering the value of grain boundary energy to surface energy detects
sintering. The process in which more decrease in the overall free energy occurs
that path is favored. Pore structure surrounded by three grains is shown in Fig. 1.13.
At the junction of pore surface with the grain boundaries, all the forces are balanced.
Solid vapor interface tension is balanced by the grain boundary energy as per the
following equation
 
γgb = 2γsv cos ψ 2

where γgb is the specific grain boundary energy, γsv is the specific surface free
energy and ψ is the dihedral angle. The angle between the tangents to adjacent pair
of boundaries is called dihedral angle.
During sintering, surface free energy decreases due to decrease in surface area.
As grain boundary area also changes during sintering the overall free energy change
in the system is presented as

E = γsv · Asv + γgb · Agb

where Asv is the change in surface area and Agb is the change in grain boundary
area.
The relative ratio of grain boundary energy to surface free energy predicts whether
grain growth is more favorable or not.
Grain growth is an associated phenomenon with densification when the sintered
mass is further heat treated after achieving full densification. In this process, grain size
increases and grain boundary area decreases. Grain coarsening is another competi-
tive phenomenon which often retards densification process. Figure 1.14 shows the
pictorial representation of the rearrangement of grains in densification, grain growth,
and coarsening process. Sometimes pores are entrapped in the intergranular region
and within a grain. Pores remain in the sintered material and cannot be eliminated
even after increasing the sintering temperature [29]. Rearrangement of pores only
takes place without any significant change in pore volume. In coarsening, larger
pores are developed at the expense of the smaller pores and the average pore size
increases. Mass transport takes place predominantly through surface diffusion or
1 Shape Forming and Sintering of Ceramics 23

Fig. 1.14 Pictorial presentation of densification, grain growth, and coarsening

evaporation-condensation mechanism. Eventually there is a decrease in surface area

without any dimensional change and no decrease in pore size [30]. In a coarsening
process pore coordination number is high and particle coordination number is low.
Reverse is the case for densification process [31]. Hence large grains and small pores
encourage densification. In a sintering process if coarsening and densification take
place simultaneously, the shape and size of pore and grain size are difficult to predict.
In the sintering of fine ThO2 powders from sol-gel method, near theoretical density
is observed at a sintering temperature of 1200 °C. On further increase in the sintering
temperature a decrease in overall density is observed [32]. At a sintering tempera-
ture of 1800 °C, 90% of the theoretical density is obtained. This is attributed to the
increase in grown growth and formation of inter-granular pores.

1.5.3 Driving Force for Sintering

In the sintering process, free energy of the system decreases due to different
phenomena. Three factors are responsible for the decrease in free energy, namely,
decrease in curvature of the particle surface, applied pressure, and chemical reaction
in the sintered mass [33]. There is a large decrease in surface area associated with
decrease in surface curvature of the particles. Hence there is an overall decrease in
the surface free energy of the system. Surface free energy can be correlated to surface
chemical potential which is the surface or interfacial energy per unit particulate mass.
Chemical potential at a point depends on chemical composition (volume free energy),
surface free energy, and strain free energy. According to Gibbs-Thomson equation
the surface chemical potential is inversely proportional to particulate radius.
24 R. K. Lenka et al.

μ(r) − μ( ∞) = 2 K/r
μ(r) = surface chemical potential of radius r
μ(∞) = surface chemical potential of flat surface
K = surface free energy
 = molecular volume
r = particle radius.
For smaller particles or particles with curved surface offers higher chemical
potential. Curved surfaces tend to flatten in order to reduce this chemical potential
difference.
In many of the ceramic systems surface free energy change is sufficient to cater the
densification process. However, slow diffusion of mass in some advanced ceramics
makes it difficult to sinter. Non-oxide ceramics are difficult to sinter through conven-
tional method, due to involvement of many non-densifying processes. Applied pres-
sure during sintering has advantages of formative mass transfer for densification. At
the contact point the stress generated is a combination of tension, shear, and compres-
sion [34]. Chemical potential in the stress and strain region is different and this differ-
ence favors mass transport. Hence, carbides (SiC, B4 C, and TiC), nitrides (Si3 N4 ),
and borides (ZrB2 , HfB2 ) are sintered via hot pressing or hot isostatic pressing
method [35–37]. Particle rearrangement and creep mechanism are the added factors
contributing to the sintering mechanism. Chemical reaction where there is a large
change in free energy associated, also favors sintering. In the reaction sintering,
phase formation and densification take place simultaneously. The exothermic heat
of reaction is utilized for both purposes. This change in free energy is highest among
the other driving forces. However, its advantages cannot be utilized due to lack of
control over the grain growth. Non-uniform grain size affects the physical properties
of the advanced ceramics where microstructure plays an important role.

1.5.4 Mass Transport Mechanism

There are various factors responsible for the sintering process. However, actual
sintering process is associated with transport of atoms, ions, and molecules via
defects. In a crystalline material there are regions of imperfection where the lattice
positions are not regular. These defects are point defects, line defects, and planar
defects. Point defects are more common in crystalline materials. Intrinsic defects like
Frenkel defects and Schottky defects are formed due to inherent abnormalities in the
lattice positions. Extrinsic defects are formed due to non-stoichiometry, atmosphere,
and dopant addition. As intrinsic defect concentration is very low, it cannot affect
much to the mass transport mechanism. Extrinsic defect like temperature, atmo-
sphere, and dopant concentration controls the mass transport, hence the sintering
mechanism. For example, doping of Y2 O3 in Ce2 O3 generates oxygen vacancies as a
charge compensation process. If diffusion of oxygen vacancy is the rate limiting step,
the addition of Y enhances the sintering process. It is observed that Y2 O3 doping
1 Shape Forming and Sintering of Ceramics 25

level less than 0.5 mol % enhances oxygen conductivity and sintering rate [38]. It
is not definite to assign a single mechanism responsible for sintering. Hence, it is
difficult to tailor the sintering process, and ultimately control of microstructure.
Sintering takes place due to the transport of matter through different mass transport
processes and sintering mechanism defines the transport mode by which densifica-
tion takes place. In the sintering process, pores are considered as bunch of vacan-
cies. Transport of mass takes place using these vacancies [6]. Figure 1.15 shows
the different mass transport phenomena visualized at a junction of three contacting
particles. Different mass transport processes associated with sintering phenomena
are namely surface diffusion, lattice diffusion from the surface, vapor transport,
grain boundary diffusion, lattice diffusion from the grain boundary, and plastic flow.
Broadly all mass transport phenomena fall into two categories, namely, surface trans-
port and bulk transport. Processes like grain boundary diffusion, lattice diffusion
from the grain boundary, and plastic flow where transfer of mass takes place to
the porous region enhance densification. Plastic flow is more prominent in case
of a metallic powder system. However, the other three processes such as surface
diffusion, lattice diffusion from the surface, and vapor transport, though lead to
neck growth does not contribute to densification. Hence these processes are called
non-densifying processes. The above phenomena are discussed for polycrystalline
materials. However, similar mechanism is not valid for amorphous materials like
glasses where viscous flow of materials along with particle deformation contributes
to sintering and densification.
Diffusion is the major means of mass transport during sintering. Three major diffu-
sion processes are lattice diffusion, grain boundary diffusion, and surface diffusion.
Point defects move through the bulk of the lattice, hence the name lattice diffusion.
Point defects like vacancies and interstitial positions take part in the diffusion mech-
anism. Atom from a normal site jumps to the nearby vacant site, the vacant site move
in the opposite direction to a normal site. When some atoms are there in the inter-
stitial positions, they also participate in the diffusion process. They act in a similar

Fig. 1.15 Mass Transport processes at the contact point between three particles
26 R. K. Lenka et al.

way as a vacancy for mass transport. A regular atom may exchange its position with
an interstitial atom or interstitial atom may move from one interstitial position to
another interstitial position.
In a polycrystalline material grain boundary separates the crystals, i.e., regions
of regular lattice sites. Hence, it is the highly defective or irregular region between
the lattices and more facilitates mass transport through diffusion. A typical width of
a grain boundary is limited to ~1 nm. For fine particles (nano-materials), the area
covered by grain boundary is higher. Hence grain boundary diffusion will be more
prominent in nano-materials.
When transfer of mass or vacancies takes place along the particle surface it is called
surface diffusion phenomena. Like grain boundaries, surface of a polycrystalline
material is not perfect and associated with defects, vacancies, ad-atoms, terraces, and
kinks. Hence the diffusion process is assumed to be similar to grain boundary diffu-
sion limited to ~1 nm thickness over the crystal surface. Unlike grain boundaries, one
side of the surface is free with less number of neighboring atoms. Hence, it is easier
for the atoms to migrate through the defects and have lower activation energy for the
diffusion process. As activation energy is less, surface diffusion is prominent in the
lower temperature region. Population of surface defect sites and their migration are
temperature-dependent and atmosphere-dependent process. Surface diffusion takes
place at low temperature region till the surface defects are consumed. In this process
transfer of mass takes place from surface to surface without affecting any shrinkage.
Hence this does not favor densification. As it is a low temperature process rapid
heating at low temperature minimizes surface diffusion effect for densification.
Viscous flow is essentially a major mass transport process in amorphous material.
In case of amorphous materials like glass and polymers, viscosity decreases with
temperature then flow of material under applied stress takes place. Sintering of an
amorphous material is different from a polycrystalline material. As there is no grain
boundary, the two particles sintering phenomena or the neck formation process does
not exist. The effective viscosity is inversely proportional to the volume diffusion
coefficient.
Evaporation-condensation is another mass transport phenomenon where reloca-
tion of atoms from a surface to a nearby surface takes place through pores. The net
result is the decrease in surface area without densification. As population of atoms on
a convex surface decreases with increase over concave surface, atoms number on the
surface decrease. This mode of transport depends on temperature and equilibrium
vapor pressure and is defined by Arrhenius equation. Fine powder with high surface
area and high vapor pressure favors evaporation-condensation phenomena as a major
transport process.
When transport of matter takes place through the lattice interior it is either by
viscous flow or volume diffusion. Mass transport via dislocation structure is called
plastic flow. Though neck growth is facilitated by both surface and bulk transport
process, their role is different with respect to sintering. Processes like volume diffu-
sion, grain boundary diffusion, and plastic flow, where mass transfer from bulk inte-
rior to neck takes place and facilitate densification. Role of plastic flow is limited to
low temperatures only. Viscous flow is more prominent in metals where liquid phase
1 Shape Forming and Sintering of Ceramics 27

is formed at the grain boundary. There are different theories altogether for validating
a sintering process. Different geometrical models are assigned to these theories.
Sintering process is modeled with temperature pressure and different dopants with
respect to different mass transport mechanisms.

1.5.5 Stages of Sintering

Green compact formed by different shape forming methods is heat treated at a specific
temperature, under desired atmosphere and heating rate. Initially the powder parti-
cles are packed in a definite manner. Loose powders when come close to each other
during compaction adhere each other via weak forces in random orientations. A
particle with an average coordination number ~7 is obtained initially. With progress
of sintering the bonding between the particles grows and grain boundary is generated.
This grain boundary developed has some associated grain boundary energy which
is a function of crystal orientation at the boundary. As crystal orientation at the
grain boundary, particle coordination and surface energy change with the progress
of sintering, particle rotation takes place to minimize the change and increase the
packing density [39, 40]. New contacts develop due to these changes. Particle coor-
dination as high as ~14 is observed at the latter stages of sintering. In the sintering
process with time or density of the compact, it undergoes distinct microstructural
changes. Based on this changes three stages have been assigned as the initial stage,
intermediate stage, and final stage of sintering. In each stage, there is a certain
change in surface energy, contact between particles, porosity, and pore volume apart
from microstructural changes. Microstructural changes in a sintering process are
pictorially shown in Fig. 1.16.

1.5.5.1 Initial Stage

This is the first stage of sintering where neck formation between the particles takes
place and neck growth with other contacting particles are independent of each other.
Initial step is limited to neck growth up to 0.4–0.5 of the particle radius. Growth at
neck region is associated with material deposits at the neck. In this process, gradient
in the curvature decreases and surface becomes smoother. Surface curvature gradient
facilitates mass transfer to the sinter bond position [41, 42]. Linear shrinkage around
3–5% is observed in this stage along with a marginal increase in the density. Initial
neck growth is associated with the transfer of mass through diffusion, vapor transport,
viscous flow, and/or plastic flow. Both surface and grain boundary diffusions become
prominent when size of the particles decreases. Shrinkage takes place with formation
of new neck and decrease in inter particle space. It has been observed that lower grain
boundary energy favors grain growth instead of neck growth.
28 R. K. Lenka et al.

Initial green compact First stage of sintering

Intermediate stage Final stage

Fig. 1.16 Microstructural changes in the sintering process

1.5.5.2 Intermediate Stage

Initial stage is limited to neck formation and a small neck growth. In the intermediate
stage the major change includes densification, rounding of pores, and grain growth
[43]. As curvatures are smoothened in the beginning of the second stage the surface
energy change is the driving force in this stage [44]. With neck growth, stable pores
are generated at the grain edges. These cylindrical pores around the grain edges are
continuous and distributed. At the end of the second stage, pore rounding takes place
and pores are isolated at the grain corners. Both coordination number of pores and
grains are frozen. This transformation from second to third stage can be visualized
from Fig. 1.17. Now this continuous pore structure changes to discrete ones. Rate of
densification is inversely proportional to the cube of the grain size. Hence, smaller
is the grain size, larger is the densification rate. Though all mass transport means
contributes in the intermediate stage, grain boundary diffusion, and volume diffu-
sion caters to densification. Pores adhere to the grain boundary annihilates rapidly.
As grain boundary is an effective path for mass transport, pore structure is largely
1 Shape Forming and Sintering of Ceramics 29

Fig. 1.17 Change in pore morphology from intermediate to final stage of sintering

affected. Small pores are annihilated and big pores are enlarged. Though surface
transport is active, but it does not contribute to densification. It only helps in migra-
tion of pores during grain growth and rounding of pores. This stage is associated
with maximum in densification and linear shrinkage. Density reaches to a value of
~90% of the theoretical value.

1.5.5.3 Final Stage

Third stage is quite important in getting full density in the material. In the final
stage densification is very slow. Final stage starts when continuous cylindrical pores
break into discrete pores. These pores are adherent to the grain corners. Coarsening
is a competing phenomenon with densification in this stage. Pores may either attach
to the grain boundary or may stay inside the grains. Spherical shape of pores is
visualized if the pore is inside the grain. Lenticular pore structure is generated when
pores are attached to the grain boundaries. As densification, grain growth, and pore
shrinkage rate are different, it’s uncertain to predict the final density. If pores are
isolated from the grain boundary due to higher grain growth rate compared to pore
mobility, densification rate decreases due to long range volume diffusion. If pores
are attached to the grain boundary, annihilation or shrinkage takes place via surface
diffusion or evaporation-condensation. In general, pore mobility is less compared to
grain boundary motion leading to decrease in grain growth [45]. Larger pores cannot
remain adherent to moving grain boundary for a larger time and move inside the
30 R. K. Lenka et al.

grain interior. There is always a scope in changing the grain boundary energy by
doping and getting near theoretical density in materials.

1.6 Assisted Sintering Processes

1.6.1 Liquid Phase Sintering

Previously the sintering mechanism via solid-state diffusion was discussed. However,
in some cases the solid-state diffusion is very slow and densification requires very
high temperature. A small amount of additive phases are introduced to form a liquid
phase which enhances densification by increasing the diffusion rate of the species
and simultaneously enhancing grain growth. This has been practiced long back for
the fabrication of glass-bonded ceramics and potteries. However, the actual theory
has been extensively studied while working on tungsten heavy alloys during 1930s.
Cobalt is the minor liquid forming phase for low temperature processing of these WC
alloys [46, 47]. Magnesium oxide addition to alumina [48], bismuth oxide addition to
zinc oxide varistors [49], and Al-Si addition into calcium stabilized zirconia system
[50] are some of the examples of liquid phase sintering in ceramic systems. In many
of the technical ceramics a small glassy phase is observed at the grain boundary as
seen from the high resolution transmission electron microscopy [51, 52]. So it is
believed that liquid phase enhances sintering in many ceramic systems.
Sintering rate is influenced by the surface tension of the liquid formed. Once
liquid is formed at the boundaries, its effect on sintering depends on (1) solubility
of the solid particles in the liquid, (2) wetting properties of the liquid for the solid,
and (3) diffusivity of the solid particles in the liquid medium [47]. In the liquid
medium, diffusion of solid particles will be higher compared to a solid-state diffusion
process. Here, the capillary force of the liquid medium favors the liquid to cover
the solid particle surfaces and enter into the porous region. Compressive capillary
stress generated by the liquid phase enhances the sintering process, though grain
coarsening is a drawback. Agglomerated powder particle surfaces dissolve in the
liquid phase. In liquid phase sintering, the liquid phase should form a eutectic phase
with the solid phase. Solubility of the solid in the liquid medium or the reverse case
ultimately influences the liquid phase sintering. Limited densification is achieved
when the solid has lower solubility in the liquid and liquid has limited solubility in
solid. Cases where the solid has extensive solubility in the liquid, densification is
more favored. In case, liquid has more solubility in solid, its effect is detrimental
to densification and leads to swelling of the mass with abnormal grain growth. A
mixed effect of swelling and densification is observed when solid has good solubility
in liquid and vice versa. Hence, we need to have a good choice of the liquid phase
forming additive in a definite proportion to encourage the densification process.
Liquid phase sintering is divided into two types based on the existence of liquid
phase during sintering. When the liquid phase formed remains whole through the
1 Shape Forming and Sintering of Ceramics 31

sintering process, it is called persistent liquid phase sintering. This liquid phase
solidifies at the grain boundaries as an amorphous phase or a crystalline phase. Most
of the liquid phases sintering mechanism are discussed based on persistent liquid
phase sintering. In the other case, liquid phase disappears at the end of the sintering
process either via incorporation into the grains through reaction or evaporation at
elevated temperatures. In the liquid phase sintering of aluminum nitride with CaF2
additive, CaAl12 O18 liquid phase is formed which transforms to CaAl2 O4 phase at
higher temperatures. This is called transient liquid phase sintering [53].
Prior to the formation of liquid phase, solid-state sintering of the compact takes
place. Initial contact between the particles forms a rigid framework. Subsequently,
liquid phase is formed at the grain interfaces. Similar to solid-state sintering liquid
phase sintering also progresses through stages. The three stages are (1) rearrangement
(2) solution precipitation, and (3) final stage sintering. This is pictorially presented
in Fig. 1.18. Volume of the liquid phase formed due to the additive phase detects the
particle rearrangement. At a higher level of liquid phase content, more rearrangement
of particles takes place leading to full density. On the other hand at a lower level of
liquid phase, rigid solid to solid bond formation inhibits sintering.
In the first stage of liquid phase sintering the driving force is the capillary force
exerted by the liquid on the solid surface. Materials from the grain surface start
dissolving in the liquid. Grains shrink and rearrangement of grains takes place. When
solid-liquid surface energy is lower compared to solid-vapor surface energy, a good
wettability is observed. Liquid enters into the porous intergranular space. This grain
rearrangement step may contribute a major part in the densification process. However,
initial solid-state sintering forms a rigid bond and inhibits further rearrangement.
The second stage of liquid phase sintering starts when the rearrangement process
comes down and solubility effect predominates. In this solution precipitation stage
solid solubility of the smaller grain surface is more compared to the larger size
grains. Mass transport from the smaller size grains takes place, hence their popula-
tion decreases. Another event occurs in parallel called grain shape accommodation,
where grains are flattened along the neighboring faces and this increases the packing
density. Some more pores are filled by grain shape accommodation. The final step is
a very slow process where pores are removed from the liquid phase. In some cases,
residual pores enlarge due to trapped gases leading to swelling of the compact. Coars-
ening of the microstructure also continues in the third stage. Dwelling in the final
stage is crucial in deciding the sintered microstructure. This less control over the
microstructure is the biggest disadvantages of a liquid phase sintering. This leads
to decrease in many mechanical properties of the material. Advantages like lower
sintering temperature, faster sintering, full densification in material systems with slow
solid-state diffusion rate, etc. are associated with a liquid phase sintering process.
32 R. K. Lenka et al.

Fig. 1.18 Pictorial presentation of liquid phase sintering

1.6.2 Hot Pressing

In hot pressing process both external pressure and temperature are applied simul-
taneously for densification process. It is carried out by placing either powder or a
compacted preform into a suitable die and applying uniaxial pressure while keeping
the entire system at an elevated temperature. This can be done either in a controlled
atmosphere or in vacuum. Hot pressing method is suited to relatively simple shapes
and more useful for non-oxide ceramics more specifically covalent bonded ceramics
1 Shape Forming and Sintering of Ceramics 33

where it is extremely difficult to obtain the near theoretical density by conventional

sintering process. Some materials either decompose or evaporate before achieving
near theoretical density. Hot pressing is used for such materials to get full density at
lower sintering temperature. In hot pressing, densification can be achieved at rela-
tively lower temperature which results in fine-grained microstructure, better mechan-
ical and functional properties [54, 55]. Die tooling in hot pressing is very important
as the die has to withstand high pressure and high temperature (usually > 1000 °C).
Hence, materials with high creep resistance are suited for this kind of applications.
Further, the coefficient of thermal expansion of the die material should be less than
the material whose shape forming has to be carried out. Else during cooling there is
a chance that the compact may break due to the compressive stress from the die.
Graphite is the most commonly used die material due to its lower cost, ease of
machinability and high creep resistance. Graphite is the best choice for pressing
refractory materials, where the operating temperatures vary from 1000 to 2500 °
C.Graphite exhibits a gradual increase in strength, almost double the room tempera-
ture strength at 1500 °C. However, due to oxidation of graphite above 500 °C, either
vacuum or inert atmosphere is required for protection. Therefore, suitable contain-
ment such as high vacuum chamber and pumping system is essential. The limitations
for graphite die are the low operating pressure and interaction with some powders. In
hot pressing of most ceramics, the die life can be increased by applying boron nitride
powder coating to the graphite die to prevent the reaction with the powder. Other
die materials that can be used for high temperature hot pressing are SiC, WC, etc.
But the cost and machining challenges limit its use for specific high end applications
only. Multi-cavity die can also be used in order to increase the number of products in
one cycle. Figure 1.19 shows schematic picture of a vacuum hot pressing machine.
Hot pressing technique is extensively used for consolidation of SiC [56, 57], B4 C
[58, 59], di-boride-based ultra-high temperature materials like ZrB2 , HfB2 ,TiB2 , etc.
[37, 60, 61], oxides like BeO [62], MgO [63] and thermoelectric materials like FeSi2 ,
Bi2 Te3 , etc. [64, 65].

1.6.3 Hot Isostatic Pressing (HIP)

Hot isostatic pressing technique involves sintering of a compact at high temperature

and high pressure. In this process the compact can be either made impermeable to
the pressurized gas (where powder compacts are first sintered to remove surface
connected porosity; sinter hipping) or encapsulated in a gas-tight container. Powders
are usually encapsulated in a metallic container but sometimes in glass. Initially
the container is evacuated; the powder is out-gassed to avoid contamination of the
materials by any residual gas during the consolidation stage and sealed-off. Further
the compact is subjected to isostatic pressure. Figure 1.20, shows the schematic of
the hot isostatic pressing (HIP). The application of high inert gas pressures (usually
Ar) at elevated temperatures results in the removal of internal voids and creates
a strong metallurgical bond throughout the material. As densification occurs, the
34 R. K. Lenka et al.

Fig. 1.19 Schematic of

vacuum hot pressing

Fig. 1.20 Schematic of hot

isostatic pressing
1 Shape Forming and Sintering of Ceramics 35

powder compact shrinks. The external metal or glass envelope shrinks with it to
the same extent in all the directions due to the isostatic pressure. Thus the densi-
fying powder is formed into the same shape as that of the envelope. This result is a
clean homogeneous material with a uniformly fine grain size and a near theoretical
density. The technique requires considerable financial investment as the pressure
vessel has to withstand the internal gas pressure and allow the powder to be heated
to high temperatures. Similar to cold isostatic pressing, only semi-finished prod-
ucts are produced, either for subsequent working to smaller sizes, or for machining
to finished dimensions. The use of hot isostatic pressing leads to additional densi-
fication and increased strength in ceramics. Specific advantages of HIP technique
for shape forming are reduction in porosity, uniform microstructure, near net shape
(more than 80% material utilization), complex shaping, and improved mechanical
properties of the product. Broader applications of HIP technique include consol-
idation of metal/alloy/ceramic powder, near net shape forming, diffusion bonding
of dissimilar materials, cladding, and component repair [66]. Literature indicates
that many transparent polycrystalline ceramics [67, 68] like magnesium aluminate
[69, 70], zinc sulfide [71–73], Nd-YAG [74, 75], PLZT [76] have been successfully
prepared using HIP by many research groups.

1.6.4 Field Assisted Sintering

Field Assisted Sintering Technology (FAST) alternatively known as Spark Plasma

Sintering (SPS) is a relatively new sintering technology in the field of materials
science and engineering. This process is similar to hot pressing process; however,
instead of an external heating source a pulsed electric current is passed through the
pressing mold and sample. Typically current in the range of 5000–10,000 A is applied
across the sample. When current passes through the sample, granular boundaries of
the initial powder particles are heated up and creates an electric field with a plasma
effect. Schematic of the spark plasma sintering setup is shown in Fig. 1.21.
In this sintering technology, a very rapid heating cycle and short process time is
achieved which leads to suppressed grain growth. Materials with novel properties
can be prepared by this process which cannot be achievable in conventional sintering
technique [77]. Typical electrical pulse, duration, and strength play a pivotal role
in realizing the SPS effect. Electric field induces microstructural evolution through
complex multi-physical phenomena take place at the surfaces and interfaces.
Several mechanisms have been suggested to explain the influence of external field
on the materials like field-induced ponderomotive forces, generation of defects like
Frenkel pairs, localized heating pairs around grain boundaries, etc. As a consequence
of ultra-high heating rate, field assisted sintering process can readily alter the mass
transport phenomena in ceramics and promote chemical reactions, phase transfor-
mation, microstructural evolution, densification, and grain growth [78]. Some of the
products and components prepared through this technique are diamond and cubic
BN-WC/Co composites for cutting tool applications [79], ZrO2 -HAP composites for
36 R. K. Lenka et al.

Fig. 1.21 Schematic

diagram of the SPS process

biomaterials [80], magnesium aluminates as transparent ceramics [81], (Kx Na1-x )

NbO3 piezoceramics [82], layered ternary carbides and nitrides based MAX phases
[83], etc.

1.6.5 Microwave Sintering

Conventional microwave heating is being extensively used for heating/processing

of foods, rubber, polymers, and laboratory synthesis. Nowadays this has also been
used for sintering of ceramics [84]. The electromagnetic radiation interacts with the
material and heats the sample internally. The dipoles and charge species align in the
direction of the applied electromagnetic wave. As the sign of the electromagnetic
wave changes, polarity change. In this process, heating of the sample takes place
due to internal resistance of the material. A material can be transparent, opaque,
or absorbent to the microwave radiation depending on the dielectric properties of
the material. Higher the loss tangent more is the interaction of the electromagnetic
radiation with matter and hence more heating of the substrate. This loss tangent is
related to the conductivity, magnetic permittivity of the material, and frequency of
microwave. The imposed power per unit volume of a material is proportional to the
loss tangent and square of the electric field strength as per the following relation.

P = π.E 02 . f.εo .εr .tanδ

where E0 is the amplitude of the electric field, f is the frequency, εo is the permittivity
in vacuum, εr is the relative permittivity and tan δ is the loss tangent.
1 Shape Forming and Sintering of Ceramics 37

In conventional sintering process indirect heating (radiation heating) from the

heating elements is used to heat the sample. However, microwave heating takes
place throughout the sample. The advantages of microwave sintering compared to
conventional sintering are high energy efficiency and short sintering time. Thus, grain
growth of the sintered body is restricted. Many engineering properties are improved
due to finer grains in the sintered materials. It has also been reported that microwave
sintering improves dielectric and ferroelectric properties in ceramics owing to fine
grain structure [85]. However, in some cases rapid sintering results in entrapment of
gases and contaminants.
Although there is clarity in microwave heating mechanism, the role of microwaves
in sintering process is not clear. One of the theories indicates that microwave enhances
grain boundary diffusion thus favoring densification [86, 87]. Another theory tells
about the large thermal gradient generated between the surface and the grain inte-
rior which results in large gradient in defect concentration [88]. This concentration
gradient generated is the driving force for mass transport and densification. Some
functional ceramics which can be processed through microwave sintering are SiC
[89], B4 C [90], WC [91], ZrO2 -Y2 O3 [92], hydroxyapatites [93], strontium barium
niobate (SBN) [85], etc.
Ceramics such as SiC absorb microwave energy more efficiently at room temper-
ature. However, materials such as alumina, magnesia, and silica are transparent to
microwave at room temperature. But these materials begin to couple with microwave
at elevated temperature. In case of microwave transparent materials the sample is
placed in a cage of susceptor material (usually graphite) which is an absorbent of
microwave. Figure 1.22 shows the schematic diagram of the microwave sintering
setup. Sample is placed inside the SiC susceptor and microwave generated from
magnetron is imposed on the susceptor. Radiation heat from the susceptor heats the
sample.

Fig. 1.22 Schematics of the microwave heating set-up

38 R. K. Lenka et al.

1.6.6 Reactive Sintering

In a reactive sintering, reactive process (combustion reaction) is carried out along

with sintering and densification. Combustion reaction is initiated within the powder
mixture and this exothermic reaction proceeds spontaneously. The exothermic heat
produced is utilized for sintering. Once this exothermic reaction is initiated, it
proceeds on its own without any external heat. This reactive process is also known
as self-propagating high temperature reaction (SHS), self combustion, and gasless
combustion reaction. One example of reaction synthesis is the fabrication of B4 C
components. A mixture of boric acid and carbon is heated initially to start the
combustion process [94]. Similar to combustion process, the maximum achievable
temperature called adiabatic temperature can be calculated theoretically [95]. In this
calculation it is assumed that the process is adiabatic and there is no heat loss to the
surrounding. Adiabatic temperature depends on the thermodynamic parameters like
heat of reaction, enthalpy of melting, heat capacity of the reactants and products.
Reaction sintering is a self-sustaining and self-propagating combustion reaction.
Hence the velocity of the combustion wave depends on the heat transport rate of the
reaction zone. However, reaction rate can be controlled with the addition of inert
materials. Mixture of two components mixed intimately when heated, one of the
components melts and forms a eutectic with the other component. As the wave front
proceeds, product is formed at the tail. Reaction rate and product quality depend on the
initial powder size. Homogenously mixed powder with both phases inter connected
has a good control over the reaction rate. By two ways reaction sintering is different
from liquid phase sintering (1) liquid forming component ratio is almost half of the
reactant and (2) liquid phase is not segregated separately at the grain boundaries.
However, the advantages of enhanced mass transport through the liquid medium are
achieved in this process. Reaction sintering is mostly used for the production of SiC
and SiC composites [96, 97]. A preform of SiC and graphite powder is prepared
first through the pressing method. Molten silicon is infiltrated into the preform to
produce SiC components. As reactive sintering process requires large control over
many variables, it is not practiced in industry.

1.6.7 Additive Manufacturing in Ceramics

Additive manufacturing (AM) alternatively known as Solid Freeform Fabrication

(SFF), Rapid Prototyping (RP), or 3D printing has the potential not only to change the
way of conventional industrial manufacturing processes but also have demonstrated
broad range of products with complex geometry. It is the process of manufacturing
objects by depositing layer upon layer, from 3D model data, as opposed to subtractive
manufacturing methodologies, such as traditional machining. Schematic of a 3D
1 Shape Forming and Sintering of Ceramics 39

printing machine is shown in Fig. 1.23. Here the feedstock is typically fed into the
system as powder or granules (some time as paste or suspension also) and the desired
object shape is built up layer by layer [98, 99]. Sintering of the powder particle is
facilitated by the laser beam from the top. AutoCAD programme is used to draw the
product with exact dimensions. Feed material is deposited in the places as designed
in the AutoCAD drawing. Depending on the form of feedstock and the consolidation
technique different terminologies are used for additive manufacturing as listed in
Table 1.2.

Fig. 1.23 Schematic

diagram of a 3D printing
machine

Table 1.2 Ceramic additive

Feedstock form Additive manufacturing Abbreviation used
manufacturing technologies
technologies type
Slurry-based Stereolithography SL
Digital light processing DLP
Two-photon TPP
polymerization
Inkjet printing IJP
Direct ink writing DIW
Powder-based Three-dimensional 3DP
printing
Selective laser sintering SLS
Selective laser melting SLM
Bulk solid-based Laminated object LOM
manufacturing
Fused deposition FDM
modeling
40 R. K. Lenka et al.

In the field of additive manufacturing of ceramics, all the efforts are being made to
address the technical challenges associated with either obtaining porous components
or fully dense monolithic components. Accordingly it is further categorized as (1)
technologies not capable of producing dense structures, (2) technologies capable of
producing fully dense monolithic ceramic bodies with restriction in dimension, and
(3) technologies capable of producing fully dense monolithic ceramic bodies without
restriction in dimension [100, 101]. The additive manufacturing technology enables
the production of complex-shaped porous structures with precise control on dimen-
sion, shape, and amount of pores. Thus, it is opening up completely new fields of
research and applications which was not possible with any of the traditional manufac-
turing technologies. Another application of this technique is to develop reproducible
fine filigree structures, which are not possible by any other ceramic shaping tech-
niques. The additive manufacturing technique is being extensively used in the field of
dental ceramics [102], hydroxyapatite scaffolds for bone implant applications [103],
zirconia impellers [101], and more recently in the field of solid oxide fuel cells [104].

1.7 Factors Affecting Sintering

Sintering is aimed at getting a dense product of desired shape, size, and density with
necessary functional properties. As many factors affect sintering at different stages,
their role has to be meticulously monitored. These factors are powder quality (size
and distribution, degree of agglomeration), powder packing, additives (composition,
impurity, liquid phase), temperature/heating rate, atmosphere, external field, and
applied pressure. Sintering is largely influenced by the interaction of particles, pores,
grain boundaries, impurity, and atmosphere.
Particle size effect: Size of the initial particles influences some of the mass transfer
processes at different stages of sintering. Smaller size particles will have higher
interface contacts per unit volume, hence higher diffusion rate is expected. Surface
diffusion and grain boundary diffusion processes depend on particle sizes. Volume
diffusion is less dependent on particle size whereas viscous flow doesn’t depend on
size at all. Lastly, evaporation-condensation has moderate sensitivity to change in
particle sizes. Finer particles show higher sintering activity due to higher surface
area, more unbalanced surface forces, pores associated with higher energy per unit
volume, and high surface curvature. Sintering time for different particle sizes of same
system is better explained by Herring [25].
Particle size distribution influences the pore size distribution and hence the trans-
port mechanism. In the final stage of sintering wide initial particle size distribution
influences much on densification. It offsets the balance between pinning and sepa-
ration of grain boundaries from pores, allowing grain growth to initiate in sintering
resulting in a lower final density [27]. However, as large number of small particles
are there in a wide particle size distribution, early sintering benefits are obtained.
But this benefit is nullified if sintering is carried out for a longer sintering time and
1 Shape Forming and Sintering of Ceramics 41

high sintering temperatures [28, 30]. When mono-sized particles are taken, higher
density can be achieved with minimal in-homogeneity and control over grain growth
during sintering. In this case no grain boundary curvature is observed between grains
of equal size. Similarly, grain size also influences the densification rate. Grain sizes
inside the particle have different grain boundary areas per unit volume. Polycrys-
talline materials with more number of grain boundaries have better mass transport
mechanism and favors fast sintering [31]. Particle shape influences surface area per
unit volume, responsible for accelerating sintering process in case of non-spherical
particles. However, these non-spherical particles generate low green density also.
This porosity in the particles decreases the sintered density.
Particle packing: The journey of microstructural development with time is decided by
arrangement of initial powders in the compact. In-homogeneity due to small packing
defects and random packing arrangements are the sources of disorder. Generation
of differential sintered regions surrounded by large pores is observed due to this
disorder apart from flaws [6]. Similarly, when there is a wide initial pore size distri-
bution, mostly it hinders densification in the final stages of sintering. In random
packing of particles, different particles will have different coordination number. Two
particles with different coordination number will sinter differently. Lower density
is observed for particles with lower coordination compared to particles with more
number of touching neighbors. Hence, better sintered microstructures are expected
for homogenous green microstructure.
When sintering proceeds, neck growth takes place and simultaneously new contact
points are generated due to shrinkage. Due to this changing coordination number,
the generated torque inside the microstructure favors particle motion. Some of the
existing sinter bonds rupture to accommodate the unbalanced force and particle
motion. When mono-sized powder is taken, initially they have sufficient number of
contacts which do not favor much for repack. New contacts are developed without
any broken bonds; this helps to generate a homogenous microstructure.
Green density: Better green density is essential in getting good sintered density.
When green density is more, there will be more initial particle contacts and initial
pore sizes will be smaller. Sintering needs less shrinkage or densification to get
full density with more dimensional control. Green density gradient also should be
minimum in compacts to avoid any defects in the product. Minimum 40–50% green
density is essential to get a full density. Lower green density compacts lead to particle
bonding with long chain, grain growth, and open pore structure with little shrinkage.
Porosity: If the particle size distribution is over a wide range, then the adhered pore
will also be over a wide range. In the intermediate stage stable pore structure is
developed which controls the sintering rate. Due to higher affinity of a pore with
the grain boundary, pore remains attached to it [35]. Pores are mostly attached to
the larger grains in the latter part of sintering process. The equilibrium dihedral
angle formed by the intersection of grain boundary with pore influences the sintering
curve and for systems with very high dihedral angle, pore closure is not favorable.
In some occasions, there is overall decrease in porosity and increase in pore size.
42 R. K. Lenka et al.

When a pore is developed, the grain boundary is also extended, consequently the
system energy also increases. The relative size of pores compared to the size of
grains also matters. Very big pores are difficult to remove. As a thumb rule if the
pore size is half or less than the grain size, the pore is removed during densification
[36]. These phenomena are more prominent in agglomerates or poorly consolidated
samples with sintering difficulties. Hence particles with narrow pore size distribution
and high packing density favors densification. In case of agglomerates, cluster of
small particles sinter rapidly and independently. This preferential sintering generates
regions of high density with pores in the inter particle space between the clusters
[105]. Smaller intra agglomerate pores close first leaving behind large pores in the
inter agglomerate region. Hence a bimodal pore size distribution is generated in the
agglomerates. This bimodal pore size distribution can be avoided by increasing green
density with applied pressure.
As pore tries to spheroidize at high temperatures, pore shape greatly influences
the densification mechanism. Elongated pores generated during uniaxial compaction
shrinks in the direction perpendicular to the compression axis and leads to anisotropic
shrinkage. It is observed that more number of pores are attached to the grain faces of
largest grains and at the grain corners for the smallest grains. From the observation
it can be concluded that grain growth takes place when pore is attached to the grain
faces and pore closure takes place when it is attached to the grain corners [94]. Late
in the densification process, rapid grain growth takes place as pinning effect from the
residual pores diminishes. Hence for a homogenious green structure, uniform grain
size and pore size distribution delay the onset of grain growth to a higher density.
Pore has a binding energy to the grain boundary and this energy increases with
porosity. This increases the system energy equivalent to the newly created interface
area compared to separate pore and boundary areas. As pore reduces the total grain
boundary area, the system energy is lower for pores occupying grain edges. Large
grain size to pore size leads to breakaway at the time of grain growth. Surface trans-
port processes govern pore mobility whereas transport across grain boundary governs
grain boundary mobility and both are associated with some activation energies sensi-
tive to temperature. In the final stage of sintering if sufficient mobility developed in
the pores they can migrate with the grain boundaries to avoid the breakaway.
Temperature and heating rate: There are four competitive phenomena like pore
shrinkage, grain growth, pore growth, and densification in the sintering process that
control the final microstructure. For uniform microstructure small pores with narrow
size distribution are essential during microstructural development. Microstructural
defects are generated in the early stages of sintering and grow at high temperatures
[95]. Here temperature is an important parameter in sintering. At a relatively high
temperature when the compact has achieved around ~90% of the theoretical density,
increase in the temperature increases the rate of grain growth instead of densification,
i.e., rate of grain growth is more than the rate of densification. By suitably adjusting
temperature-time profile one can control the grain growth during the final stage of
densification.
1 Shape Forming and Sintering of Ceramics 43

Heating rate not only affects sintering but also influences final microstructure.
Surface diffusion dominates sintering at low temperatures and bonding between
particles takes place without densification. At high temperatures, densification is
a predominant phenomenon apart from grain growth and grain coarsening. One
should be careful about the goal of sintering; its sinter bonding without densification
or without grain growth. To reduce the low temperature effects ultra-high heating
rate is practiced. This improves densification and controls grain growth. Temperature
difference is a driving force for sintering when ultra-high heating rates is imposed [96,
97]. In the large compacts poor heat transfer is an issue while going for high heating
rates. As a consequence of large thermal gradient cracks or defects are developed.
Applied pressure: Pressure is applied either in shape forming method or during
sintering due to some added benefits. In many of the shape forming methods pres-
sure is applied on the powder before sintering. Pressure helps in decreasing porosity
and increasing dislocation population in the green compacts [46]. Density, coordi-
nation number, and contact size increase with high compaction pressure and with
reduced neck growth. This essentially leads to densification with less shrinkage, i.e.,
good dimensional control. Most of the industrial products are prepared through die
compaction where dimensional control is achieved by using powder of larger size,
low temperature sintering, high compaction pressure, short sintering time for simple
structures.
There are certain conditions like low sintering temperature (decomposition issue),
coarse powder, composite materials, etc. which requires external pressure during
sintering. Through conventional sintering approach it is difficult to achieve the desired
functional properties related to density. Pressure removes some of the sintering
difficulties and good sintered density could be achieved for larger particles, at low
sintering temperature and short sintering time. The residual porosity in the solid-state
sintering is eliminated due to the applied pressure. Concentrated stress is developed
at the contact regions for compressed particles. Hence, factors like particle size,
pressure, temperature, and compact density influences pressure assisted sintering.
At a small inter particle contact, large stress is developed and with growth of this
contact region stress reduces. Pores do not carry stress, hence the actual pressure
experienced is much higher than the pressure applied [47, 48]. Hence, actual stress
can be correlated with the applied stress by using the fractional density.
Powder packing with wide distribution of particles will have more contact points.
Hence higher effective pressure will be experienced on the particles. This will lead to
more densification. In a study it has been observed that particles with bimodal particle
size distribution gives better sintered density compared to uniform size of particles
under similar pressure assisted sintering conditions [49]. However, in case of uniaxial
pressing, the contact along the pressure direction is higher compared to perpendicular
direction, which leads to non-uniform densification. Grain growth is also an issue in
the pressure assisted sintering. With the increase in pressure, packing/coordination
increases, hence densification also. This implies to the prior onset of grain growth and
increase in grain size for pressure assisted sintering compared to traditional sintering.
44 R. K. Lenka et al.

Impurity/contamination: Impurity generated during sintering like moisture, carbona-

ceous materials, and entrapped gases influences sintering rate. For example, cemented
carbides when sintered above an alumina support, Al2 O3 reacts with carbides. The
reaction product having a higher vapor pressure generates pores in the sintered mass.
Vacancy has a great role in the mass transport mechanism and its absolute concen-
tration depends on impurity content and dopant addition. Apart from this, tempera-
ture and stoichiometry change the equilibrium vacancy concentration. For example,
when oxygen vacancy concentration increases in oxide system, densification rate
increases. Cations have higher mobility than oxide ion, so conditions favoring forma-
tion of oxygen vacancies increases the sintering rate [51]. Sometimes this impurity
or dopant forms inclusion which enhances the final stage of sintering by impeding
the grain growth.
Sintering is affected by rate of grain growth and adherence of the pores with
the grain boundary. Grain growth is related to the grain boundary mobility and in
ionic solids it is influenced by dopants and their volume. Similarly, impurities also
segregate at grain boundaries and control the grain boundary mobility and pore
mobility. Doping 0.1 wt % MgO in Al2 O3 influences the rate of grain growth and
densification in the final stage of sintering. MgO interacts with CaO impurity and
lowers the grain boundary mobility. Hence, slow moving pores adhere to the moving
grain boundaries during the final stage of sintering [52]. Exaggerated grain growth
due to glassy phase formed by CaO segregated at the grain boundaries is hindered
by MgO addition. Grain boundary mobility can be altered by suitably doping at the
grain boundaries also. This inturn minimizes the grain growth which finally alters
the sintered density [39, 53].
Atmosphere: Atmosphere not only influences sintering but also affects some of the
important properties in the sintered mass. Removal of organics used for shape forming
is essential at low temperatures to avoid any side reactions. Hence proper environ-
ment has to be monitored for organic removal at low temperature. For example,
during sintering of cemented carbides or nitrides proper protective environment is
required for stabilization of the phase. Insoluble gases are entrapped during sintering
of alumina and degrade the optical properties, hence its sintering is carried out in
hydrogen or vacuum. Some of the materials either decompose or show volatiza-
tion before getting full density. Proper atmosphere is maintained to avoid these issues.
Some of the atmosphere generates defects responsible for mass transport in sintering.
For example, ionic material when sintered in desired environment generates vacan-
cies responsible for better sintering rate. Sintering atmosphere should be chosen so
that it should not affect the environment and human life also.
In the sintering of advance ceramics, vacuum is mostly preferred, as it provides
clean and non-reactive environment. However, evaporation at high temperature is an
issue in vacuum sintering. Sintering rate is influenced by excess vacuum which alters
the diffusion kinetics. Similarly, sintering atmosphere influences different mech-
anisms responsible for sintering. For example, while sintering NiO at 700 °C in
oxygen there is less densification with greater surface area loss [44]. This clearly
shows that surface transport is the dominant process for sintering. However, when
1 Shape Forming and Sintering of Ceramics 45

Ar is used as sintering atmosphere more dense product is obtained with lesser change
in surface area suggesting bulk transport is responsible for sintering.
External field/factors: In the conventional sintering either electrical resistance heating
or burning of combustible gas is used to increase the temperature. However, in novel
sintering technology other fields like microwave, plasma, DC arc, and laser are
being implemented solely or in combination with conventional heating technique
to improve sintering. For example, many dielectrics are sintered in a hybrid furnace
where initial heating is carried out by conventional resistance heating followed by
microwave heating. Dielectric properties of the material interact with the microwave
and generate heat inside the sample. These external fields are applied for short period
at high temperatures. Hence better microstructural control could be attained. Simi-
larly nano structured carbides, nitrides, and borides are prepared using spark plasma
sintering. In the hot pressing condition a pulse DC in the sample increases the instan-
taneous temperature of the sample. Apart from the change in surface energy, diffusion
coefficient and chemical potential of particles and grains facilitate densification.

1.8 Common Defects in Ceramic Sintering and Sintering

Approaches

In a sintering process the prime objective is to achieve desired density, strength, func-
tional properties, control over dimensions, and microstructure. In reality, the sintering
studies from the lab experiments and theoretical calculations differ from industrial
practices. Laboratory experiments are carried out with small scale and well-defined
furnace heating. In actual, the availability of furnace construction material, heating
element, environment, contamination, etc. used in industry are different from lab
practices. In theoretical studies, many of the assumptions like mono size powder
distribution, powder sphericity, and uniform heating do not match with the actual
conditions. In practice, many process variables are manipulated to get some improved
properties. However, these variables create some other difficulties. Often it is being
argued to decrease the particle size to increase the diffusion rate by changing the
surface area to volume ratio. Higher shrinkage in the smaller size particles offers
challenge in getting precise dimensional control. Apart from dimensional control,
contamination, cost, and health hazards are the added disadvantages. Sintering time
can also be increased to achieve good density. More sintering time implies more
shrinkage and grain growth. Hence less control over microstructure and less dimen-
sional reproducibility. It also adds extra cost to the product. Similarly, increase in the
sintering temperature gives some unwanted phenomena like decomposition and evap-
oration apart from added cost and energy. High temperature sintering implies higher
shrinkage, distortion, and warpage which need additional cutting and polishing step.
Grain growth is another detrimental aspect of high temperature sintering. Furnace
life time also decreases for prolonged use of it at high temperatures. Improvement in
initial green density is practiced to improve densification. But this leads to wear in the
46 R. K. Lenka et al.

die components due to higher friction between walls and powder. Gradient in green
density can be observed for components with complicated shape and components
with large variation in length to width. This density variation is reflected in form of
warpage in the final densification. Sintering aids are introduced when densification in
conventional sintering is difficult due to various reasons. However, products prepared
using sintering aids lead to distortion and grain growth. As there is no control over
the grain growth some of the mechanical properties like toughness and ductility are
degraded.
Few parameters have to be checked meticulously to achieve products of desired
intension. One is a dimensional parameter, getting reproducible component with less
variation in dimension. Forming methods are mainly responsible for dimensional
variation in the components. The defects in the forming are amplified in the sintering
step. Hence uniformity in the packing during shape forming step has to be care-
fully inspected first if dimensional reproducibility is an issue followed by inspecting
the sintering schedule. Friction from the sintering support, gravity induced creep,
and non-uniform heating also contributes to the variation in the dimensions [45].
Lower sintering temperature is preferred for impeding dimensional changes. At the
same time, higher green density is preferred to lower shrinkage. Other scenarios
where dimensional changes expected are (1) sintering involving liquid phase (2)
binder assisted techniques like slip casting and injection molding having lower
packing density and subsequent more shrinkage and (3) nano scale systems with
lower packing density with an overall shrinkage of around 20–25%.
Green density gradient is the greatest culprit for dimensional irregularity. Low
density regions or regions of lower packing density shrinks more and responsible for
wrap. In die compaction, non-uniform density regions are developed due to wall fric-
tion with the powder. Hence isotropic green microstructure developed by injection
molding and iso-pressing shows uniform shrinkage and less dimensional distortion.
Pore developed in uniaxial pressing also alters the uniformity in shrinkage. Compact
mass from uniaxial pressing shows flat pores in the pressing direction and elongated
pores in the perpendicular direction. Spheroidization of pores during sintering results
in enlargement of pores in the pressing direction and shrinkage in the perpendicular
direction. For low green density structure or bigger compact gravity plays an impor-
tant role and shrinkage gradient is generated in the gravitational direction. Dimen-
sional change due to anisotropy generated by uniaxial compaction can be minimized
by use of low compact pressure and graded particle size distribution. High fluidity
generated by formation of liquid phase also contributes to sagging of the structure.
This can be avoided by judicious use of liquid phase forming component. A residual
force is generated by the support on which the compact is placed during shrinkage. In
the lower part retarded shrinkage is observed. Hence use of smooth surface nullifies
the retardation effect of the support. Both gravitational force and retardation from the
surface together induce distortion for massive components [41]. As we move from
top to bottom the cumulative pressure favors axial compaction and a radial flaw.
Dimensional irregularity is also generated due to temperature gradient in a furnace.
Shrinkage takes place in the hotter region at a faster rate and cooler region is distorted
due to differential shrinkage between the hotter and cooler region. For a distorted
1 Shape Forming and Sintering of Ceramics 47

component the warpage developed shows bend toward the hotspot. Such situation
can be avoided by placing the compact at the center of the furnace and maintaining
a slower heating rate in the lower temperature region. Error in the measurement
of temperature and time contributes to differential shrinkage. A small variation of
temperature at a high temperature region has more shrinkage error. However, at high
temperatures a small variation in time has less effect on shrinkage error. The trend is
opposite in the low temperature region. It can be concluded that the shrinkage error
is less at low temperature and longer time.
In the initial stages the compact has low strength. With progress of sintering,
sintering stress is developed; at the same time inter particle bonding takes place.
In a situation where the compact has not attained enough strength, the sintering
stress generates cracks. This crack propagates in the latter stages of sintering. To
overcome this issue slow heating rate is preferred where sufficient sinter bonding
develops which resists the defect generation from stress or shrinkage. Strength is
lowered in materials having weak inter particle bonds and large grains [42, 43].
Higher ductility and higher toughness are achieved for highly dense materials. Higher
thermal conductivity is obtained for highly dense materials with coarse grain structure
and thermal properties are reduced by porosity.
Final density, microstructure, defects, flaws all depend on green microstructure
and are enhanced during densification. Use of small powders with narrow size distri-
bution and uniform packing can avoid such situations to a larger extent. Binder and
lubricants used for shape forming need to be removed initially else will be trapped
in the sintered product. This issue is more prominent in case of nano-powders where
sintering starts well before the binder burnout temperature of organics. Residual
carbonaceous materials affect density, porosity, phase, and many physical proper-
ties also. For non-oxide ceramics sintering atmosphere play an important role. For
example, to prevent silicon loss in the sintering of SiC, a combination of vacuum and
residual gas environment solves the evaporation problem. Shadowing is a common
problem when two components are very different in size and placed in the same
furnace. The radiation heat is blocked by the large component and the small compo-
nent experience less heat. However, increase in the sintering time compensates for
this non-uniform heating effect.
In some transient liquid phase sintering fast heating rate is required to minimize
the surface diffusion at low temperatures. However, this will have adverse effects
like incomplete binder removal and non-uniform heating. For large components,
slow heating rate is advisable to reduce the thermal stress which generates crack at
low temperatures. Similarly, cooling rate has to be very fast in case where impurity
segregation is an issue. During solidification, porosity developed decreases strength
of the materials.
In a furnace, support material role is equally important in holding the compact
during sintering without deformation and preventing the compacts to join with each
other. The support should be rigid and inert to the compact during the sintering cycle,
neither it should react with the compact nor should evolve any impurity. Alumina is
widely used as support up to 1800 °C in oxidizing, inert, or vacuum environment.
However its use is limited to 1500 °C in reducing and carburizing environment.
48 R. K. Lenka et al.

Reduction of alumina takes place in carburizing environment above 1500 °C. Hence
for high temperature operation in reducing environment one can think of refractory
like molybdenum and tantalum. Similarly, for ultra-high temperature ceramics like
titanium diboride, hafnium diboride the choice of support materials is limited.
There are certain instances where the stoichiometry or chemistry of the material
changes during sintering either due to evaporation, decomposition, or atmosphere.
In such situations the material is packed with special materials inside the support to
retain the chemistry. For example sintering of beta alumina components or lithium
titanium-based components have to be sintered in a bed of the respective powders to
maintain the chemistry.

1.9 Case Study of Sintering Cycles

Two case studies are discussed here in which how sintering approaches are adopted
in oxide and non-oxide ceramics will be discussed.
Sintering of SiC components: SiC is among the advance ceramic materials having
excellent corrosion resistance, high temperature stability, chemical resistance to
many systems, excellent mechanical strength, high wear resistance, etc. This non-
oxide ceramic is used for heat exchangers, gas turbines, chemical reactors, nuclear
reactors, space shuttles, and many protective coating applications. Hence SiC is
required in different dimensions with tailored functional properties to suit these
applications. Conventional sintering is not advisable in these covalently bonded
compounds due to slower diffusion process and requires additives for sintering.
In the latter stage of sintering, lower solid-vapor surface energy in comparison to
grain boundary energy inhibits pores closure and favors grain growth. Hence both
high temperature and high pressure are used during sintering. Sintering aids like
C, B, Al, B4 C, Y2 O3 , Al2 O3 , TiO2 , and few rare earth oxides are used to assist
sintering at a lower temperature and pressure. When solid-state sintering aids like
C, B, Al, and B4 C are used, the grain surface-boundary energy is decreased which
enhances the diffusional mass transport. A mixture of boron and carbon additives
is used in practice where boron prevents the low temperature surface diffusion and
carbon decrease the evaporation loss of Si at high temperatures. Carbon reacts with
the surface SiO2 to form SiC at high temperature. Increasing the carbon content in
SiC increases the conductivity, which is useful for cutting the component through
EDM wire cutting. Near theoretical density is achieved at a sintering temperature
around 2100 °C. Heating schedule up to 1700 °C is carried out in vacuum to avoid
the oxidation of SiC. Afterward the atmosphere is maintained as inert to avoid the
evaporation loss. Use of fine powders of silicon carbide raw material and decrease in
dwelling time at the maximum sintering temperature helps to control over the grain
size.
1 Shape Forming and Sintering of Ceramics 49

Liquid phase sintering of SiC is also tried with additives like Y2 O3 , Al2 O3 , CaO,
and Sm2 O3 . The additive forms a liquid phase with SiC and enhances the diffu-
sion process. Some of the nuclear applications do not require boron as an additive,
for these applications other additives like Al2 O3 -Y2 O3 mixture can be used. Some
components which requires very high strength have to be sintered at low tempera-
tures with minimal liquid phase forming additives. In such cases, pressure assisted
sintering schedule is preferred. Novel sintering techniques like spark plasma sintering
and flash sintering techniques are employed along with pressure to further reduce
the sintering temperature.
Sintering of alumina: Alumina is among the commonly used refractory for high
temperature applications and electronic applications. Surface diffusion at low temper-
ature is the issue in sintering alumina, though grain boundary diffusion via vacancy
motion manipulates sintering. Ionic compounds like alumina are sensitive to oxygen
ion mobility. Sintering aids like MgO or NiO in small quantities are used to enhance
densification and retard grain growth. Rate controlled sintering schedule is opti-
mized for getting near theoretical density. Initial small size powders with narrow
size distribution are required to have lower sintered grain size. From room temper-
ature to 1200 °C first sintering rate is maintained to decrease the surface diffusion
phenomena. Slow heating rate is maintained between 1200 °C and 1300 °C to effec-
tively observe the liquid phase sintering. Again fast heating rate is maintained to the
sintering temperature of 1600 °C, to avoid the grain growth. In this rate controlled
sintering, density close to theoretical density is obtained with a grain size of 2 μm.
For high temperature applications the use of additives has to be minimized, else they
will change the mechanical properties. Sintering difficulties increases with decrease
in the additive content. Hence balance in the composition is essential for end user
applications.

1.10 Future Directions in Shape Forming and Sintering

Over decades there has been significant progress both in theories and practices on
shape forming and subsequent sintering of ceramics. This drive is motivated due
to the demand of materials or components of desired properties for medical, space,
nuclear, strategic, and energy applications. In a powder metallurgy process, every
step is inter dependant and hence the success in manufacturing a component remains
in the selection of appropriate processing technique in each step. Development of
new techniques and improvement in the existing techniques through modeling and
simulation will continue to take place to cater the stringent requirement in dimen-
sional control of the components. Over the last decade more thrust has been given
on sintering under external stress, novel sintering processes, sintering of nano parti-
cles, and constrained sintering like sintering of layers, sintering of composites, and
subsequent microstructural evolution. Some improvement in the product quality is
achieved by changing sintering schedules, like two-step sintering, flash sintering,
50 R. K. Lenka et al.

etc. In the theoretical side, multiscale models and microstructure-based models have
been studied extensively.
Sintering process is aimed at developing controlled microstructure choosing right
kind of sintering technique and sintering equipments. Microstructural evolution and
its co-relation with grain boundary structure in both solid-state sintering process and
liquid phase sintering process have been a topic of intense investigation these days.
Only diffusional mass transfer could not explain the solid state reaction mechanism.
Meaningful co-relation between theoretical prediction and experimental investiga-
tion is obtained for a solid state sintering process when interface reaction is incorpo-
rated as a plausible mass transfer process apart from diffusional mass transfer. Grain
growth is a major concern in the liquid phase sintering process and it depends on
the equilibrium grain boundary structure. Solid-liquid interface structure and grain
boundary mobility contribution can be studied extensively to explain the abnormal
grain growth in liquid phase sintering process.
Sintering process is influenced by powder characteristics (such as shape, size,
size distribution, surface chemistry), temperature, external field, environment, and
chemistry of sintering aids. It is important to know how the external fields influence
fundamental sintering parameters such as chemical potential gradients, diffusion
coefficients leading to enhanced mass transport. As sintering phenomenon takes
place in multiple length scale there will be a lot of research interest in multiscale
material modeling to understand the process.
Constrained sintering is an issue for multilayer and composite systems. Minor
phase in a composite system may sinter faster or slower with respect to the matrix.
Over all sintering rate and localized sintered density need to be further studied to
decrease the gap between the theoretical and experimental results. In a multilayer
system, densities at the intermediate time need to be evolved. At this situation the
substrate and layers are not fully constrained. Geometrical changes at different stages
of sintering process need an extensive study.
Sintering becomes more complex and challenging when it comes to nano-
materials. In case of nano-materials retaining the nanostructure in the sintered body is
utmost important. Agglomeration of nanoparticles is a common phenomenon which
leads to differential sintering and grain growth. Pinning of grain boundary also affects
the sintering process in nano-materials. Sintering stress is developed due to this
nonhomogenous densification which affects the sintering kinetics. Research interest
in densification and microstructure evolution in nano-materials will be continued
both in experiment and modeling directions.
New sintering techniques have been evolved where other forms of energy are
used apart from thermal energy. These include pressure assisted sintering (e.g., hot
pressing, hot isostatic pressing), and field assisted sintering (spark plasma sintering,
flash sintering, and microwave sintering). Distribution of temperature, pressure, or
applied field has positive effects on the sintering process. There remains a scope to
development large components using these field assisted sintering techniques using
meso-scale modeling and design of equipments.
Sintering is associated with large shrinkage in different directions. Lot of stress is
generated during sintering that may lead to failure of the components. This is more
1 Shape Forming and Sintering of Ceramics 51

prominent in sintering of complex shapes. Modeling of stress distribution during

sintering can be useful in understanding the process and sintering rate or component
design can be suitably modified to avoid failure.
Additive manufacturing will remain an evolving field particularly in making
miniature components and complex shapes. A slurry-based, powder-based, or bulk
solid-based feed stocks are being used for this process. A deep understanding of the
powder properties, slurry rheology, binder bur out, ceramic to laser interaction, and
sintering under thermal gradient is required. However, the process is highly localized
and the dynamics of sintering is quite different. Hence more focus is required to make
the process more convenient.

1.11 Conclusion

Ceramic products with desire shape and functional properties are used for advance
applications. Ceramic powders are shaped into desired dimensions and sintered at
required temperature for getting near theoretical density. Ceramic shape forming and
sintering are interdependent. Based on the end application, density and microstructure
is fixed first. To achieve the desired properties, shape forming is chosen accordingly.
Different factors affecting sintering are discussed in this chapter. Different mass
transport phenomena responsible for the sintering process are discussed. There is
positive effect of different fields like microwave, DC arc, plasma, etc. on sintering.
There is an evolution of new sintering technologies with time. Additive manufac-
turing is the recent one in which complex as well miniature ceramic structures could
be prepared.

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Chapter 2
Growth of Single Crystals for Nuclear
Radiation Detection

Mohit Tyagi and S. C. Gadkari

Abstract Single crystals are the vital components for the technology develop-
ment having various applications in industries including semiconductors, electronics,
watch, detectors, medical diagnostics, homeland security, etc. The performance char-
acteristics of single crystals usually change with increasing the dimensions. A system-
atic approach and strategy are essential to grow large size single crystals with desired
properties. This chapter briefs the challenges in the growth of large size single crys-
tals for radiation detection applications. The growth of single crystals from melts
strongly depends on the thermal properties of the material, stoichiometric ratio of
the constituent oxides, dopant concentration, growth ambient, etc. In addition to
the effects of crystal growth parameters on their properties, an approach to further
improve the performance characteristics has been discussed in details.

Keywords Single crystal · Czochralski technique · Scintillator · Co-doping ·

Defects · Annealing

2.1 Introduction

2.1.1 Crystalline Structure

A material is usually found in three states: solid, liquid and gas; however, plasma
and Bose–Einstein condensate have also been considered as the state of matters in
the modern science. In the gaseous state the molecules are moving at high speeds
and situated at large distances. Due to the attraction, molecules begin to come closer
if the temperature of the system is reduced. The liquid state is eventually formed

M. Tyagi (B)
Technical Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India
e-mail: [email protected]
Homi Bhabha National Institute, Mumbai 400 085, India
S. C. Gadkari
Department of Atomic Energy, Raja Ramanna Fellow, Mumbai, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 55
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_2
56 M. Tyagi and S. C. Gadkari

Fig. 2.1 The different states of matter

after cooling down where the molecules are in denser state and the energy of the
system is reduced to favor the stability of the state. A more energetically favored
ordered state can be achieved by further reducing the temperature. Molecules are in
relatively fixed position and cannot move freely in the solid state. This arrangement
in solids can be ordered either in a long range or in a random manner which are called
crystalline and amorphous/glass materials respectively (Fig. 2.1). In polycrystalline
materials several crystallites are separated by grain boundaries across which their
relative orientation may different (random). In the long-range ordering, position and
surrounding of any atom can be known if we know the position of one atom even if
these atoms are situated far away. However, reducing the temperature is necessary to
form the solid state; it is not the sufficient condition to form crystals. The formation
of an ordered state from a disordered state introduces a barrier to the formation of the
first tiny crystal. The formation of this first baby crystal is called nucleation [1]. This
barrier leads to the liquid state to be cooled even below its freezing temperature. The
liquid state below its freezing temperature is called supercooled, and this occurrence
is called supercooling [2]. The nucleation and supercooling are the most important
phenomena for growing single crystals which have been described in more details
in the next sections.

2.1.2 History

The crystallization of materials has been occurring in nature, and it has been carried
out even by human beings over the long ages. It was usually expressed as condensation
or coagulation before the 17th century. Various crystals like quartz, gem-stones etc.
have been formed in the nature, while the transformation of sea water to salt can
be considered as the oldest method of crystallization by human. Bohm has nicely
compiled the history of crystal growth in details [3]. The crystallization of various
salts has been described in a Roman literature “Naturalishistoria” written well before
2 Growth of Single Crystals for Nuclear Radiation Detection 57

the Christian era. An article by the alchemist Geber in 12th century is considered to
be the oldest article about the preparation and purification of various materials [3].
Some of the important events towards the modern era of crystal growth are listed as
below [3]:
• In the 17th century the theory of crystallographic structure and crystal angle was
suggested with the help of snow crystals. [Kepler (1611) and Hooke (1665)] [4, 5].
• The role of impurities and growth rate in the formation of crystals from solution
was observed experimentally by Boyle (1666—1672) [6].
• The supercooling of water and heat of crystallization in ice formation was observed
in 18th century (Fahrenheit 1724) which is one of the fundamental theories for
the crystallization [7].
• In 19th century, the idea of periodic structure was introduced and Bravais (1849)
derived the 14 lattice types. The crystal structure could be well understood after
the invention of Laue X-ray diffraction [8].
• The start of modern large size crystal growth era can be considered to be started
after the growth of large ruby crystal by Verneuil (1902–1904) using his flame
fusion method which is still adopted by various industries [9].
• The hydrothermal solution growth of large size quartz crystals, otherwise
occurring naturally, by Spezia (1905–1909) encouraged to generate nature-like
conditions in laboratories [10].
• Czochralski (1918) and Kyropoulos (1926) modified Nacken (1915–1916)
method to grow single crystals from melts by using a cooled rod or seed and
pulling crystal from melts [11–13].
• Bridgman (1923–1925) introduced the melt to be freezed in the crucible by
lowering it to a lower temperature zone and this method was extensively used
to grow large size alkali halide crystals [14, 15].
• Burten Cabrera and Frank (BCF) gave a revolutionary generalized theory for the
crystal growth [16].
• The large size germanium crystal was pulled from the melt by Teal and Little
(1950) [17].
• The concept of constitutional supercooling was established by Rutter and
Chalmers (1953) to achieve the inclusion-free single crystal growth [18].
• Bundy, Hall, Strong and Wentorf (1955) synthesized diamond in laboratory [19].
• The growth of sapphire crystals (Al2 O3 ) on industrial scale by Verneuil method
(1977) [20].
• The development of scintillator crystals starts from the invention of NaI(Tl) by
Hofshtadter followed by the invention of PbWO4 , Bi4 Ge3 O12 and Lu2 SiO5 [21].

2.1.3 Applications

Most of the properties of any material can be realized the best in their single crys-
talline form. The absence of grain boundaries makes single crystals as the most suit-
able choice in numerous applications. The anisotropic properties of single crystal
58 M. Tyagi and S. C. Gadkari

also make it possible to study the dependence of various properties indifferent direc-
tions of propagation in materials which is otherwise not possible in any other form.
The industrial applications of single crystals increased manifold during the world
war and has been growing continuously after that. The single crystals have a vast
range of studies from academic research to the advanced technologies including
ICs, detectors, turbine blades, etc. and therefore have become the vital component
of the technology development. Semiconductor industries have the maximum share
applications of crystals. Single crystal silicon is used in almost all electronic equip-
ment [22]. It is also used in solar panel fabrications, radiation detectors and as a
substrate for various applications. Single crystals of metals or metal-alloys have the
best electrical and thermal properties in single crystalline form and are therefore
useful in various applications having extremely high temperature and force, e.g., jet
engine turbine blades [23]. The wide transparent regions of single crystal insulators
find applications in various devices like electro-optical, acousto-optical, fiber optics,
laser hosts, non-linear optics, scintillation detectors, etc. Single crystalline diamonds
are also now being synthesized in laboratories for various applications in extreme
conditions of temperature and pressure [24].
This chapter mainly emphasizes the synthesis and properties of single crystals of
scintillating materials used in the radiation detection applications. The scintillating
materials are characterized with the emission of visible light when irradiated with
higher energy radiations like x-ray, gamma or with charged particles like electrons,
alpha, etc. [25]. The single crystalline form of such materials is preferable especially
in the spectrometry. The single crystals are rich in electrons which interact with the
radiation and could transmit the emitting light from the bulk without any scattering
losses from grain boundaries. The single crystalline form ensures the light output
to be proportional to the deposited energy which leads to the distinct photo-peak
unlike that observed in glasses or liquid scintillators. The excellent energy resolution
makes it possible to identify different radio-nuclides by radiation detectors based
on single crystals [26]. Therefore, the single crystalline form is essential for the
spectrometry applications. The single crystal scintillators have major applications
in homeland security, medical imaging, high energy physics experiments, oil well
logging, nuclear industries, etc.
The applications of single crystals are continuously increasing beyond the
academic interests, which have made them to be one of the most vital components
of the current technology development. The single crystal of materials which can
perform under extreme conditions like high temperature in advanced reactors, high
luminosity in advanced accelerators, high flux in advanced synchrotron beam lines,
etc. are continuously attracting various research groups to work in collaboration with
the industries.
2 Growth of Single Crystals for Nuclear Radiation Detection 59

2.2 Growth of Single Crystals

2.2.1 Basic Concept

As mentioned earlier, to bring an ordered state to disordered state does not require
any thermodynamic barrier, e.g., melting ice into water. In general, the liquid state
can be transformed in to more ordered solid state by decreasing the temperature.
However, lowering the temperature to transform liquid state into more ordered solid
state is not the sufficient condition and the molecules need to overcome a thermody-
namic barrier to forma first tiny aggregate unit usually called nuclei and the process
is known as the “Nucleation” [27]. This temperature region where the state is still
in the liquid form even below its freezing temperature is called supercooling[28].
For example, water may not freeze into ice even below −20 °C in the absence of
any seed crystal. The nuclei usually considered to be spherical for various energy
calculations. For smaller radii of nuclei, the surface energy term dominates while
attraction volume energy dominates as the radii increases. The competition between
surface and volume energies decides a critical radius for the nuclei corresponding
to the inflection point that indicates the minimization of the energy and stability
of the phase. In the presence of impurities, surface, interface dust, etc., the energy
required for the nucleation is reduced by the contact angle and the nucleation takes
place heterogeneously or it may occur homogenously in a few cases which obviously
requires overcoming a higher energy barrier [27]. The rate of nucleation not only
depends on the thermodynamic barrier but the kinetic barrier also plays a role as
the temperature of the system decreases that consequently slows down the nucle-
ation rate. An increase in the degree of supercooling limits the kinetic motion of
the molecules. The energetically favorable nuclei grow further and eventually the
growth starts. In a similar manner as of the nucleation, the growth rate also attains a
maximum and limited by the atomic mobility in a more viscous melt with decreasing
the temperature further (Fig. 2.2) [29].
Therefore, the transition from liquid to solid state is mainly governed by the
balance of internal energy and a transformation from disordered to ordered state.

Fig. 2.2 Temperature dependence of a nucleation and growth rates and b Enthalpy/volume [30]
60 M. Tyagi and S. C. Gadkari

The Gibbs free energy can be defined to include both the terms as G = H–TS,
where temperature dependent term describes the disordering called entropy and H
represents the internal energy called enthalpy and behaves like the volume [29]. The
enthalpy decreases similar to the volume of the system with decrease in temperature.
While decreasing the temperature of liquid state, if the cooling rate is significantly
high, it does not allow sufficient time for the nucleation. Further a fast cooling rate
will lead the melt to more and more viscous state and then the liquid in due course
transforms into a rigid glass phase. However, on the other hand, if cooling rate is kept
slow that allows the nucleation to take place the enthalpy drops sharply and liquid
transform into the crystalline phase [29].

2.2.2 Various Methods and Techniques

The growth of a crystal is basically attaining a long-range order from the randomly
moving molecules. A single crystal is characterized by the absence of any grain
boundary and requires the growth of only a single grain. Depending on the application
and requirement of size, the crystals could be grown from vapor, melt or solution.
Various growth methods and techniques are listed in Table 2.1.
Different growth techniques have some advantages and disadvantages over other
techniques. Melt growth techniques are the most preferred ones to grow large size
single crystals. Although the crystals grow at much faster rate when grown from the
melt as compared to the solution growth, the melt growth is limited to only materials
that melt congruently. In addition to the application and size of the crystal, thermal
properties like expansion, conductivity, viscosity, chemical stability and require-
ment of composition, size and quality are the major factors to decide a technique
which should be used to grow single crystals of a particular material [31]. Majority
of single crystals used in various applications including the most extensively used
semiconductors are grown using melt growth techniques. We are mainly focusing
on scintillator single crystals in this chapter, which are mostly grown from melts
using the Czochralski or Bridgman techniques [32]. In the Bridgman technique, a

Table 2.1 Crystal growth methods and techniques

Melt growth techniques Solution growth techniques Vapor growth techniques
Czochralski (CZ) Aqueous solution Direct synthesis (DS)
Bridgman Travelling heater (THM) Physical vapor transport (PVT)
Floating zone Solute solution diffusion (SSD) Chemical vapor transport (CVT)
Verneuil Solvent evaporation (SE) Solid phase reaction
Temperature difference under
controlled vapor pressure
(TDM-CVP)
Hydrothermal synthesis
2 Growth of Single Crystals for Nuclear Radiation Detection 61

crucible containing the melt is lowered from a zone at a higher temperature to the
zone at a temperature lower than the melting point through a temperature gradient.
In the other scheme called the Czochralski technique (CZ), the crystals are grown by
pulling the melt to a lower temperature zone. The crucible is kept stationary, while
the position of solid-melt interface shifts into the hot zone. The use of an oriented
seed allows the growth along a specific crystallographic direction in this technique.
The ambience of growth chamber can be also selected according to the material
and crucible properties. The possibility to observe seeding and growth process in
the CZ technique enables to take corrective measures in real time during the growth
process unlike the Bridgman technique. In this chapter the single crystal scintillators
grown by the CZ technique are mainly discussed. In this technique, the powders of
constituent metal-oxides are mixed in their respective stoichiometric molar ratio and
filled in a suitable crucible to melt through inductive or resistive heating. A seed
crystal, mounted on a suitable seed holder and a seed road attached to the weighing
load cell, is brought in contact with the melt. The speed of lowering the seed has to be
also optimized based on the properties of melt which is kept in thermal equilibrium
with the rotating seed. The seed may be the single crystal of the same material to be
grown or an iso-structural material for better nucleation and minimization of disloca-
tions and other defects propagating from the seed. The weight signal is used to adjust
the heater power such that there is no growth and the melt maintain the state. This
complete process is called “seeding”. This first key step decides the fate of whole
growth run and therefore considered as one of the most crucial steps. The growth is
progressed thereafter by withdrawing the seed crystal with an optimized rate. The
growth rate is increased in a controlled manner to slowly increase the diameter to a
desired value. The maximum diameter is usually attained to the half of the crucible
diameter [33].
The growth is eventually completed after achieving the desired length. The
crystal/melt interface is snapped off by either through rapid lifting or by raising
the melt temperature. The grown crystal is subsequently cooled slowly to the room
temperature (Fig. 2.3) [34].

Fig. 2.3 Schematic diagram of a Czchrolaski and b Bridgman technique to grow single crystals
from melts [34]
62 M. Tyagi and S. C. Gadkari

A typical CZ crystal puller is mainly consisting of a power supply, suitable

crucible, a growth chamber to provide housing for crucible, thermal shield and
controlled ambient, a mechanism for pulling, rotation and weighing the crystal and a
computer controlled system. An iridium crucible is generally used for the growth of
materials with high melting temperatures. Therefore, the growth chambers need to be
closed to provide suitable ambient for the crucible material containing high temper-
ature melts. The main input parameters for a computer based close-loop control
systems are height and diameter of the crystal parts like seed, shoulder, cylindrical
and tail portions, pull rate, rotation rate, solid and melt densities, and translation
height for crystal detachment. The difference between the mass growth rates calcu-
lated from the input parameters and measured in the real time generates an error
signal to provide a feedback for the power supply. When the growth rate is slow the
negative error signal would lead to the lowering of power while in case of a faster
growth rate the power (hence temperature) would be increased due to a positive feed-
back from the error signal. The system may be put in the automatic control when
the error signal reaches close to zero. Inputs on the proportion and integration terms
decide how to respond with the power changes and mainly governed by the thermal
inertia and temperature oscillations stirring in the melt. This real-time feedback and
corrective measures make the CZ technique the most useful for various single crystals
specially required in larger sizes.

2.2.3 Challenges and Strategies

Although the mechanism of crystal growth from melts seems very simple but one
has to face numerous challenges in growing device quality single crystals. Each
single crystal needs to comply for some specific criteria before being used them in
any application. Single crystals for laser applications require insignificant absorption
coefficient and negligible refractive index variation, while single crystal scintillators
for radiation detection require high light output, fast radiative decay, high radiation
hardness and absence of afterglow. The devices based on single crystalline semicon-
ductors like c-Si and Ge desires high resistivity and long carrier life time [34]. Since
the crystal growth is a high temperature process, it needs a systematic optimization
of various parameters to achieve good quality crystals having the desired properties.
The selection of various growth parameters significantly varies from material to
material and strongly depends upon the material properties along with the dimen-
sional and quality requirements. The main properties of materials, to decide the
growth parameters, include thermal conductivity of solid and liquid phases, melt
viscosity and microstructure, chemical properties, anisotropy in thermal expansion,
difference in solubilities of dopant in liquid and solid phases, etc. Therefore, any small
change in the material needs multiple trial growth runs to optimize various growth
parameters. The control of growth parameters is usually governed by adjusting the
power rather than the temperature which is difficult to monitor. Some materials
have higher tendencies to grow in glassy phase and therefore require a very slow
2 Growth of Single Crystals for Nuclear Radiation Detection 63

growth rate for the crystallization [33]. The difference in ionic radii of constituents
and dopants lead to a low segregation and the concentration varies in the melt and
solid phases [35]. The presence of strong cleavage planes makes the crystal prone to
cracking along particular planes and therefore requires the growth to be carried out
using a seed oriented in a specific direction.
The shape of the solid-melt interface is one of the most important parameters that
determine the stability of the growth process. A slightly convex shape toward the
melt prevents an unpredictable detachment of the growing crystal. The presence of
strain and dislocations also depends on the shape of the solid-melt interface. Based
on the density, viscosity and conductivity of the melt, the rotation and pulling rates
are adjusted for the required interface shape [36].
There are various kinds of heat flows and convective currents in the melt during
the growth process which include gas and melt convection, solid and liquid heat
conduction and the heat of fusion [36]. Heat from the melt and the latent heat of
crystallization are required to be conducted through the growing crystals for a stable
growth. The various heat flows mainly depend on the thermal conductivities of melt
and solids and governed by radial and axial temperature gradients. The thermal
gradients could be optimized by the geometry of growth station, dimension and
material of the seed holder, flow and pressure of ambient gas, diameter of seed and
crystal, etc. [37].
The pull rate of crystals is related to the growth rate which varies from few tenths of
mm/h to a few of cm/h from material to material. The growth rate is basically limited
by the thermo-elastic properties of the crystal, segregation of dopants/impurities and
the generation and propagation of defects. Metals that have higher thermal conduc-
tivities for releasing the heat of crystallization can be pulled at a much faster rate
which is usually limited by the thermal gradient above the solid-melt interface [32].
The axial temperature gradient has to be optimized based on the radius of crystal,
the heat loss from the crystal, thermal expansion coefficient and the breaking strain
of the crystal. A small value of anisotropy in thermal expansion and thermal conduc-
tivity can also cause crystal cracking during the growth or annealing. The growth
should preferably be along the axis that has the smallest thermal expansion coeffi-
cient to minimize the cracking problem during the growth and cooling of the crystal.
The cooling rate of the grown crystal also depends on the breaking strain, thermal
expansion coefficients and the crystal diameter [32].
The differences in vapor pressures of constituent oxides make selective evapo-
rative losses and lead to stoichiometric variations during the growth. The variation
from the stoichiometry in the grown crystal and in the melt (left over charge after
the growth) causes cracking and coloration in the grown crystals. The most volatile
component is usually compensated in the starting powder to avoid variation from the
stoichiometric ratio [35].
The oxide crystals usually have defect centers related to the oxygen sublattice.
These defect centers can be controlled by selecting appropriate growth ambience and
after growth annealing treatment. The exchange of cations also causes to the antisite
defects in some oxide crystals which can be compensated with the appropriate co-
doping in some cases [38]. Since the growth process usually takes 7–10 days to get a
64 M. Tyagi and S. C. Gadkari

crystal with a decent size, sometimes there are unpredictable parameters which may
cause the crystal yield to be less than 100% in most of the cases.

2.3 Characterization Techniques

2.3.1 Thermal and Structural Characterization

The phase formation and melting/solidification behavior are the essential properties
that need to be known before planning any crystal growth experiment. The temper-
ature variations of material properties are generally studied by Differential thermal
analysis (DTA) experiments. In this technique, the difference between the temper-
atures of two crucibles (reference and sample) is measured as a function of time to
measure endothermic/exothermic reaction or phase change. The DTA of a compound,
that melts congruently, would have a single sharp peak. A material which decom-
poses before its melting temperature or have multiple peaks corresponding to more
number of phases cannot be grown from melt growth methods. The crystalline or
glassy nature of transition can also be observed from the DTA plots [39].
The X-ray powder diffraction (XRD) is used to identify the phase formed during
material synthesis and after the crystal growth. The structural parameters of the
crystal, grain size, texture, residual stress, presence of foreign phase, etc. can be
obtained by analyzing the XRD pattern [40]. The regular pattern of atoms in a crys-
talline solid lead to constructive interference between reflected x-rays corresponding
to certain angles satisfying the Bragg condition (2dsinº = nλ). The pattern of a
single crystal has single peak corresponding to a single plane. The powder samples
have randomly oriented numerous crystals, and therefore the pattern is consisted of
multiple peaks (Fig. 2.4).

Fig. 2.4 XRD patterns of

perfect crystal, real crystal
and glass/amorphous
2 Growth of Single Crystals for Nuclear Radiation Detection 65

The perfection of crystallinity and presence of any strain or mosaicity in the single
crystal scan be measured by recording the rocking curve using a triple axis high reso-
lution XRD (HR-XRD) employing a well collimated X-ray beam. The orientation
of a single crystal is determined from the symmetry of projections measured by the
Laue techniques [40].

2.3.2 Electronic And Optical Characterization

The fraction of incident light transmitted through a sample is measured using a double
beam UV/VIS spectrophotometer for transmission/absorption properties [41].

Transmittance (% T) = Light passing through a sample Incident light

Absorbance (A) = − log (%T 100)

The value and nature of the band gap can be calculated by applying a power law
equation on the fundamental absorption edge data. In addition to the near edge funda-
mental absorption with urbach tail, atypical absorption spectrum represents various
features in the crystal arising due to the absorption from high lying energy levels,
excitons, impurities and free carriers also. The radiation hardness of a scintillator
crystal is calculated from the radiation induced absorption by measuring absorption
spectra before and after the irradiation.
The emission followed by the absorption is called luminescence and measured
using either a photoluminescence spectrometer (UV–VIS excitation) or a radio-
luminescence setup (X-ray excitation) [42]. The wavelength dependent emitted inten-
sity and the distribution of intensity that causes luminescence are called emission
spectrum and excitation spectrum respectively. The time spent in the excited state,
i.e., life-time of the excited state is measured as the luminescence decay time. These
are the important parameters to be determined for any scintillator crystal and the
emitted light wavelength should match with the available photo-sensors efficiencies,
and the emission decay should be fast enough to handle higher count rates of incident
radiation. The excitation spectrum represents the presence of bands corresponding to
the excited states of activator ions in forbidden band gap and their position relative to
the conduction band edge. The excited states of the activator should not be very close
to conduction band to minimize the thermal ionization of excited carrier to conduc-
tion band and should not be very far as well to minimize the available sites for trap
centers. The temperature dependence of luminescence helps to understand the elec-
tronic band structures and describes the activation energy for thermal quenching of
the emission. Time resolved photo-luminescence helps to identify the excited states
that contribute to the different components of the emission decay times [42]. The
presence of long-lived trap centers may result in the afterglow of the emission which
can be measured using a fast shutter to stop the irradiation of the excited light and
measuring the remaining emitted light as a function of time.
66 M. Tyagi and S. C. Gadkari

The presence of defect structure in the materials can be probed by measuring

the thermally stimulated luminescence (TSL) or optically stimulated luminescence
(OSL) [43]. The excited charge carriers are trapped in the defect centers present
in the crystal scintillators due to various imperfections. These trapped carriers are
excited thermally or optically which consequently recombine to emit photons that
are measured by suitable photo-sensors. The position of these trap centers in the
forbidden gap can be calculated by plotting the temperature as a function of emitted
intensity, called a glow-curve. The intensity of the stimulated light is proportional to
the deposited dose of radiation in the dosimeter materials [43].

2.3.3 Scintillation Properties

The main characteristics for ideal scintillator crystals are high effective atomic
number, high light output, fast decay, high mechanical, chemical and radiation hard-
ness, emission matching with photo-sensors and energy proportionality. As there is
no single material that fulfils all the criteria, different single crystal scintillators are
used as radiation detector in different applications. For examples, medical imaging
like PET requires fast coincidence timing resolution while high energy physics exper-
iments require high density and high radiation hardness [21]. Therefore, the grown
single crystals need to be characterized for their scintillation properties useful for a
particular application before developing devices based on them [44]. For basic scin-
tillation characterizations, the single crystals are usually coupled with photo-sensors
like PMT, photodiodes or SiPM using optical grease due to the variation in refractive
indices. All other surfaces of the single crystal except the surface to be coupled with
photo-sensors need to be covered with some kind of reflector like Teflon tape, Spec-
tral on hemisphere or reflecting paint to collect the maximum number of photons
generated from high energy radiation. The output of photo-sensor is subsequently
fed to a setup consisting of a pre-amplifier, a shaping (spectroscopic) amplifier and a
multi channel analyzer (MCA). The pulse-height spectrum (PHS) represents counts
(on ordinate y-axis) as a function of the MCA output voltage proportional to the
number of photons which are proportional to the deposited energy (the pulse height,
on abscissa, x-axis). The radiation interacts via three processes: photoelectric absorp-
tion, Compton scattering and pair production which are observed in the pulse-height
spectrum. The dominance of these processes is mainly governed based on the inter-
acting medium and the energy of the incident radiation. The photo-peak represents the
full energy deposition peak. Therefore, the x-axis representing the energy describes
the light output of any scintillator crystal corresponding to the position of the photo-
peak. Light output (ph/MeV) can be defined as the number of photons generated per
unit energy deposition. The relative position of the photo-peak that was measured
with a known scintillator like BGO or NaI:Tl gives the relative light output of a scin-
tillator [25]. A higher light output leads to better statistics and better energy resolution
to identify the radio-nuclides having close energies. The energy resolution is defined
as the ratio of full width at half maxima (FWHM) to the energy. Ideally, the light
2 Growth of Single Crystals for Nuclear Radiation Detection 67

output should be proportional to the deposited energy but most of the single crystals
have non-proportionality which affects their energy resolution and therefore need to
be investigated for this deviation to understand the basic scintillation mechanism in
addition to the performance of devices.
The kinetics of scintillation is mainly characterized by measuring the scintil-
lation decay times using the anode pulse fed to a fast oscilloscope or using a
complex Thomas-Bollinger setup based on time correlated single photon counting
[45]. The scintillation decay time of an excited state limits the application of a
scintillator crystal in high count rate (high activity) applications. The presence of
multi-components in the exponential decay times makes it possible to discriminate
various kinds of excitations, e.g., alpha, gamma, etc. if the ratio of different decay
components depends on the mode of excitation.
Based on the applications, other scintillation properties like coincidence timing
resolution, pulse-shape discrimination, etc. can be measured by using standard
nuclear electronics modules or advanced digitizers [25].

2.4 Improvement of Performance Characteristics

A systematic approach to grow single crystals of a promising scintillating garnet

material and a strategy based on defect engineering to improve its scintillation char-
acteristics is briefed in this section. Some of the results have been represented from
our articles published in J. Phys D: Appl. Phys. 46 (2013) 475302 and Phys Stat
Solidi-Rapid Research Letters 9 (2015) 530 with the proper permission [46, 47]
(Fig. 2.5).

2.4.1 Material Designing and Dopant

Metal-oxide single crystals, having a garnet structure, usually have high density to
stop high energy radiation, broad transmission range to accommodate suitable dopant
and transmit the emitted light, and have significantly improved mechanical, radia-
tion and chemical resistance. These host materials can be doped with an activator
ion Ce3+ which has efficient and fast emission originating from the allowed tran-
sition between 5d to 4f states and therefore makes it a suitable choice as a dopant
in scintillating crystals with trivalent cations. Crystal field due to the surrounding
legend ions, dominantly, affects the splitting and positioning of 5d states and there-
fore resulting in a broad range of emission wavelengths of Ce3+ ions depending on
the host lattice. An extensive investigation was carried out on the multi-component
garnet compounds by combinatorial band gap engineering approach. The results of
these comprehensive studies found Ce doped Gd3 (GaAl)5 O12 crystals having very
promising scintillation properties [49]. These materials crystallize in a cubic struc-
ture where the Gd/Ce is dodecahedrally coordinated with oxygen in the D2 point
68 M. Tyagi and S. C. Gadkari

Fig. 2.5 a A schematics of basic scintillation process and b characterization setup with a typical
pulse-height spectrum

group symmetry while Ga and Al cations are in octahedral and tetrahedral config-
urations with oxygen ions as shown in Fig. 2.6a. This symmetry splits the 5d level
of Ce3+ in 5 sublevels where three sublevels having higher energies are buried in
the conduction band and two sublevels reside in the forbidden band gap region. A
larger Ga ion (0.62 Å) et al. (0.54 Å) sites induces a compression on the adjacent
Gd/Ce ions, coordinated with oxygen in dodecahedral, and therefore consequently
changes the crystal field splitting of Ce 5d levels. It subsequently leads to a change
in the position of the lowest excited 5d level with respect to the conduction band
and causes the blue shift (towards lower wavelength) in the emission as shown in
Fig. 2.6b. Therefore, with the help of material engineering the relative position of
the conduction band and Ce 5d1 level can be optimized to provide an adequate gap
for minimizing the room temperature thermal ionization of excited charge carriers
[48]. However, the gap should not be too high to accommodate more trap centers.
This material engineering should consequently result in an enhancement of the radia-
tive recombination to increase the scintillation light output. The ratio of Ga:Al was
optimized to be 3:2 for the best combination of light yield and decay kinetics [49].
Due to the high melting temperature, the Czochralski technique was used to grow
single crystals of Ce doped Gd3 Ga3 Al2 O12 (henceforward will be represented as
GGAG only). An automatic diameter-controlled crystal puller system was used along
with starting charges prepared by mixing the constituent metal-oxides of Gd2 O3 ,
Al2 O3 , Ga2 O3 in respective stoichiometric molar ratio and doped with 0.2 at% CeO2 .
Several crystal growth experiments were carried out as per the following details:
2 Growth of Single Crystals for Nuclear Radiation Detection 69

Fig. 2.6 a The crystal

structure of Gd3 (Ga,
Al)5 O12 and b the shifting of
Ce3+ emission with respect
to Ga concentration [46]
[Reproduced with the
permission from “IOP
Publishing”]

• As-prepared powder pressed in the form of pellets and loaded in a crucible.

• The mixed powder sintered at 1400 °C to pre-synthesize the phase before growing
the crystal.
• Partial oxygen pressure maintained in the growth chamber by flowing nitrogen
and air to avoid oxidation of iridium crucibles.
• To avoid the oxidation of Iridium crucible and Ce3+ ions, Argon gas was constantly
flown during the growth in a closed chamber.
• After loading the as-prepared or pre-synthesized material, the crucible was heated
to about 50 °C more than the melting temperature for homogenizing the melt.
• In initial growth runs, a single crystal seed, prepared from the Y3 Al5 O12 (YAG),
was used to pull some single crystalline chunk. Later, an un-oriented GGAG seed
was prepared and used to grow larger single crystals.
Initially, due to the higher density (~6.5 g/cc), the loaded material was not suffi-
cient to provide an appropriate melt height for the required thermal gradient and
growth could not be initiated. Therefore, the initial material was pressed into pellets
to load in a larger quantity and melted and reloaded after cooling. The process was
70 M. Tyagi and S. C. Gadkari

Fig. 2.7 Single crystals

grown a in the first attempt
and b after the optimization
of various parameters

(a) (b)

repeated to attain the required melt height. However, to avoid any stoichiometric
deviation due to higher evaporative losses of Ga2 O3 , an excess amount was taken
accordingly and initial material was also prepared in multiple batches. In initial
growth attempts the seed got melted during the optimization of power and the crystal
could be grown from the iridium seed holder. The grown crystal was found to have
multiple cracks with poorly controlled diameter. A seed was cut perpendicular to the
growth axis and used in next growth runs. A good quality single crystal could be
grown after multiple attempts as shown in Fig. 2.7b. The poor quality in the lower
region may be assigned to the deviation from stoichiometry due to different evapo-
rative losses of constitute oxides. The diameter control was improved significantly
after the optimization of growth parameters. The solid-melt interface was found to
be nearly flat. The optimized parameters, for a successful growth run after multiple
trial runs, are listed in Table 2.2.
The effect of co-doping and growth ambient has been discussed in the next
sections.

Table 2.2 Crystal growth

Melting temperature 1850 °C
parameters
Pull rate 1 mm/h
Rotation rate 10–20 rpm
Initial chamber pressure 1 × 10–5 mbar
Ar gas pressure 1100 mbar
Temperature gradient 30–50 °C/cm
Cooling rate 20–30 °C/h
2 Growth of Single Crystals for Nuclear Radiation Detection 71

2.4.2 Effect of Co-Doping

Single crystals usually have point defects including cation or anion vacancy centers.
Additionally, the materials, having a garnet structure, usually have antisite defects
also (such as LuAl in Lu3 Al5 O12 , LuAG). These defect centers play a crucial role
in the luminescence efficiency and decay kinetics of these materials. Similar to the
ratio of Ga:Al cations as shown in Fig. 2.6b, the aliovalent and/or codopants of
different ionic radii may also modify the crystal field affecting the transitions in Ce
ions and have an effect on the scintillation properties consequently. The codoping
may also affect the defect structure of single crystals. Therefore, in addition to Ce
activators, the single crystals were grown with various co-dopants. The significant
changes were observed in calcium (Ca) and boron (B) codoped crystals as discussed
in the following paragraphs.
The absorption spectra recorded for differently codoped crystals are presented
in Fig. 2.8. The forbidden band gap of GGAG crystals was found to be ≥5.8 eV.
The dominating absorption bands observed at 440 and 340 nm can be assigned to
the transitions from 4f ground state to the 5d excited states located in the forbidden
band gap. The narrow absorption bands at 274 and 310 nm and increased absorption
in the lower wavelength region can be assigned to the transitions of Gd3+ ions. The
small difference between these transitions to Ce3+ states indicates a larger possibility
of resonant transfer from Gd3+ to Ce3+ ions. Calcium (Ca) codoping was found
to significantly increase the absorption at lower wavelengths near the absorption
edge resulting in suppression of the absorption band at 340 nm corresponding to
Ce3+ 4f-5d2 higher energy transitions. This can be assigned to the occurrence of the
additional energy levels of Ca2+ . Boron (B) codoping induces a slight improvement of
the transmission in the lower wavelength region near the absorption edge. However,
no additional lower energies (in the visible region) absorption bands were observed
due to these co-dopants and therefore indicating the absence of any additional defects
in codoped crystals. The transitions from the excited 5 d1 state of Ce3+ results in an
emission band consisting of two bands at 520 nm and 565 nm corresponding to the
splitting up of the 4 f ground state into 4 F5/2 and 4 F7/2 states. The emission spectrum
was observed to be unaffected with the co-doping. This indicates that there is no
considerable change in the band gap, crystal field, or the relative position of Ce
excited states due to the codopants. Therefore, the effect of codoping should be
mainly assigned to the modification of the defect structure of crystal.
The effect of co-doping on the scintillation light output is shown in Fig. 2.9. The
pulse-height spectra were recorded using a Cs137 source. The position of the photo-
peak describes the relative light output. Ca codoping decreased the light output
significantly, while B codoping was found to increase the light output of GGAG:Ce
crystals. The absolute light outputs of GGAG:Ce and Ca and B codoped crystals were
measured as 47,000 ph/MeV, 32,460 ph/MeV and 52,000 ph/MeV, respectively[46].
The B codoping significantly improves the energy resolution also, from 9 to 7.8%,
measured at 662 keV gammas. The effect of codoping on scintillation kinetics of
these crystals by gamma excitation and measured at room temperature is represented
72 M. Tyagi and S. C. Gadkari

Fig. 2.8 The effect of

codoping on a absorption
and b excitation and
emission spectra of a
GGAG:Ce crystal [46]
[Reproduced with the
permission from “IOP
Publishing”]

in Fig. 2.9b. The decay curve consists of mainly two components and indicates the
presence of more than one mechanism for the de-excitation. The decay curves were
fitted exponentially having two decay components and the obtained values are listed
in Table 2.3. While the Ca codoping accelerates the scintillation rise and decay times,
no considerable effect was observed with the B codoping.
However, the co-doping did not have any significant effect on the photo-
luminescence (PL) decay times. The difference between intrinsic PL and scintillation
decay time can be attributed to an energy transfer mechanism that plays a signifi-
cant role when electrons are excited deep into the conduction band by higher energy
gamma excitations in scintillation decay time measurements.
These results suggest that the co-doping affects the defect structure of the crystal.
The possible effects of codoping on defect structures may be envisaged as given
below [Reproduced with the permission from “IOP Publishing”]:
2 Growth of Single Crystals for Nuclear Radiation Detection 73

Fig. 2.9 Effect of codoping

on a relative scintillation
light output and
b scintillation decay time of
GGAG:Ce crystal measured
using a Cs137 source. The
light output is on a scale
where a reference BGO light
output was set at channel 100
[46] [Reproduced with the
permission from “IOP
Publishing”]

Table 2.3 The fitted values

Composition τr (ns) τ1 (ns) (R%) τ2 (ns) (R%)
of scintillation rise (τr ) and
decay times (τ1 and τ2 ) and GGAG:Ce 8 52 (74%) 335(26%)
their relative ratios for GGAG:Ce, Ca 6 44 (76%) 260(24%)
differently codoped crystals
GGAG:Ce, B 8 58 (75%) 350(25%)

(1) The Ca co-doping introduces a few additional energy levels or traps in the
forbidden band gap as confirmed by the absorption spectrum. These levels
provide a non-radiative bypass path for relaxing the excitation, thus affecting
the energy transfer from Gd3+ to Ce3+ and consequently quenching the light
output together with reducing the decay time. The Ca ions have a larger ionic
74 M. Tyagi and S. C. Gadkari

radii (1.0 Å) and lower valence state (2+) which cause increasing the concen-
tration of cation vacancies and hole trap centers by replacing smaller cations
Gd3+ (ionic radius 0.94 Å), Ga3+ (0.62 Å) or Al3+ (0.54 Å). The lower valence
state of Ca may also enhance the formation of optically inactive Ce4+ ions in
place of the efficiently emitting Ce3+ ions. In addition, the charge transfer from
O2− to Ce4+ increases the absorption at higher energies, as observed in the
absorption spectrum [46].
(2) The co-doping with B3+ that has a much smaller ionic radius of (0.27 Å), may
readily fit into interstitial sites and therefore may act as competing electron trap
centers due to excessive charge. This consequently causes a decrease in the trap
centers related to the oxygen vacancies and improves the transmission at higher
energies as revealed in the absorption spectrum. Therefore, the excitation in a
higher Ce3+ excited state also increases and eventually leads to a better light
output [46].
(3) The creation of defects in anion sublattices related to trapped holes at interstitial
oxygen (O− ) or trapped electrons at oxygen vacancies (F or F+ ) may also be
affected which could be further investigated by the post growth annealing
treatment [47].

2.4.3 Growth Ambient and After Growth Treatment

In addition to the defect centers related to the anion sublattice, the tendency of
multi-valence state of activator Ce ions (+3 or +4) can also be influenced with the
growth ambient, pre-growth and after-growth annealing. Therefore, single crystals
were grown and annealed under different conditions and the scintillation properties
were studied. The single crystal grown from a pre-synthesized material (sintered at
1400 °C) was found to have poor absorption at characteristics Ce3+ bands suggesting
the presence of Ce4+ ions in the material used for the growth. Therefore, crystal
growth experiments were planned with as-mixed powders of constituent metal-oxides
without any sintering. Since boron codoping was found to improve the scintillation
performance, single crystals of GGAG:Ce (0.2 at%) codoped with B (0.2 at%) were
grown using the Czochralski technique in a partial oxygen ambient (90% N2 + 10%
air) and in flowing argon (Ar) in separate experiments.
Figure 2.10a exhibits absorption spectra recorded for the crystals grown in varying
conditions. In addition to the characteristics Ce3+ absorption bands at 340 and 445 nm,
the presence of optically inactive Ce4+ ions can be inferred from an increased absorp-
tion at higher energies due to the charge transfer transition from O−2 to Ce4+ ions
below 300 nm. The presence of cerium ions in the tetravalent state (+4) was found to
be maximum in crystals grown from a material synthesized in air which consequently
leads to the lesser light output.
The absorption near the fundamental edge is slightly higher in crystals grown in
a partial oxygen ambient compared to that measured for the crystals grown in argon.
However the characteristic absorbance bands at 345 and 445 nm due to Ce3+ ions are
2 Growth of Single Crystals for Nuclear Radiation Detection 75

Fig. 2.10 a The absorption

spectra of GGAG:Ce, B
crystals grown using
pre-synthesized charge in air
(——), in partial oxygen
pressure (—•—) and in
argon ambient (—o—). b
The photoluminescence
excitation and emission
spectra of GGAG:Ce, B
crystals grown in partial
oxygen pressure (—•—), and
annealed in air after the
growth in argon ambient
(—▲ —) [47] [Reproduced
with the permission from
“Wiley–VCH Verlag GmbH
& Co. KGaA”]

similar in these crystals and therefore the scintillation properties can be compared
for these two crystals grown in different ambient conditions. Figure 2.10b shows the
effect of the growth ambient on PL excitation and emission spectra of a GGAG:Ce,
B crystal. The relative intensity of higher energy excitation band is suppressed in
the crystals grown in partial oxygen due to a higher absorption near the fundamental
absorption region as shown in Fig. 2.10a.
The effect of growth ambient and after-growth annealing treatments on scintil-
lation light output and decay time are shown in Fig. 2.11. The scintillation light
output was found to increase and decay-time becomes faster after annealing. The
crystals grown in argon ambient and annealed in air were found to have the highest
light yield. On the other hand, a crystal grown in a partial oxygen ambient did not
show any change after the annealing in air or vacuum at 1000 °C for 10 h. The light
yield improved from 54,000 ph/MeV for crystals grown in partial oxygen ambient
to more than 60,000 ph/MeV for the crystals grown in argon and annealed in air
after the growth. The energy resolution also improved to 5.8% at 662 keV for the
76 M. Tyagi and S. C. Gadkari

Fig. 2.11 The pulse-height

spectra and scintillation
decay time measured for a
137 Cs gamma source using a

GGAG:Ce, B crystal grown

in partial oxygen (–•–),
argon ambient (— —), and
annealed in air after the
growth in argon ambient
(—▲ —) [47] [Reproduced
with the permission from
“Wiley–VCH Verlag GmbH
& Co. KGaA”]

annealed crystals. The best value for the energy resolution of about 4.7% is reported
for a GGAG crystal having 1% Ce and coupled with APD (Hamamatsu S8664-010).
However, the scintillation decay time was not significantly different for these two
types of crystals.
The post-growth annealing treatment did not make any significant change in the
absorption spectrum suggesting that the effect of annealing is not responsible for
the change in the valence state of cerium from 4+ to 3+. Therefore the change in
the valence state and crystal field splitting cannot be considered for improving the
light output in crystals grown in Ar ambient and annealed in air. Since these crystals
were grown in different ambient conditions, the defect centers may play a major
role for any change in optical or scintillation properties. The crystals grown in argon
are more prone to have defect centers related to the anion sub-lattices which can
be generated either due to oxygen vacancies (F or F+ ) or presence of interstitial
2 Growth of Single Crystals for Nuclear Radiation Detection 77

Fig. 2.12 a Effect of

codoping and b growth
ambient/after-growth
annealing on the
thermo-luminescence
properties of GGAG:Ce
crystal [47] [Reproduced
with the permission from
“Wiley–VCH Verlag GmbH
& Co. KGaA”]

oxygen (O− ). Annealing in air decreases the concentration of these defect centers
that consequently increases the light output and makes the decay faster.
Thermo-luminescence measurements were performed to understand the defect
structure in crystals grown under varying conditions (Fig. 2.12). The thermo-
luminescence measurements below room temperatures and at elevated tempera-
tures were performed respectively in a liquid nitrogen cryostat and in conventional
thermo-luminescence measurement set-up. The size and weight of the samples for
TL measurements were kept the same, and the TL glow curves were normalized for
the luminescence intensity and its temperature dependence. Therefore the intensity
of glow peaks can be considered proportional to the concentration of trap centers.
The codoping with Ca greatly reduced the shallow charge traps. However, new
deeper traps dominated at 390 K in the Ca codoped crystals. The co-doping with
boron also had a significant effect on the TL glow curve by eliminating the 200 K
trap and the deeper traps above room temperature.
78 M. Tyagi and S. C. Gadkari

The crystals grown in argon ambient had a higher concentration of defect centers
that was reduced significantly after the annealing of crystals in air. The glow peak
at 550 K completely diminished after the annealing of crystals in air and there-
fore can be assigned to oxygen vacancies. The trap centers in the as-grown crystals
grown in argon ambient compete with other electron trap centers like antisite defect
centers etc., which affected the light output of these materials. An absence of glow
peaks around 250 K also indicates elimination of this kind of trap centers in the
crystal grown in Ar ambient. The post-growth annealing of crystals in air reduced
the concentration of trap centers related to oxygen sublattices which already had a
lesser concentration of other trap centers. Consequently, the crystals grown in argon
and annealed in air will have the least concentration of defect centers and therefore
improved scintillation properties.

2.5 Conclusion and Future Outlook

In summary, a systematic approach has to be adopted for growing single crystals of

multi-component garnets having promising scintillation properties of radiation detec-
tion. With a better understanding of underlying processes, the scintillation perfor-
mance characteristics could be further tailored with the help of appropriate selection
of co-dopants. An optimization of growth ambient and after-growth annealing treat-
ments can be also made useful for further modification of the defect structure of single
crystals in a favorable manner to achieve a higher light output and better energy reso-
lution. The defect centers related to the oxygen sub-lattice, caused by the reducing
growth ambient, may compete with the formation of other trap centers having detri-
mental effects on scintillation properties. The concentration of trap centers related to
the oxygen vacancies/interstitials may be subsequently reduced by the after-growth
annealing treatment in an appropriate ambient. This chapter demonstrated that this
scheme could eventually improve the performance characteristics of GGAG crystals
but it can be successfully adopted for other oxide scintillators as well.

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Chapter 3
Techniques for Thin Films of Advanced
Materials

K. R. Sinju, A. K. Debnath, and Niranjan S. Ramgir

Abstract With the advent of nanoscience and nanotechnology, there has been an
upsurge in the synthesis, characterization, and application of numerous functional
materials. This has been attributed predominantly to the enhanced surface area to
volume ratio and ease of control over the surface functionalities requisite for targeted
applications. The numerous functionalities and tailor made properties are obtained
by careful choice of process parameters involved in different synthesis strategies.
Thin film deposition techniques have become the obvious choice of synthesis as
it is possible to envisage the desired control in the resulting advanced materials.
In order to introduce the novel functionalities in these advanced materials, the thin
film deposition techniques have been modulated, upgraded, and even developed. The
present chapter focuses on the recent advancement in the thin film techniques that
have been utilized effectively to realize advanced materials for targeted applications.
Each technique has been discussed elaborately explaining the basic principle and
importantly highlighting the novel functionalities introduced, its merits and demerits
citing advanced materials synthesized using the same.

Keywords Thin films · Advanced materials · Metal oxide semiconductor ·

Nanoscience · Nanotechnology

3.1 Introduction

With the advent of nanoscience and nanotechnology there has been an upsurge in
the synthesis of novel functional materials or the so-called advanced materials. This
upsurge has demanded the development of novel techniques like vapor phase growth
using furnaces, Langmuir Blodgett (LB), and Self assembled monolayers (SAM)
or modulation of existing conventional techniques. In order to sustain the growth in
this field, various conventional thin film deposition techniques have been upgraded or
modified so as to achieve possibility of advanced material synthesis. Films having the

K. R. Sinju · A. K. Debnath · N. S. Ramgir (B)

Technical Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 81
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_3
82 K. R. Sinju et al.

thickness less than 1 μm are generally referred to as thin films. They are alternatively
defined as the films having the thickness at which the material possess the properties
that are markedly distinct from its bulk counterparts. Thin film deposition techniques
have a good blend of process parameters that can effectively be used to realize
advanced materials. The beginning of the advanced material may be assigned to
the observation of two dimensional electron gas (2DEG) observed in metal oxide
semiconductor field effect transistor (MOSFETs) synthesized using the conventional
C-MOS technique mainly thin film techniques [1]. Herein, electrons are confined to
a 2D plane probably because of a Schottky barrier that exist between metal and oxide
(MOSFET), or different semiconductors (heterostructures) [2]. This has marked the
growth in synthesis of such and other allied materials that now arrive to the recent
discoveries of 2-D nanostructures such as graphene and metal dichalcogenides like
MoS2 [3, 4].
Nanotechnology is an advanced and fast growing technology and has gained
enormous attention due to its noticeable performance in science and thereby all
disciplines of human life. It deals with the materials, devices, and other structures
having at least one dimension in the size from 1 to 100 manometers. At this scale
quantum effects are noticeable and have been explored for their usage in various
device applications. Accordingly, various synthesis routes have been developed and
reported for nanomaterials. Thin films have its own great role in the nanoscience
and accordingly, have found unique applications such as antireflection coatings [5],
reflection coating for mirrors [6], corrosion or oxidation protection coatings, sensors
for liquid or gaseous chemicals, SQUID, and semiconductor industry [7]. For the real-
ization of novel advanced materials, the conventional thin film deposition techniques
become an important part of the set of tools used for their synthesis or fabrication [8].
For examples, to realize nanowires using top down approaches, the thin film of the
required materials is first deposited using thin film techniques (like thermal evapora-
tion, sputtering) and later etched out (like deep anisotropic etch, Inductively coupled
plasma (ICP), reactive ion etch (RIE), anisotropic wet etch and metal assisted etch
(MAE)) in controlled manner to realize different nanomorphologies [9–11]. Same
is the case with the growth of different nanoforms using the bottom-up approaches.
Herein, again the conventional thin film techniques like thermal evaporation, e-beam
deposition and sputtering, are employed to realize the seed layer of catalyst that
are later grown using the vapor–liquid–solid (VLS) mechanism [12, 13]. Thus, it
is evident that the thin film techniques form the backbone to various strategies or
methodologies required for the reproducible and repeatable synthesis of various
advanced materials. The main dependence on the thin film techniques is attributed
mainly to its great potential for scale up required for batch or bulk production crucial
for commercial viability.
The aim of the present chapter is to provide the state of the art of the thin film
techniques that have been used and modulated where required realizing advanced
materials and describing the novel thin films techniques that have been recently
introduced for the same. Care has been taken to provide basic introduction to the
techniques covering the working principles and then elaborating their utility in real-
izing the novel materials citing results from the literature. The chapter ends briefing
3 Techniques for Thin Films of Advanced Materials 83

the important advancement in the field and discussing the future prospects. Growth
of advanced materials using thin film techniques is a wide field and it is difficult to
incorporate all the important findings. Although attempts were made to include all
the important advancement, it is possible to miss some of them.

3.2 Basic Introduction and Fundamentals of Thin Film

Techniques

Thin film refers to a coating or formation of a film on a substrate that is few nanome-
ters to 100 μm thick [14, 15]. The controlled synthesis of material in the thin film
form is the most fundamental step in numerous fields including optical electronics,
microelectronics, communication, catalysis, and energy [16, 17]. Film deposition in
general involves processes such as impingement, desorption, nucleation and growth,
coalescence of islands and eventually development of continuous film structure [18].
The nucleation step is very important as it governs microstructure and crystallinity
of the resulting film. In chemical synthesis, nucleation is considered to be a physical
reaction that occurs when the components in a solution precipitate out, forms nuclei
which eventually attracts more precipitate. For physical methods, there are mainly
three modes of film growth given as follows:
(i) Island or Volmer—Weber growth
(ii) Layer by Layer or Frank—Van der Merve growth and
(iii) Mixed or Stranski—Krastanov growth
Island growth occurs when the atoms or ions of precursors are more strongly
bound to each other. This bond is stronger than the one between atoms and the
substrate. Further growth results in the merging of the islands into a continuous
film. Deposition of alkali halides, metals on insulators show this type of mechanism.
Normally it is a slow diffusion process. In layer by layer growth film atoms are more
bound to substrate rather than each other. First a complete monolayer is formed
and then the second layer begins. It is a fast diffusion processes and results in high
crystalline quality. In mixed growth, initially film growth takes place as per layer by
layer model and then it forms three dimensional islands.
The techniques of thin film deposition are often classified into three main
categories namely.

1. Physical deposition (e.g., chemical vapor deposition, thermal evaporation,

molecular beam epitaxy, sputtering, atomic layer deposition, etc.) and
2. Chemical deposition (electro chemical deposition, Langmuir–Blodgett films
and self-assembled monolayers) and
3. Organic monolayers

The sub-classifications of the techniques are given in Table 3.1.

84 K. R. Sinju et al.

Table 3.1 Sub classifications of the thin film deposition techniques

Physical deposition Chemical deposition Organic monolayers
• Evaporation technique • Sol—gel technique • Langmuir-
– Vacuum thermal • Chemical bath deposition Blodgett
evaporation • Spray pyrolysis • Self assembly
– Electron beam evaporation • Plating
– Laser beam evaporation – Electro plating
– Arc evaporation – Electroless deposition
– Molecular beam epitaxy • Chemical vapor deposition(CVD)
– Ion plating evaporation • Low pressure chemical vapor
• Sputtering technique deposition(LPCVD)
– DC sputtering • Plasma enhanced chemical vapor
– RF sputtering deposition(PECVD)
• Atomic layer deposition(ALD)

3.3 Physical Deposition Techniques

Physical deposition is a purely physical process involving high temperature vacuum

evaporation that is considered as the common/general technique for the thin film
deposition. There are basically three steps involved in the physical vapor deposition
namely evaporation from the source, transport, and condensation of the evaporants
on the substrates. Depending upon the methodology employed for the evaporation
of the material from the source following methods have been adopted; Thermal,
Electron beam, Molecular beam, Laser, or Sputtering.

3.3.1 Thermal Evaporation

The technique involves vaporization of the source material at an elevated temperature

under controlled conditions, such as pressure, substrate temperature, and quantity of
material, to form thin film with desired thickness. The material vapor condenses
in the form of thin film on the substrate surfaces kept in vacuum at a pressure of
~10–6 torr. At this pressure, the mean free path of the vapor atom is nearly similar
to vacuum chamber dimension implying that the particles travel in straight line from
the evaporation source to substrate. The average energy of the vapor atoms reaching
on the substrates is low, ~few tens of eV, and has a strong effect on the adhesion and
morphology of the resulting film. Here, source of material has to be taken in metal
boats, filaments, etc. Generally Tungston (W), Tantalum (Ta), and Molybdenum
(Mo) are used as heating resistance materials which have been attributed to their
high melting points of 3380, 3000, and 2620 °C, respectively. The vapor pressure at
the evaporation temperature (1000–2000 °C) comes to zero. The resistance heated
evaporation has some unique features over the other thin film deposition methods,
such as
3 Techniques for Thin Films of Advanced Materials 85

• Simple, robust, and in widespread use

• Can be used for pure atomic elements including both metals and non-metals.
• There is a wide choice for substrates such as semiconductor wafers, solar cells,
and optical components.
• Process is carried out in high vacuum and therefore could be used to achieve films
with high purity.
• Higher deposition rate such as 1000 monolayers per sec can be achieved [19].
• Damage to the substrate during deposition can be minimized.
• The source of material can be solid in any shape or form
• When deposition is not desired, the particular areas can be avoided from the
deposition by suitable masks.
• Common evaporent materials are Au, Ag, Sn, Cr, Sb, Ge, PdS, KCl, and PbCl2 .
The method also has some limitations such as
• Can only achieve the temperature about 1800 °C, hence not possible to deposite
materials with high melting points
• Poor step coverage because of the shadowing effect
• Forming alloys can be difficult
• After deposition post annealing may be required especially for oxide films.
Using this simple method of thin film deposition various advanced functional
materials have been deposited by employing careful choice of process parameters.
For example, Zhang et al. realized high-quality topological insulator Bi2 Se3 thin
film [20]. The precursor powders were evaporated from Mo boat and deposited
on the single crystal Si(100) substrate. Wang et al. reviewed the progression of
fabrication of efficient metal halide based perovskite solar cells (PSC) by thermal
evaporation [21]. Liu et al. has reported dual-cell thermally evaporated PSCs with
high power conversion efficiency (PCE) of 15.4% [22]. Some of the device structure
and performance of PSCs with the perovskite layer deposited by thermal evaporation
method are listed in Table 3.2.
For gas sensing application, using thermal evaporation researchers were able to
fabricate various nano-morphologies with improved response kinetics. For example;
Navale et al. fabricated ZnO hierarchical nanostructures for NO2 gas sensor [27]. In
particular, they could fabricate nanorods and bunch of nanowires on glass substrate by
thermal evaporation method. The chemi-resistive sensor films were able to respond
to the lease quantity such as 1 ppm of NO2 gas at 200 °C. Some of the advanced
metal oxide semiconductor (MOS) films realized using thermal evaporation and their
sensing properties are listed below in Table 3.3.
Another important application is in the field of batteries. In particular, for deposi-
tion of solid electrolyte interface (SEI) coating between the electrolyte solution and
lithium with no direct contact. The formation of SEI using various materials such as
LiF [32], Li3 N [33], Li2 O [34], and carbon based materials [35] has been reported.
Hwan et al. deposited LiF on Li surface by thermal evaporation and demonstrated it to
be best material for protecting the lithium surfaces [36]. LiF’s wide electrochemistry
 86

Table 3.2 Device structure and performance of PSCs with the perovskite layer deposited by thermal evaporation method
Device structure VOC (V) Isc (mA/cm2 ) FF PCE (%) Active area (cm2 ) Refs
FTO/SnO2 /MAPbl3 /spiro-OMeTAD/Au 1.08 19.18 0.738 15.28 0.08 [23]
FTO/C60 /MAPbl3 /CuPc/Au 1.04 18.91 0.7811 15.33 0.08 [24]
ITO/PEDOT:PSS/polyTPD/MAPbl3 /PCBM60 /Au 1.07 17.9 0.57 10.9 0.95 [25]
FTO/TiO2 /CsPblBr2 /Au 0.959 8.7 0.56 4.7 – [26]
Isc —Short circuit current, FF—Fill factor, Voc —Open circuit potential
K. R. Sinju et al.
3 Techniques for Thin Films of Advanced Materials 87

Table 3.3 Advanced MOS films and their sensing properties

MOS Gas Concentration Response time Recovery time Operating Ref
(ppm) (s) (s) Temp. (°C)
SnO2 NO2 1 10 123 200 [28]
CuO H2 S 0.1–0.4 60 90 200 [29]
Fe modified H2 S 10 98 90 225 [30]
SnO2
ZnO modified H2 S 5 6 30 200 [31]
CuO

stability window and negligible solubility in most electrolytes and an ability to regu-
late the surface tension [37] leads to its widespread usage. The most stable cycling
performance was achieved for the cell with 300 nm thick LiF layer. In industrial
application, the thermal evaporation techniques have been widely used. Pan et al.
fabricated Sb2 S3 solar cell with an overall efficiency of 1.76 and used for device
fabrication [38].
More importantly, the technique has also found its utility in the position control
growth of various nanomorphologies like nanorods and nanowires realized using
vapor phase growth [39]. In particular, using thermal evaporation a thin coating of
~5 nm of seed layers (e.g., Au, Ag) has been deposited on to the substrate followed by
annealing that results in the uniform distribution of seed layer on the substrate which
are then subjected to nanowires growth [40–42]. Additionally, this technique is also
used with other approaches like nanosphere lithography and phase shift lithography
to realize accurate position control of the nanostructures [43, 44].
Over all the thermal evaporation method offers advantages over deposition
techniques that includes
• Uniform coating can be realized on the substrate
• Process is solvent free
• Good control over the deposition rates thereby film thickness;
• Simple and easy to operate
• Good quality films having good adhesion to the substrate can be obtained
• Suitable for scale up device fabrication for the industry application.

3.3.2 Electron Beam Evaporation

Electron beam evaporation technique is yet another simple and commonly used
technique for the deposition of thin films. Herein, the intensive beam of electrons
emitted from a filament falls on the target vaporizing it under vacuum environment.
A high difference of potential (kV) is used to accelerate emitted electrons towards
an anode (source of material). A strong magnetic field is often applied to bend and
88 K. R. Sinju et al.

enhance the effective trajectory of the electron beam and allow it to fall on the source
of material. The technique offers some advantages which are listed below
• Electron beam is focused on a specific area on the crucible that allows the control
over the evaporation rate
• High melting point (above 1800–3300 °C) materials can be deposited by e-beam
evaporation.
• Alloys could be congruently deposited i.e., without dissociation of constituent
elements which are suited for reactive evaporation (for oxides, nitrides, etc.)
• Contamination from the crucible is less.
• High quality films can be obtained.
• High deposition rate of 50–500 nm/min.
The technique also has fewer disadvantages like at high energy (>10 keV), the
incident electron beam could cause X-ray emission and importantly the deposition
equipment is costly. Large categories of materials can be prepared by electron beam
evaporation technique such as oxides [45], semiconductors [46], metals and even
molecular materials [47]. The films of advanced materials prepared using e-beam
techniques have found tremendous applications in various fields such as saturable
absorber in Q-switched ytterbium doped fiber laser [48], fuel cell electrodes [49],
solar cells [50], optical, and photoconductive studies [51]. Now, MEMS (micro
electro mechanical systems) technology has been used for the structural and device
fabrication of the devices. It merges at the nano-scale into nano-electromechanical
systems and nanotechnology. Normally, crystalline silicon or polycrystalline thin
films and more recently amorphous silicon (a-silicon) have been used as the struc-
tural material in MEMS applications [52]. E-beam evaporation is a good choice for
formation of a-silicon thin films for MEMS applications. Michael et al. studied the
a-silicon thick film (>10 μm and ultra-smooth) deposited by e-beam evaporation
for MEMS application [53]. Joseph et al. have demonstrated the applicability of
ultra-smooth a-silicon thin film (<500 nm) in MEMS applications [54]. The inherent
tensile stress is found to be doubled, and surface roughness is found to be reduced.
Thus, a-Si thin film deposited by e-beam evaporated is demonstrated to be a potential
candidate for low thermal budget MEMS applications.
E-beam technique has also been found useful for several bio-applications. For
example, Gnanavel and his co-workers [55] have demonstrated that the HA (hydrox-
yapatite) films deposited by e-beam evaporation on bio inert metal namely Ti-13Nb-
13Zr (near β titanium alloy) exhibited excellent bioactivity. This work is of particular
significance and desired to realize HA ceramics bone implants. For other application
like corrosion resistance novel compositions were realized using e-beam method
viz., TiO2 , Ti0.41 W0.59 Ox [56, 57]. Other interesting applications of e-beam is in the
development of electrochromic (EC) materials. In EC materials application of a small
voltage causes a significant variation of the optical state (darkness/lighten). Accord-
ingly, they have found promising relevance’s in the field of antiglare automobile rear-
view mirrors, optical displays, energy efficient smart windows, etc. [58–60]. Tung-
sten oxide (WO2 ) is one of the smart materials among the electrochromic materials
that has high coloration efficiency, stability, and contrast ratio along with low power
3 Techniques for Thin Films of Advanced Materials 89

consumption and excellent memory effects [61, 62]. Eevecan et al. fabricated tung-
sten oxide thin films using e-beam evaporation that exhibited good electrochromic
properties for use in electrochromic devices. Karaca et al. [63] have found that
the inclusion of gold/poly (3,4-ethylenedioxythiophene)/platinum (Au/PEDOT/Pt)
microtubes into WO3 resulted in an increase in optical modulation by 26% with
improved response times (tb : 13.83 and tc :19.25 s) and electrochromic stability.
Although e-beam is considered to be a good approach for the synthesis of metal
and alloy coatings, it is not good for ceramics due to charge build up on the ceramic
target. Accordingly, for deposition of ceramics usually sputtering techniques have
been employed. However, this technique itself is very expensive and needs high
vacuum environment. Because of their resistance to mechanical shock ceramic
oxides, nitrides and carbides (e.g. BeO, Al2 O3, AlN, SiC/Si) are attractive for applica-
tion in protective coating materials [64]. Using e-beam evaporation Yushkov and co-
workers were able to deposit alumina coating on using a fore vacuum plasma cathode
electron source [65]. Ceramic is a dielectric (insulating) material, and during the
deposition process, the negative charged electrons gets accumulated on the ceramic
surface giving it a high negative potential. This causes electron beam to reflect and
deflect, consequently no further deposition could take place. The solution to this
problem could be provided by the fore vacuum pressure plasma cathode electron
beam source. Electron beam generated by this kind of source, typically of energy
up to 20 keV, current upto 1A, and under residual gas pressure of ~75 mTorr could
lead to plasma that provides excellent neutralization of the electronic charge accu-
mulated on the ceramic surface. As a result, a good functional ceramic coating of
alumina from its bulk alumina ceramic is obtained. Importantly, the ceramic target
material evaporation rate was found to be up to 4.2 g/h, which is high as compared to
other vacuum coating methods. The film deposition rates of ~18 μm/h could also be
achieved [66]. The e-beam method offers several advantages over other techniques
such as high material utilization efficiency, good control over evaporation rate, possi-
bility of depositing high melting point (above 1800 °C) materials, and alloys without
dissociation of constituent elements.

3.3.3 Laser Beam Evaporation (Pulsed-Laser Deposition)

Pulsed-laser deposition (PLD) is another technique that allows the stoichiometric

transfer of complex materials such as YBiO3 and Ag2 S3 onto the substrates [67]. The
laser ablation method allows good control over films thickness and could be used
effectively to obtain films of easily decomposable compounds or nano-layered struc-
tures [68]. In this technique, the ablation of the material to be deposited is achieved
employing high power pulsed laser beam that is focused on the target. The target is to
be melted, evaporated, and ionized by high power laser beam. Different laser sources
are being used to ablate the target material, and the most common laser sources are
Nd-YAG laser, KrF (248 nm), and XeCl (308 nm). When the laser beam strikes the
target material, it produces the plume which could deposit on various substrates. The
90 K. R. Sinju et al.

created plume may contain neural- and ground-state atoms and ionized species. The
deposition can be carried out in ultrahigh vacuum or background gas like oxygen or
nitrogen [69]. The film quality is governed by various process parameters such as
laser wavelength, pulsed duration, repetition rate energy, ambient gas pressure, and
substrate temperature [70, 71]. The technique has some advantages over the other
physical deposition systems because of its fast deposition rates and capability to
grow films under oxygen or other environments. Some of the advantages are listed
below
• Material displaced is deposited onto the substrate without decomposition
• This method is highly preferred when complex stoichiometries are required.
• High quality of thin films
• Ease of operation and reproducibility
• Films do not required post-deposition annealing.
The technique also suffers from drawbacks like the target is ablated to form
“chunks” and thus the main challenge is to minimize the chunkse-beam evaporation.
PLD has been demonstrated a good technique to control the surface polarity of
the ZnO films [72]. Surface polarity has a strong influence on the material prop-
erties especially the optoelectronic and chemical properties [73]. The thickness of
MgO layer can be tuned to get the different polarity of ZnO surface. In partic-
ular, for MgO thicknesses <2 nm and >3 nm results in O-polar and Zn-terminated
polar surface respectively. PLD has been effectively used to realize novel nanomate-
rials like CuSbS2 , [74] multi-walled carbon nanotubes (MWCNTs) decorated CdO
nanoparticles, [75] and Au NPs in TiO2 [76].

3.3.4 Epitaxial Growth Techniques

Epitaxial growth technique have been largely used in the fabrication of electronic
circuits which is attributed to the compositional uniformity, good control, and under-
standing of the growth parameters. Several epitaxial techniques have been used for the
growth of epilayers of III-V, II-IV compound semiconductors, and other materials.
The most commonly used among them are liquid phase epitaxy (LPE), vapor phase
epitaxy (VPE), molecular beam epitaxy (MBE), chemical beam epitaxy (CBE), and
atomic layer epitaxy (ALE).

3.3.4.1 Liquid Phase Epitaxy

LPE is an excellent method to realize thin layers of group III-V, II-IV, and IV-VI
compounds [77]. This method is flexible for device applications and in the fabri-
cation of the device structures such as hetrostructure laser diodes, gundiodes, pin-
photodiodes, avalanche photodiodes, integrated bipolar transister laser circuits, and
3 Techniques for Thin Films of Advanced Materials 91

rare earth doped injection lasers. In LPE, the films usually grow from metallic solu-
tions onto a crystalline substrate. The solvent contains a small quantity of solute
example, as in Ga for epitaxial growth of GaAs layers which is transported towards
the liquid–solid interface. There are three kinds of LPE growth techniques: tipping,
dippind, and sliding. In tipping techniques, the substrate is placed tightly at the upper
end of a graphite boat while the growth solution is placed at the lower end. Tipping
of the substrate is performed to bring the solution into contact. The furnace is then
slowly cooled, and an epitaxial layer is grown on the substrate. The growth is termi-
nated by tipping the furnace back to its original position. The solution remains on
the film surface is removed by wiping and dissolving in a suitable solvent. The appa-
ratus used for tipping and dipping techniques is very simple and easy to operate.
For multilayers growth, sliding technique using multi bin graphite boat is used. The
growth is usually carried out in an atmosphere of hydrogen.

3.3.4.2 Vapor Phase Epitaxy

VPE is a technique used for the growth of III-V compound semiconductors. As the
name indicates vapor phase epitaxy, the growth is carried out by vapourizing the
source material. Inorganic or organic materials which reacts with the other materials
to form the compound semiconductors on the substrate. Growth is controlled by the
partial pressures of each of the components of the source materials. There are two
different forms of vapor phase epitaxy growth (i) chloride VPE and (ii) hydride VPE.
In chloride VPE, GaAs has been grown successfully using an AsCl3 -Ga-H2 system
and PCl3 -In-H2 system has been used to grow InP. The advantages of trichloride VPE
arises from the fact that AsCl3 and PCl3 can be distilled into very pure liquids and the
fact that AsH3 , and PH3 are not used. In hydride VPE, the growth of GaAsP was first
demonstrated using the group V hydride arsine (AsH3 ) and phosphine (PH3 ). These
are added to gas flows containing the group III metal chlorides and or InCl which
are formed by reaction of HCl gas with liquid Ga and In sources. Both the source
reactions and the deposition reactions are done inside a hot walled quartz reactor.
The major advantages of hydride VPE are that epitaxial growth on large wafers and
on multiple wafers is possible simultaneously.

3.3.4.3 Molecular Beam Epitxy (MBE)

MBE is a technique that is used for the deposition of thin film compound semicon-
ductrors, metals, and insulators. It is a mono crystal film growth technique and a
commercial production technique for compound semiconductor materials such as
GaAs. In MBE, beams of atoms and molecules direct on to a crystal surface. It
works under ultrahigh vacuum and hence produced extremely pure material film.
The beam pressure is extremely low that the molecular flow regime is maintained,
and the incident fluxes can be controlled rapidly and efficiently by simple shutters
or needle valves. The evaporated elements (atoms/molecules) travel straight to the
92 K. R. Sinju et al.

substrate without interacting with each other or the gases present in the chamber.
This is because of their long mean free path involved in the deposition process.
Under appropriate conditions of beam flux and substrate temperature, epitaxial film
is formed. This technique is widely used to produce superlattice structures having
multilayer with single layer thickness of ~10 Å.
Recently semiconductor/superconductor hybrids have gained a great attention
wherein the interface governs the induced superconducting gap. Krogstrup et al. have
studied the epitaxial growth of semiconductor–metal core–shell nanowires [78]. They
demonstrated a new route for controlled electrical contacts to nanostructures enabling
device designing for topological and gate-controlled superconducting electronics.
Their choice of material was epitaxial InAs/Al grown with single-plane interfaces. At
the boundaries of different topologies, quasiparticles have been found to exist. Such
quasiparticles—“Majorana modes”—can be formed in semiconductors nanowires
(NWs) coupled to conventional superconductors. So far, conventional methods have
shown some unexpected low-energy states below the proximity-induced supercon-
ducting gap. The disorder in the semiconductor/superconductor (SE/SU) interface is
attributed to be the source of such soft gap. The device performance has also been
found to increase together with interface quality. Kronstrup et al. have studied the
electrical properties of Al/InAs hybrid. To investigate the superconducting proper-
ties of the Al film, four terminal devices were fabricated on a 90 nm diameter with
a 13 nm full shell, as illustrated in Fig. 3.1a,b. Figure 3.1c depicts the temperature
dependence of the four-terminal resistance.
The Al shell has a normal state resistance of ~50  for temperature above 1.6 k,
showing a gradual transition to the superconducting zero-resistance state, which is

Fig. 3.1 A schematic illustration of the four-terminal device made from a full-shell Al/InAs
nanowire with a 13 nm thickness of Al, b SEM image of the device, and c measurement of four-
terminal resistance as a function of magnetic field. Reprinted with permission from P. Krogstrup
et al., Nature Mater. 14 (2015) 400–406, Copyright © 2015 Springer Nature Publishing AG [78]
3 Techniques for Thin Films of Advanced Materials 93

fully developed by 1.3 K. For temperature below the superconducting transition, Al

induces superconducting gap into the InAs by virtue of proximity effect.
MBE has also been demonstrated as a tool to grow catalyst-free nanostruc-
tures. For example, Tchoe et al. demonstrated a catalyst free growth of coaxial
nanorod heterostructures of InAs/InGaAs on large-area graphene layers [79]. Inter-
estingly, the nanorods on the graphene exhibited homogeneous composition. They
used combination of the technique namely CVD and MBE for the fabrication of
nanostructures. Graphene has high mechanical strength and flexibility. The large-
area graphene layers were prepared by CVD as a substrate for InAs/InGaAs coaxial
nanorod heterostructures growth.
Among other Group III nitrides, indium nitride (InN) has some promising features
such as excellent electron mobility (4400 cm2 V−1 s−1 at 300 K) [80], small direct band
gap of 0.65 eV [81]. Accordingly, it could be a good candidate for long wavelength
optoelectronic devices like photodiodes, optical sensors, and band solar cells. For the
fabrication of a heterojunction solar cell, the combination of InN with Si can form a
hetrojunction. In order to minimize the resistance between both cells, establishing a
tunnel junction between InN and Si is required. For this a favorable way is to grow InN
directly on Si without any buffer layer which still remains a daunting challenge. Use
of nanowires (NWs) could possibly overcome this problem, as the lattice mismatch
strain can relax through the NW sidewalls because of their small foot-print. Weiszer
et al. have studied the systematic growth of self-assembled and position-controlled
InN nanowires (NWs) on Si (111) substrates by plasma-assisted MBE without using a
buffer layer [82]. For device fabrication, two factors are important (i) growth of NWs
with a defined diameter and length at a specific position in a reproducible way, and
(ii) structures should not suffer from statistical in homogeneities in NW morphology.
Authors achieved this with the help of an additional pre structured Ti-mask on top of
the substrate and is called position-controlled or selective area growth (SAG). For the
nanowire growth substrate temperature, growth time and III/IV flux ratio are found
to be major factors. With substrate temperature of 480 °C, growth time of 90 min,
and III/IV flux ratio of 1:10−3 homogeneous InN NWs with a maximum aspect ratio
were successfully grown.
HgCdTe has been used in IR detectors for a decade attributed to its excellent
performance advantage and technical maturity. The near perfect lattice match with
HgCdTe makes Cd0.96 Zn0.04 Te (CZT) ideal substrates for fabricating high perfor-
mance infrared focal plane arrays (IRFPAs). However, low mechanical strength and
thermal conductivity, high cost, and poor quality pose serious limitations [83]. Gu
et al. have demonstrated alternative substrate namely GaSb for epitaxial growth of
HgCdTe films with lower Etch Pit Density (EPD) and higher minority carrier lifetime
than other conventional substrates.
Tanaka et al. have studied photoluminescence (PL) of ZnTe/ZnMgTe multiple
quantum well structures (MQW) deposited on ZnTe [84]. PL properties of MQW
structures strongly depend on the well widths and Mg content in the barrier layer
as they affect the quantum energy levels formed in the ZnTe well layer and the
crystallinity of epilayers. In ZnTe/ZnMgTe MQWs, it was found that a carrier escape
out of the ZnTe quantum well is a dominant origin for thermal quenching and the
94 K. R. Sinju et al.

design of QW structures with a higher barrier was found to be crucial to obtain

PL at higher temperature. The MQW structures with an adequate well width and
Mg content showed PL at room temperature, which demonstrate a potential for
pure-green LEDs.
All the above studies clearly indicates that MBE is a versatile technique among
the other deposition technique. However, one has to keep in mind that being a slow
process it may not be useful for mass production in industrial applications.

3.3.5 Sputtering

Sputtering technique is mostly used for depositing metal and oxide films by control-
ling the crystalline structure and surface roughness. In sputtering, a voltage is
applied between the target material (cathode) and the substrate (anode) placed in
a vacuum chamber. Initially the plasma is created by ionizing a sputtering gas
(Ar) which bombards the target and sputters off the material, which eventually gets
deposited onto the substrates. The sputtering is referred to as the process in which
the momentum transfer between the sputter gases and target atoms causes removal of
material to be deposited. One of the reasons for the popularity of the technique is the
possibility of depositing the materials with very high melting points with a complete
composition transfer from the target. This technique is widely used for depositing
metal and oxide films by controlling the crystalline structure and surface roughness.
One of the important parameter of the process is the sputtering yield ‘S’ which refers
to the number of atoms ejected per incident ion. It takes the values typically in the
range of 0.01 and 4. The yield is a strong function of the target material its mass
and composition, binding energy, sputter power, nature of the incident ion, and the
overall geometry. For accelerating ions the plasma is maintained between target and
substrate. Magnetrons giving very strong electric and magnetic fields are generally
employed to confine plasma close to the target surface and accordingly, the technique
is referred to as the magnetron sputtering. In magnetic field, electrons follow helical
paths increasing the effective electron path length thereby causing more ionization
of the gases. DC power sources are employed for depositing metals and referred to
as DC sputtering herein sputtering target and the substrate are held in parallel plate
configuration. More often RF sources (13.56 MHz) are used to avoid charge build-up
on the insulating targets and is referred to as RF sputtering. The quality of the films
is easily controllable by careful choice of process parameters namely base vacuum,
sputter gas and its pressure, sputter power, target, and substrate temperature [85].
This technique is a good choice for the synthesis of advanced materials. These
days, supercapacitors have been developed for the applications in electronic devices,
portable power sources, and electric vehicles. They offer the advantages of high
charging and discharging efficiency, long cycle life time than that of batteries, high
power density, and low sensitivity to temperature. Some of the active materials for
supercapacitors includes carbon materials [86, 87], metals oxides like MnOx , NiO,
RuO2 , and Co3 O4 [88–91]. Among these active advanced materials, a manganese
3 Techniques for Thin Films of Advanced Materials 95

oxide (MnO2 ) is found to be promising electrodes in supercapacitors (SC) [92].

The research has thus focused on one dimensional (1-D), two-dimensional (2-D)
metal oxide nano-structured materials, which can have superior electro chemical
performance [93]. MnO3 has high theoretical specific capacitance (CSP ~1370 F/g),
easy preparation, low toxicity, and low cost. The electrochemical properties of SCs
depend on the morphology and structure of the active material, electrical contact with
current collectors, amounts of cations, and exposed surface area. For 1-D nanostruc-
tured morphologies such as nanorods, nanowires, and nanoflakes, the sufficiently
high surface area and shorter diffusion paths for electron/ion transfer helps to realize
high capacitance [94, 95]. Fabrication of such a nanostructure has been developed
by many methods such as sol–gel, electrochemical deposition, chemical reduction,
thermal decomposition, and precipitation with use of polymer binders and additives
[96, 97]. These binders and additive fused with active materials and reduced the
capacitance of super capacitor [98]. This implies that an effective way to fabricate
binder free, low cost, high quality, and contamination free nanostructure is employing
PVD techniques, particularly sputtering.
Recently, transition metal nitrides, such as VN, Mo2 N, TiN, CrN, and NbN, based
supercapacitors have been studied [99–103]. Prakash et al. have studied the tungsten
nitride thin film electrode deposited by reactive sputtering for supercapacitor devices
[104]. Among various transition metal nitrides, tungsten nitrides (W2 N) are more
attractive for SCs because of tunable electrical conductivity, high melting point, and
excellent chemical and thermal stability with superior mechanical properties.
Other advanced materials are thermoelectric materials that have gained tremen-
dous attraction. These are the materials that converts waste heat into electricity
directly and reversibly employing Seebeck and Peltier effects and accordingly have
promising applications in power generation and cooling [105, 106]. Somdock et al.
studied the bismuth telluride (Bi2 Te3 ) compound for thermoelectric application
[107]. Bi2 Te3 is an anisotropic material wherein the material property varies with
structure and orientation. Somdock et al. have synthesized Bi2 Te3 film on the (00l)
plane wherein the thermo electric properties were found dependent on the orientation
of (00l) plane and chemical composition. Among the deposition techniques sputtering
is a good option for the highly oriented (00l) seed layer and stoichiometric thin film
of Bi2 Te3 . In order to get the preferred orientation plane the substrate temperature
plays a key role. Le et al. found out that the film with preferred orientation of (00l)
layers having lowest surface energy can be achieved in the temperature range of
220–380 °C [108]. Nuthongkum et al. found out that the working pressure plays a
significant role for composition control and improve thermoelectric properties of Bi-
Te thin film [109]. The thermoelectric properties of the Bi2 Te3 thin films fabricated
by sputtering have been compared in Table 3.4.
Orientation of bismuth telluride thin film, carrier concentration (n), electrical
conductivity (σ), carrier mobility (μ), and power factor (PF).
Another application of sputtering technique is in the fabrication of electrochromic
devices. Gomes et al. have reported indium-zinc oxide (IZO) film deposition with
a ceramic IZO target onto using RF and DC sputtering [113]. Further, Gomes et al.
reported that IZO films could be achieved possessing low sheet resistance (‘20 /sq)
96 K. R. Sinju et al.

Table 3.4 Thermoelectric properties of the Bi2 Te3 thin films fabricated by sputtering
Sample Orientation n (cm−3 ) × σ (s/cm) S (μV/K) μ (cm2 /Vs) PF (W/Mk2) Refs.
1020
Bi2 Te3 (00l) 7.87 14.9 −76 118.0 8.62 × 10–3 –
(00l) + (015) 1.3 952.4 −55 45 2.75 × 10–4 [110]
(00l) + (015) 0.51 549.5 −128 67.2 9 × 10–4 [111]
(00l) + (015) 6.94 710 −75 6.39 4× 10–4 [112]

and 80% optical transmittance in visible part of the spectrum and the electrical
stability above eight months. Baptista et al. have reviewed about the evolution of
magnetron sputtering process for industrial applications [114]. PVD processes have
the higher energy consumption as compared to that of CVD processes. The DC
source is the most commonly used source in magnetron sputtering. The combination
of RF and MF (microwave frequency) sources led to a new technique namely Dual
Anode Sputtering (DAS) with reduced heat load in the substrate.

3.4 Chemical Techniques for Thin Film Deposition

This refers to the technique that involves use of chemicals or solution to realize the
thin films. In particular, at a solid surface the fluid precursor undergoes a chemical
change leaving a solid layer. This type of techniques have attracted much attention
owing to numerous advantages that includes low cost, ease of synthesis, and potential
for scale up for commercial deployability. Depending upon the phase of the precursor,
the technique is further classified into following techniques.

3.4.1 Sol–Gel Method

Sol–gel process refers to a method for material synthesis from solutions, in which
there is a change from a liquid state to a gel state through polycondensation reaction.
A sol is a stable dispersion of colloidal particles or polymers in a solvent. A gel
consists of a 3-D continuous network of the sol particles, which encloses a liquid
phase [115].
Bahuguna et al. reviewed about the sol–gel techniques for the thin film growth.
There are several advantages of a sol–gel method over the other thin film deposition
methods [116]. These include significant ease of coating the complex shapes, cost
effective owing to the requirement of smaller quantities of the material. Importantly,
the process is feasible at room temperature with possibility of getting the desired
morphology careful choice of the reaction condition. This method also has fewer
drawbacks like gel drying, extreme volume shrinkage during gelation, removal of
3 Techniques for Thin Films of Advanced Materials 97

Table 3.5 List of materials, nanostructure grown by sol–gel method, and their applications
Material Nanostructure Applications Refs.
b/Tourmaline/TiO2 Nanotubes Photocatalysis [117]
Silver doped titanium oxide Thin film Gas sensing [118]
Yttrium iron garnet (YIG) Thin film Spintronics [119]
Erdoped SnO2 Nanoparticles Photoluminescence [120]
Sr2 Bi4 Ti5 O18 (SBTi) and Nd-modified SBTi Thin film Ferroelectrics [121]
(SBNT)

the redundant residuals, and the occurrence of pores. Leitzke et al. described the
low temperature and cost effective synthesis of amorphous WO3 films on ITO/PET
flexible substrate [117] to be used as a working electrodes in flexible electrochromic
devices. Table 3.5 provides examples of material with nanostructure and applications.

3.4.2 Spray Pyrolysis

Spray pyrolysis is another approachable technique for the thin film deposition. Herein
the thin film is deposited by spraying a solution onto a hot surface facilitating the reac-
tion of the constituents forming a chemical compound to be deposited. The chemical
reactants are so chosen that the undesired products are volatile and automatically do
not form the part of the film composition. Generally, it forms an aerosol droplets
comprising of metallic salts solution or colloidal solution which are consequently
heated in a furnace (thermolysis) wherein they undergo to different stages before
forming a thin film. First, microporous particles with defined phase composition
are formed, followed by formation of solid particles, and finally sintering of these
particles to form a thin film coating on the substrate.
The technique offers numerous advantages over other synthetic techniques. First,
it has simple equipment so it is easy to handle. Secondly, it does not require
high-quality reagents or compositions. By varying the chemical conditions, addi-
tives, concentration of the precursors, it is possible to get a good control over the
morphology and size of resulting particles. It has some disadvantages also that include
possibility of the oxidation of the reactants and difficulty for scale-up. However,
the technique has demonstrated good potential to realize novel advanced materials
for applications in the field of superconductor powders, multicomponent ceramics,
catalysts, electrode materials, energy storage, and conversion. For example, Yoon
et al. have reported a facile one-pot spray pyrolysis method for the preparation of
SnO2 spheres having 3-D interconnected and size-tunable trimodal (micro-, meso,
and macro-scale) pores [122]. This was achieved by employing sacrificial templates
of macroscale polystyrene spheres and mesoscale-diameter long carbon nanotubes
(CNTs). Figure 3.2 shows the schematics of the process for the formation of SnO2
nanospheres with trimodal porosity [123]. The resultant spheres with different modal
98 K. R. Sinju et al.

Fig. 3.2 Schematic representation of the steps involved in the formation of SnO2 nanospheres with
trimodal (3 M) porosity. d Dynamic gas-sensing transients of the 3 M-SnO2 spheres to 0.25–5 ppm
of ethanol at 400 °C. Reprinted with permission from J.-W. Yoon et al. NPG Asia Materials 8(2016)
e244. Copyright © 2016 Springer Nature Publishing AG [123]

pores (sizes ~3, 20, and 100 nm) have shown unprecedentedly high response to ppb
levels of ethanol (Fig. 3.2). From the figure, it is evident that the SnO2 spheres with
trimodal porosity exhibited remarkable sensor response towards ethanol.
Another interesting application of the spray pyrolysis method has been found in
the development of anode materials for application in lithium ion batteries (LIBs).
Park et al. have investigated cobalt hydroxychloride [Co2 (OH)3 Cl] as anode material
for LIBs [124]. For this, the cobalt chloride salt solution was spray coated during
which ultrafine nanocrystals with spherical geometry were formed. The Co2 (OH)3 Cl
powder exhibited high thermal stability below 220 °C and superior electrochemical
properties than CoCl2 : (H2 O)2 and CoO deposited using the similar process. Supe-
rior electrochemical properties are attributed to the spherical shape of Co2 (OH)3 Cl
powders. In particular, the discharge capacity of bare Co2 (OH)3 Cl powders is found
improved. Besides, it acts as a buffer layer for large volume changes during cycling.
Very recently, Leng et al. have critically reviewed spray pyrolysis as a versa-
tile synthetic technology to realize powdered materials and thin films for potential
application in energy storage and conversion [125]. As shown in Fig. 3.3, using
3 Techniques for Thin Films of Advanced Materials 99

Fig. 3.3 Different nanostructures designed by spray pyrolysis. Reprinted with permission from J.
S. Cho et al. Nano Energy, 2016, 26, 466–478. Copyright © 2016, Elsevier [126]

spray pyrolysis different nanostructured products like hollow or dense spheres, yolk–
shell, or core–shell structures, composite materials and thin films were successfully
synthesized [126].

3.4.3 Chemical Bath Deposition (CBD)

Chemical bath deposition (CBD) technique is a well-suited technique to produce thin

films for large area applications. It involves mainly two steps, nucleation and growth.
In this technique, the substrate to be deposited is generally immersed in a solu-
tion containing the precursors. Accordingly, the choice of substrate and the solution
parameters like composition, temperature and duration, are found to play a crucial
role in determining the quality of the thin film. Importantly, CBD is known to give
well adherent, stable, and uniform coatings on the substrates. Kim et al. have studied
the hierarchical interconnected nickel cobalt sulfide (NiCo2 S4 ) nanosheets deposited
on a flexible stainless steel foil [127]. These interconnected NiCo2 S4 nanosheets as
electrodes have shown a specific capacitance of 1155 F/g at 10 mV/s with superior
cycling stability retaining 95% of capacity up to 2000 cycles. Guo et al. studied the
coercivity enhancement of sintered Nd-FeB magnets realized by CBD of TbCl3 . The
coercivity was observed to increase from 11.89 to 14.72 kOe without any reduction
100 K. R. Sinju et al.

of reminiscence and excellent thermal stability [128]. This coercivity enhancement

is attributed to the formation of a core–shell structure with the (Pr, Nd, Tb)2 Fe14 B
phase surrounding the (PrNd)2 Fe14 B phase.

3.4.4 Chemical Vapor Deposition (CVD)

Chemical vapor deposition (CVD) as the name suggest is a process in which the
chemical interaction takes place between the precursors molecules in the vapor phase
and the corresponding product as solid material gets deposited as thin film or collected
in powder form. The process is often carried out inside a flow reactor wherein the
precursors are activated (thermal, photo, or plasma energy) leading to deposition on
the substrate surface to produce the desired film. This process has been adapted in
the semiconductor industry especially for the fabrication of device and importantly
for protective coatings on precision machine parts.
Metal organic frame works (MOFs) are class of compounds that comprises metal
ions or clusters coordinated to organic ligands to give 1-, 2-, and 3-D structures that are
often porous. They have disruptive potential in microelectronics. Suitable film depo-
sition methods are crucial for MOFs. The films fabricated by solvent based processes
often face corrosion and contamination risks. Stassen et al. demonstrated CVD
process to achieve high quality zeolitic imidazolate framework films of ZIF-8, with a
uniform and controlled thickness, even on high-aspect ratio features [129]. Later
MOF-CVD integrated on microelectronics devices by lithography. Solvothermal
transformation of metal oxides to generate 2-D and 3-D MOF patterns have also
been studied extensively [130, 131]. Formation of pinholes, rough films, and homo-
geneous nucleation in solution faced risk by solvothermal method. Stassen et al.
demonstrated that these problems could be avoided by employing combined MOF-
CVD approach wherein the organic linker is supplied as a vapor instead of in-solution.
Figure 3.4 shows the SEM image of the deposited zif-8-coated silicon pillar array

Fig. 3.4 SEM image of a ZIF-8-coated silicon pillar array, b MOF-CVD coated PDMS pillars, and
c identical PDMS pillars after conventional processing of ZIF-8. Reprinted with permission from I.
Stassen et al. Nature Mater. 15(2016)304–310 Copyright © 2016 Springer Nature Publishing AG
[129]
3 Techniques for Thin Films of Advanced Materials 101

Fig. 3.5 Description of the flame vapor deposition process. a Schematic, b photograph of flame
vapor deposition setup, and c photograph of metal foil substrate with dark blue deposit consisting
of Mo17 O47 nanowire-arrays. Reprinted with permission from Allen et al. Nature Sci. Rep.6 (2016)
27,832. Copyright © 2016 Springer Nature Publishing AG [132]

exhibiting a homogeneous coverage of pillars, MOF-CVD coated PDMS pillars and

identical PDMS pillars after conventional processing of ZIF-8.
Mo17 O47 nanowires as active materials are employed as conductive supports for
batteries and related applications. Generally, Mo17 O47 nanowires are synthesized by
electrically-heated CVD under vacuum conditions. Allen et al. demonstrated an alter-
native way based rapid atmospheric flame vapor deposition (FVD) to grow Mo17 O47
nanowire-arrays on metal foil substrates. The nanowires could be obtained with faster
growth rate and were of high-purity, thinner, longer, and densely packed [132]. The
FVD synthesis conducted at atmospheric pressure in the flow of hot gaseous combus-
tion products from a flat CH4 -air flame with no enclosing walls or chamber as shown
schematically in Fig. 3.5. The synthesis relies on the flame to provide the heat and
oxidizing gases required to evaporate and degenerate molybdenum oxide vapors from
a solid molybdenum source that is placed above the flame. The vapors then deposit
onto a substrate.
As compared to electrically-heated vacuum deposition methods, FVD synthesis
allows the total concentration of MoOx vapors to be larger, resulting in denser nucle-
ation of nanowires with smaller diameters, and faster axial growth rates thereby
assuring higher aspect ratio and surface area. In addition, a benefit of this approach
is that the partial pressure of oxygen in the synthesis environment can be directly
controlled over many orders of magnitude through control over the ratio of CH4
(fuel) and air (oxidizer) supplied to the flame. The FVD method can be scaled up
for large-scale area deposition on to substrate, and the atmospheric operation of the
FVD synthesis is less energy-intensive than maintaining a vacuum.
Liu et al. have demonstrated the vapor–solid growth of Mox W1-x Te2 nanobelts
by facile CVD method [133]. They adopted one-step CVD method, in which Mo
(W) and Te precursor are both evaporated during the heating, transported by carrier
gas, deposited on the substrate, and reacting with each other finally. In general, there
102 K. R. Sinju et al.

are two proposed mechanisms for the growth of nanobelts, including the vapor–
liquid-solid (VLS) and vapor–solid (VS) growth, respectively. In general, the CVD
process begins with the vapor precursors and ends with solid products, and there is
no liquid involved in the growth. For a typical VS growth, the solid is evaporated at
high temperature, transported by carrier gas, and deposited on the substrate at lower
temperature. For this reason Liu et al. said that Mox W1-x Te2 nanobelts are governed
by VS mechanism. They emphasized that the H2 carrier gas played a significant role
for the nanobelt growth.
Zhang et al. demonstrated highly ordered arrays of WS2 grown by low pressure
CVD (LPCVD) [134]. Figure 3.6 shows the LPCVD synthesis of WS2 on sapphire
grown with jagged edges under pure Ar gas flow and flakes synthesized under mix
Ar and H2 flow [135].
Some of the advantages of CVD are listed below.
• High growth rates
• Possible to deposit materials which are otherwise hard to evaporate
• High reproducibility
• Epitaxial growth of films
• Formation of films at low-temperature.

Fig. 3.6 LPCVD synthesis of WS2 on sapphire. a Schematics of the chemical reaction, b Experi-
mental setup, c, d, e SEM images of jagged edge WS2 flakes. f Corresponding AFM characterization
of the monolayer nature. g, h, i SEM images of WS2 flakes, j Photograph of bare sapphire and mono-
layer as-grown WS2 . Reprinted with permission from Zhang et al. ACS Nano. 7 (2013)8963–8971,
Copyright © 2019 American Chemical Society [135]
3 Techniques for Thin Films of Advanced Materials 103

CVD also suffers from some of the disadvantages as listed below.

• Not possible for some materials for which no suitable chemical reactions are
known
• Not suitable for complex materials also.

3.4.5 Atomic Layer Deposition

Atomic layer deposition (ALD) is a sub-class of CVD and considered to be an

advanced deposition technique that employs sequential gas phase chemical processes
to realize thin films [136]. Most common ALD processes involves two chemicals
called precursors which reacts with the material surface in a sequential and self-
limiting manner [137]. A thin film with atomic scale accuracy gets formed on the
surface slowly via repeated and sequential exposure to the precursors. A single expo-
sure to all of the precursors is referred to as ALD cycle and the maximum amount of
material deposited, i.e., growth per cycle is governed by precursor-surface interac-
tions. The thickness of the material on any arbitrarily complex and large substrates
can easily be controlled by careful choice of ALD cycles. The rate of adsorption (R)
per unit of surface area is directly proportional to the sticking probability (S), and
the incident molar flux (F) given as follows:

R = S ∗ F. (3.1)

Herein, S changes continuously reaching to zero at saturation. Depending upon

the nature of adsorption and reaction mechanism involved, ALD are often classi-
fied into but not limited to Thermal, Plasma, Photoassisted, Catalytic, and Metal
(elimination) ALD processes. The technique has been widely exploited for polymer
surface functionalization, catalytic surfaces, MOS devices, formation of composite
structures, and advanced nano morphologies [138, 139]. Using ALD it is possible
to grow films to an atomically specified thickness and even multilayer structures.
Additionally, it typically involves relatively low temperatures which is advantageous
for soft substrates, such as organic and/or biological samples and a catalyst, which
is thermochemically favored [140].
Zacharias et al. have demonstrated growth of ultra-long single-crystal ZnAl2 O4
spinel nanotubes using the Kirkendall effect [141]. In particular, they demonstrate
the transformation of nanowires into nanotubes using interfacial solid-state reaction
of core–shell ZnO–Al2 O3 nanowires. For this pre-synthesized ZnO nanowires were
coated with a alumina layer (10 nm) using ALD at 200 °C followed by annealing at
700 °C in air for 3 h. The high temperature annealing results in interfacial solid-state
reaction or kirkendall effect and subsequent diffusion. Employing similar process
various nanotubes and hollow nanoparticles have been synthesised [142]. It has been
demonstrated that using the ALD along with the kirkendall effect it is possible to
introduce superior functionality by design. For example, Guder et al. have shown the
104 K. R. Sinju et al.

successful conversion of smooth nonpolar ZnO nanowire surfaces to zigzagged high-

index polar surfaces as shown in Fig. 3.7 [143]. The resultant zigzagged nanowires
with inherent defect-rich high-index polar surfaces exhibited a superior ozone sensing
property in particular significantly higher sensitivity (ppb level) as compared to that
of nanowires with smooth surfaces and ZnO–ZnO core–shell nanowires.
Superparamagnetism has found profound applications in the field spintronics and
bio-applications [144, 145]. It is usually observed in small magnetic nanoparticles,
wherein the thermal fluctuations cause magnetization to flip randomly. A transition
from superparamagnetism to ferromagnetism usually takes place when the size of the
particle is increased. Hence, preparation of supermagnetic oxide thin film instead of
nanoparticle is a great challenge. Zhang et al. have successfully synthesized super-
paramagnetic and ferromagnetic Fe3 O4 thin films with angstrom level thickness
control using ALD [146]. These films exhibited a superparamagnetic behavior with
blocking temperature of 210 K which upon post-annealing in H2 /Ar at 400 °C exhib-
ited ferromagnetism. The low-energy growth and self-limiting surface reactions are
ideal for the superparamagnetic film depositions.
The technique was also employed effectively to realize carbon nanotubes (CNT)
forest [147]. CNT forests or fibres were grown using conformal and active cata-
lyst nanoparticles that can be obtained on concave geometries and/or inner surfaces

Fig. 3.7 a Schematic representation of transformation process of smooth nanowires to zigzagged

nanowires. Smooth ZnO nanowires are first coated with thin ZnO layer with subsequent annealling
at 800 °C for 3 h in air. SEM images of b as-grown nanowires; c 5 nm ALD ZnO-coated ZnO
core–shell nanowires; d ZnO nanowires with zigzagged high-index polar surfaces. Reprinted with
permission from F. Güder et al. Small 2012, 8 (21), pp. 3307–3314. Copyright © 2000–2019 by
John Wiley & Sons, Inc [143]
3 Techniques for Thin Films of Advanced Materials 105

Fig. 3.8 SEM cross section image of 3D nanostructure on the glass substrate formed by applying
5 and 450 silica cycles, respectively. Dose time of TDMAS is 20 ms and plasma dose time is 6 s.
Reprinted with permission from M. Zieger et al. Mater. Today Chem. 10 (2018) 112–119. Copyright
© 2019, Elsevier [148]

of porous structures using ALD. Zieger et al. demonstrated a new method to

generate 3D silver-silica nanostructures using plasma-enhanced ALD of silica with
tri(dimethylamino)silane (TDMAS) and oxygen plasma as precursors [148]. For this
method, Ag nanoparticles were used as templates, during the deposition of silica, the
repeatable process of the formation of metastable silver oxides and their decomposi-
tion is involved, leading to strong side reactions and the formation of 3D silver-silica
hybrid-nanostructures as shown in Fig. 3.8. This method is known as metastable
ALD (MS-ALD). The 3D nanostructures have promising applications in the field of
energy harvesting, photo-catalysis, and sensing [149–151].
There are also several disadvantages involved in the use of ALD processes, namely,
high cost of the instrument, relatively slower deposition rates, and chemical limitation
on the substrate to be used. For example, biological substrates cannot be used owing
to there sensitivity towards heat and fast decomposition rates [152].

3.5 Organic Monolayers

This is a novel thin film deposition technique used for realization of organic thin
films onto the substrate using chemisorbed organic molecules [153]. The ease with
which different functional groups can be anchored, and the technique is highly useful
to modify and protect surfaces for desired applications like organic electronic or
bioelectronics, wearable, and smart electronics [154–156]. Depending upon the mode
of transfer or formation of thin films, the technique is further classified into Self-
assembly (SAM) and Langmuir Blodgett (LB) techniques [157].
106 K. R. Sinju et al.

3.5.1 Langmuir–Blodgett Technique (LB)

One of the daunting challenges in materials science is to achieve designer mate-

rials (tailor made) for a specific device application [158]. Langmuir–Blodgett (LB)
technique is a good choice for achieving the goal in engineering the molecules
which would be building blocks in molecular electronics. It allows highly ordered
and ultra-thin growth of organic films. In this method, a one molecule thick layer
(Langmuir monolayer) spread at the air–water interface is transferred onto a solid
substrate by dipping. A multilayer film can easily be obtained by meagre repetition
of the process several times. Herein, first the spreading of insoluble, non-volatile
substances is carried out on the surface of a clean liquid having high surface tension,
e.g., water. This causes the formation of the insoluble monolayer over the surface.
For the molecules possessing a hydrophilic head and a long hydrophobic tail the
spreading occurs when molecules are attracted to the water more than themselves.
When the surface is sufficiently broad to accommodate all the molecules that are
spread, a Langmuir mono layer or one molecule thick film is said to be formed.
These days, researchers are focusing on the single walled carbon nanotubes
(SWCNT) since it has much potential in the field of molecular engineering. The
chirality of SWCNTs is responsible for its semiconducting or metallic characteris-
tics, and accordingly, it becomes challenging to control the electrical property of
SWCNT—based devices (Fig. 3.9). G. H. Nam et al. have studied the modulation of
the semiconducting behavior in the CNT LB films based devices by controlling the
effective channel dimension [159]. The aligned assembly of a monolayer SWCNT
bundle have shown anisotropic electrical properties. In the devices that are formed,
the channel dimensions is demonstrated to govern the gating effects. It was further
shown that a drastic decrease in the metallic pathway thereby enhancing the semi-
conducting behavior can be induced by meagre shrinkage of the channel dimension.
Using LB, it is possible to grow SWCNT film which is uniform, aligned, and with
high packing density.

Fig. 3.9 a SEM image and b Photograph of SWCNT LB film based-devices on 2-inch silicon
wafer. Reprinted with permission from G. H. Nam et al. Appl. Surf. Sci. 481 (2019) 540–544,
Copyright © 2019, Elsevier [159]
3 Techniques for Thin Films of Advanced Materials 107

Ziade et al. have described how the LB technique can be used to experimentally
determine the thermal interface conductance between polymers and solid substrates
[160]. It is a challenge to directly probe the thermal interface conductance between
polymers and inorganic materials due to the low thermal conductivity of most poly-
mers. Thickness of the polymer film is important to isolate the thermal interference
conductance, and it should be in the order of few nanometres. The LB technique
offers a way to repeatedly deposit nanometer-thick films at different phases with
a varying degree of chain ordering [161, 162]. Using LB Ziade et al. have grown
nanometer-thick films of poly(vinyl acetate) (PVAc) on Si and Au substrates in two
distinct states: Liquid condensed (Lc) and Liquid expanded (Le). They used the
frequency domain thermo reflectance for thermal conductivity and thermal interface
conductance measurements. PVAc films exhibited higher thermal conductivity than
bulk and the thermal interface conductance between PVAc and gold, and between
PVAc and silicon, were ~90 and 70 MW/m2 K for both the Le and Lc states, respec-
tively. Moreover, the thermal conductivity of the LB films was up to two times the
value for bulk PVAc, with the Le phase exhibiting higher thermal conductivity than
the Lc phase.
Figure 3.10 shows the total interface conductance (Gmeasured ) as a function of film
thickness for the Lc and Le phases on Si (circles) and Au (squares).

Fig. 3.10 Total interface conductance (Gmeasured ) as a function of film thickness for the Lc and Le
phases on Si (circles) and Au (squares). The solid blue line is the best fit curve to the mean measured
values, while the dashed green lines are the best fit curves for the upper and lower values of the
error bars. Reprinted with permission from E. Ziade et al. Appl. Phys. Lett. 107, 221603 (2015),
Copyright © 2015 AIP Publishing LLC [160]
108 K. R. Sinju et al.

Fig. 3.11 TEM images of gold nanospheres and gold nanorods in LB film. Reprinted with
permission from Y. H. Wu et al. Coll, Surf. A 532(2017) 213–221, Copyright © 2019, Elsevier

Another application of LB techniques is in alignment of technological important

nanomaterials namely gold nanoparticles. The unique physical, chemical, electrical,
and optical properties exhibited by Au nanoparticles have led to their use in indus-
trial and biomedical fields. These nanoparticles can easily be grown into different
shapes and sizes [163–166]. Different methods of synthesis namely laser ablation,
vapor deposition, electrochemical reaction, and chemical reduction have been inves-
tigated to get more characteristic properties. For example; Wu et al. have studied
surface enhanced plasmon effects by gold nanospheres and nanorods in LB films
[167]. Figure 3.11 shows the TEM image of the gold nanoparticles and nanorods
by LB technique. It was found that the film formation using LB raised the red-shift
of a plasmon band of nanorods to ~1000 nm. LB helped to realize high coverage
and particle density that provided larger enhancement factors with a potential for
utilization as photosensitizers and chemo- and biosensors.
LB technique, however, suffers from some demerits like it is a slow process to
fabricate thick film, drying time is required after each layer, mechanical and chemical
stability of the films is rather poor, and it requires a clean room [167].

3.5.2 Self-Assembled Monolayers (SAMs)

Self-assembled monolayers (SAMs) refers to the close-packed 2-D molecular assem-

blies of organic molecules that are formed spontaneously on the surfaces by
chemisorption. Self assembly involves a chemical interaction like covalent bonding
between adsorbed molecules and the surface. The growth of organic SAMs takes
place via the spontaneous adsorption from solution onto the substrates like SiO2 and
metal [168]. Although, being just few nanometers in thickness but they can signif-
icantly maneuver the surface properties. And accordingly, they have been devel-
oped as a powerful molecular platform for interface engineering [169, 170]. SAMs
comprise of three main parts: an anchor or head group, a linker and a terminal group.
3 Techniques for Thin Films of Advanced Materials 109

For example, an α,ω-functionalized alkane, has a head (α) group which is linked
with an alkyl chain to a terminal (ω) group [171]. The head groups usually have a
specific affinity for a substrate that results in selective formation of chemical bonds
with surface atoms of the substrate. Examples include thiolates on gold, silanes on
SiO2 , and phosphonic acids on metal oxides. Owing to inter-chain van der Waals
interactions that becomes stronger with chain length, the alkyl chains play a critical
role in the ordered supramolecular structure formation. The chemical structure of
the terminal/surface or tail group determines the surface properties of the SAMs.
The structure and properties of resulting SAMs are determined from the chemical
composition, monolayer thickness and packing density and molecular ordering and
crystallinity. Moreover these can easily be controlled by chemical modification of
the anchor group, the terminal group and the linker in and variation of the conditions
for adsorption and reaction. Accordingly, they have found application in various
fields including molecular electronics [172], control of wetting and adhesion [173],
molecular recognition [174], nanofabrication [175], and patterning to realize complex
shapes [176–178], and biosensors [179, 180].
Using the principles of SAMs various stable nanoclusters so-called monolayer
protected clusters (MPCs) have been realised [181]. The monolayers provides the
means not only to control the size, shape, location, and position control but also the
structural, morphological, and optoelectronic properties of the resulting nanomate-
rials [182]. Accordingly, these MPCs have found profound application in numerous
fields such as gas sensors [183], bio sensors [184], drug delivery [185], molecular
electronics [186, 187], electrocatalyst [188], and study of advanced physics [189].

3.6 Hybrid Approaches for Thin Film Deposition

With the advancement in nanoscience and nanotechnology, there has been an upsurge
in the development of novel methodologies that can be effectively employed so as
to realize a position and aspect ratio control growth or synthesis of nanostructures.
Herein, also the thin film techniques have demonstrated their excellent applicability
to realize the desired pattern configurations important for particular applications. For
example, using thermal evaporation or spin coating (polystyrene spheres) the seed
layer is provided for the growth of nanostructures using either hydrothermal or vapor
phase depositions [190]. Bent et al. have demonstrated a unique way to fabricate 3D
structures with dimensions down to the nanoscale using combination of ALD and
SAM techniques [191]. In particular, a patterned resist, typically a SAM or a polymer
can be employed area-selective film deposition through ALD and results in lateral
patterning. Importantly, high degree of packing and hydrophobicity of the SAMs
forms a means to block growth by ALD. Figure 3.12 summarizes the different steps
involved in the fabrication of the patterned thin films using microcontact printing
and selective ALD.
In order to realize organic–inorganic hybrid thin films a multiple source based
thermal evaporation technique has been effectively employed [192]. Herein, hybrid
110 K. R. Sinju et al.

Fig. 3.12 Schematics of the

steps to achieve patterned
thin films using microcontact
printing and selective ALD.
Reprinted with permission
from X. Jiang et al. J. Phys.
Chem. C 2009, 113, 41,
17613–17625, Copyright ©
2019 American Chemical
Society [191]

films were deposited by thermal evaporation employing a different source each for
the organic and inorganic components. Use of different sources enables different
power conditions for the two components. Using the approach several hybrid
films like copper phthalocyanine (CuPc)/TiOx multilayers [193], phthalocyanato
tin(IV) dichloride (SnCl2 Pc)/cadmium(II) selenide [194], CuPc/PbTe [195], and
8-hydroxyquinoline aluminum (Alq)/MgF2 [196], have been achieved.

3.7 Non-conventional Thin Film Techniques

Several non-conventional thin film techniques have also been employed for realizing
films for desired applications. Chuang et al. reported a novel ultrasound-assisted
supercritical argon electroplating process (US-SC-Ar) with no additives to produce
copper metal coatings [197]. Ultrasound applied to electroplating process creates
cavitation phenomena resulting in particle de-agglomeration, enhanced mass transfer,
increased nucleation rates and thus, cleaner deposits with finer grain sizes [198,
199]. Introduction of ultrasound accelerates metal ion mobility, yielding densely-
packed structures with finer grains and better aesthetic finish. Temperature of 35 °C,
pressure of 2500 psi, current density of 5 A/dm2 , and acoustic power density of
0.094 W/cm3 , produced coatings with enhanced mechanical and corrosion behavior
3 Techniques for Thin Films of Advanced Materials 111

compared to those produced by conventional or silent SC-Ar processes. Chuang et al.

demonstrated a novel method of fabrication for the high aspect ratio NiP nanowires
using blind-hole anodic aluminium oxide (AAO) templates by supercritical (sc)-CO2
electroless plating method (SC-ELP) [200]. Using the method 1D NiP nanowires with
relatively high AR were easily obtained.
Huet et al. demonstrated a reproducible and scalable way to realize high quality
graphene film on thin Cu substrates using a pressure-controlled CVD [201]. Using
the technique single-layer graphene with millimeter-size domains crucial for various
device applications was easily obtained.

3.8 Transfer of Thin Films from One Substrate to Another

There are certain applications like optoelectronics and high frequency/power elec-
tronics that demands the transfer of thin films from one substrate to another [202].
Herein the films with desired properties are first grown on to the substrates (single
crystal) and later are removed and transferred onto the foreign substrates like silicon,
polycrystalline metal, glass, and transparent plastics for achieving the device config-
uration [203]. For instance, single crystal nitride films can easily be grown onto
crystalline substrates while it is very difficult to grow them onto polycrystalline or
amorphous substrates. Accordingly, the films grown onto the crystalline substrates
demands their release and transfer to suitable foriegn substrates to realize device
application. Generally, the films are first deposited onto the buffer layers such
as aluminium nitride (AlN), galium nitride(GaN), aluminium oxynitride (AlON),
graphite, graphene, hexagonal boron nitride (h-BN), and ZnO [204, 205]. The release
and transfer of the films is then achieved employing thermal, chemical, and mechan-
ical techniques. For example, Kobayashi et al. have reported the successful transfer
of the multiple quantum well structures grown onto h-BN buffer substrate using
mechanical force and indium sheet as an adhesive layer for the transfer onto the
foreign substrates [206].

3.9 Future Prospects and Conclusion

From the above discussion it is evident that with advancement in nanoscience and
nanotechnology, thin film techniques both conventional and un-conventional have
evolved to cope up with this increasing field. Thin film techniques offering advantages
like flexibility of precursors, control over process parameters, possibility of bulk
production, excellent compatibility with CMOS technique and above all cost have
not only sustained the advancement but also contributed enormously for synthesis
novel functional advanced materials. Besides, these techniques have paved the way
for realizing a complete device with industrially acceptable standards. Importantly,
the advanced materials synthesised have demonstrated an excellent, enhanced, and
112 K. R. Sinju et al.

desired functionalities. To achieve these most of the techniques have to undergo

course correction and some have to be used in conjunction with other. All these
points clearly illustrate the fact that the thin film techniques are the fundamental
backbones for not only the synthesis of advanced material but also in realizing a
potential, complete, and commercially acceptable devices. Thus, thin film techniques
have hold the promise for the present and are expected to contribute enormously for
future device applications also.

Acknowledgements One of the authors, KRS, would lilke to thank CSIR-UGC fellowship for JRF.
The authors also thank the support from Dr. K. P. Muthe and Dr. T. V. C. Rao, TPD, BARC.

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Chapter 4
Inkjet Printing of Nanomaterials
and Nanoinks

O. D. Jayakumar and A. K. Tyagi

Abstract Research on nanomaterials has become a fascinating branch of science

in recent years as it offers tremendous opportunities for surprising discoveries due
to the size-dependent properties of nanoparticles. The properties of nanoparticles
completely differ from their corresponding bulk counterparts and gradually changes
with size and shape, and hence find extensive applications in new advanced smart
and intelligent technologies. Development of new dimensional-dependent advanced
materials needs novel and controlled synthsesis methods and advanced characteriza-
tion techniques, in addition to new theories and models, to explain the experimental
observations posing challenges to the scientists and engineers. This article focuses
mainly on yet another new method of synthesis and fabrication of some inorganic
materials using chemistry of nanoink development and its subsequent inkjet printing
to form nanostructures. It provides balanced and brief coverage of the fundamentals
and processing techniques with regard to the above synthesis routes and characteri-
zation techniques. It also gives a first-hand information about the recent technology
of 3D printing. This chapter is written with an intention to serve as a general intro-
duction to nonmaterial’s synthesis by nanoink printing methods. The article ends
with the future of inkjet printing technology and by introducing 4D printing where
4th dimension is time.

Keywords Nanomaterials · Nanoink · Inkjet printing · Magnetic materials ·

Semiconductors

O. D. Jayakumar · A. K. Tyagi (B)

Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
O. D. Jayakumar
e-mail: [email protected]
A. K. Tyagi
Homi Bhabha National Institute, Mumbai 400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 119
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_4
120 O. D. Jayakumar and A. K. Tyagi

4.1 Overview of Printing Technology

4.1.1 Introduction

The process of positioning of an ink droplet of miniature volume that is correlated

with an image, on a pre-treated substrate, is called Digital printing. This printing
process, can be used for the low-cost deposition of functional or non-functional mate-
rials, on preferred locations on a substrate with diameters in µm range, which nearly
matches with nozzle diameter. The minimum volume of the ink droplets that can be
printed can be as small as picolitre. Inkjet printing technique is an advanced digital
fabrication process for the modern flexible electronics because of many reasons like:
1. Inkjet printing deposits required materials selectively drop-by-drop on a
substrate by a non-contact method.
2. It is a low-cost method and needs only small working space.
3. It is suitable for industrial production of prototypes.
4. Minimum wastage of ink.
5. It can print different structures and thin films, which are key for organic
electronics.
The process of direct printing of advanced functional materials has emerged as
an alternative technology to conventional integrated circuit (IC) development partic-
ularly in developing cost-effective flexible electronics. Among few direct printing
techniques [1–3], Drop-On-Demand (DOD) inkjet printing is being rapidly growing
as an attractive patterning technique for large field of applications like organic elec-
tronics [1], nanotechnology [2], flexible electronics [2] and tissue engineering [3].
Inkjet printing technique, a non-contact and digitally controlled technique, is based
on the ejection of ink drops through fine nozzle directly to a pre-decided position.
Inkjet printing can produce and repeatedly dispense spheres of ink with diameters
in µm range. Figure 4.1 shows different kinds of materials and devices that can
be printed using printing technologies. Inkjet printing is commercially classified
as continuous and Drop-On-Demand (DOD). DOD is further mainly subdivided as
thermal and piezoelectric. Further subdivisions are given in Fig. 4.2. Continuous
inkjet printing is very useful in industrial environment because its printing speed is
quite high. Further, the printing nozzle does not easily get clogged as the ink droplets
are continuously generated and volatile inks are allowed to dry rapidly. In spite of
these advantages, continuous inkjet printing suffers from some major disadvantages
like (1) low resolution due to the high-speed of printing; (2) only charged inks can
be printed; and (3) high cost of maintenance.
4 Inkjet Printing of Nanomaterials and Nanoinks 121

Protecve Layers
Insulator structures

Fig. 4.1 The typical examples of inkjet printing technology

Multiple technologies Piezo electric Drop on Demand

Digital Printing Technology Overview (DOD)
Printing inkjet printing

Traditional Digital
(fixed image) (variable image)

Offset
Gravure Laser
Screen Flexo

Ink Jet

Inkjet Family Tree

Continuous- Impulse- Drops on demand

no colour colour also means only on
Applying an electric
signal for one drop of
Thermal Piezoelectric ink.
Delivers drops only
Piezo electric Drop on demand (DOD) ink jet printing when and where
it is desired.

Fig. 4.2 Different kinds of printing technologies

122 O. D. Jayakumar and A. K. Tyagi

4.1.2 Drop-On-Demand Inkjet Printing

It works on a simple principle of whenever the user needs a drop of ink to be placed
on a substrate, the control mechanism communicates with the inkjet head by sending
a signal to print one drop (=one signal). While both thermal and piezo electric inkjet
printing rely on printing drops of ink on to the substrate, how the drops are ejected
from the nozzles of inkjet cartridge is what differentiates the two, i.e. thermal [4, 5]
and piezoelectric [6, 7].

4.1.3 Thermal Inkjet Printer

The technology of thermal inkjet printing involves a process of heating rapidly the
ink in the chamber to a temperature in the range of 250–350 °C to create vapours of
ink which creates bubble, and hence, a pulse to force the ink droplets out through the
nozzle. The bubble collapses once the ink drop comes out through the nozzle. The
collapse of bubble forces the ink to refill again. The advantage of thermal inkjet printer
is that its nozzle density is high, and hence small ink volume (100–200 picolitres)
can be dispensed.

4.1.4 Piezo Inkjet

Unlike continuous mode, DOD does not involve recirculation of the ink; hence, colour
printing can be done. A further advantage is higher integration, as it is possible to
have larger number of channels which give more coverage area. Piezoelectric inkjet
printers use the inverse piezoelectric effect, which causes certain crystalline materials
(e.g. PZT) to change shape when a voltage is applied across them. In printers used
for commercial applications, the voltage pulse frequency n ranges from 1 to 20 kHz.
Pressure waves are generated because of piezo electric effect, and travel through the
ink channel, and droplets are generated at acoustic frequencies [8]. Thus, a small
electrical pulse makes the crystal contract slightly, squeezing ink out of the nozzle
onto the substrate (Fig. 4.3).
One more classification of Piezoelectric mode is binary and greyscale printing.
Every pixel on the substrate follows binary choice, i.e. presence or absence of ink.
Greyscale inkjet technology works in the same as binary inkjet but has the ability to
fire a range of drop sizes—up to 16 different sizes.
The piezoelectric inkjet printing technique can be applied to a wide range of
material dispensing applications, such as bio-medical materials [9], metal inks [10]
and polymers [11] and oxides [12]. The additive process of DOD with direct-write
ability in a non-contact deposition mode can be done without masks, which leads
to cost-savings, contamination-free efficient use of materials and waste elimination.
4 Inkjet Printing of Nanomaterials and Nanoinks 123

Fig. 4.3 Mechanism of ejection of ink drop from a nozzle

The past few years have seen growing applications, especially in developing organic
transistors [13], light emitting diodes [14], ceramics [15] and biopolymer arrays
[16]. It is now routinely used to form polymer and organic LEDs [16] for flexible
display applications, to fabricate electronic circuits and for the controlled deposition
of nanoparticles [17]. Further, the method is suitable for fabricating DNA microarrays
as well as for depositing SAMs or proteins. In view of the low cost compared to other
physical methods and no material waste, inkjet printing technology is now being
deployed commercially in solar cell manufacturing process. Majority of companies
now make use of inkjet printing technology in the production of second generation
thin film solar cells, and numerous groups are exploring the possibilities for even
third generation solar cell production.

4.1.5 Rheology of Inks for Inkjet Printing

The ink must be highly stable and shelf-life of ink should be high. Secondly, the ‘ink’
has to meet required viscosity and surface tension, so that the ink can be printed freely
without clogging of nozzles. Also, the solvent used for making ink must have low
volatility to avoid clogging. These properties of ink should be in such a way as to
print repeatedly and reliably to obtain the best printed pattern. The surface tension
of the ink must be around 30 mN/m, and the ink pressure should be low so as
to prevent dropping of the ink from the nozzle [18]. Particle size and structure of
the ink particle at both molecular- and nano-scale will affect as the solubility and
chemical and environmental stability of the ink. The ink droplets with diameter in
the microscale should have enough kinetic energy to exceed the interfacial energy
that holds them to the liquid meniscus in the nozzle. The viscosity of ink must be low
enough to allow the channel to be refilled as fast as possible in ~100 µs [19]. Printing
of ink with high-viscosity is difficult as the power generated by the piezoelectric and
heater membrane is limited [20].
124 O. D. Jayakumar and A. K. Tyagi

4.2 Applications

The scope of inkjet printing technology is vast, and it can solve many ranges of
problems in different fields including industrial and commercial applications. Inkjet
printing process has the advantage of skipping many steps in the manufacturing
process at the time of production. Inkjet printing process can develop novel advanced
smart and intelligent materials that can have newer applications. It can produce
new materials with superior functionality that have previously been unfeasible. Few
important applications of inkjet and devices are listed below.
Inkjet printing technique has been used for developing microlenses [21], waveg-
uides [22], rechargeable Li ion battery [23], Smart Bandage for Wireless Monitoring
of Chronic Wounds [24], Zero-power sensors for large-scale RFID-integrated smart
skins [25] and Large Area Multifunctional Smart Windows [26].

4.3 An Introduction to 3D Inkjet Printing

The very recent emergence of 3D printing technology has got significant attention
because it can be used for printing 3D structured materials for making next generation
smart, intelligent and wearable functional devices. 3D printed health monitoring
devices, implantable and biomimetic devices [27] for individual needs and robotics
got scientific community’s attention. Novel devices of complicated structures are
developed by layer-by-layer printing following the digital 3D model of devices [28–
38]. The another positive functional advantage of using the 3D printing method for
fabricating flexible electronic devices is that it can be used to fabricate devices with
necessary properties for individual as well as for company customers on demand. The
aforementioned many positive advantages of 3D printing technology for fabricating
smart and intelligent flexible devices make this technology as the future.
For example, 3D printed devices made by fused deposition modelling follows
pasting of various microelectronic devices and components and connecting with
circuit elements like resistors, capacitors and inductors. In another type of the 3D
printing, the 3D model of the product, generated by computer-aided design, can be
3D printed layer-by-layer to obtain the final product. The important advantage of this
method over other methods is its ability of delivering a final finished product without
any further processing, like heating or melting or else fusion of metals or plastics.

4.4 Highlights of Our Results On DOD Inkjet Printing

The advent of 3D printing fabrication process for development of devices by building

parts layer-by-layer has led to interest in fabrication of devices by inkjet printing tech-
nique by printing different parts and circuits of devices by layer-by-layer assembly
4 Inkjet Printing of Nanomaterials and Nanoinks 125

too. There are only few reports of inkjet printing of inorganic materials and patterns
compared to printing of organic materials and devices [39].
Here, we present our efforts in making some inorganic inks and their subsequent
inkjet printing in the form of patterns like dots, lines, junctions and films on different
substrates to make their oxide form after proper heat treatment to study their magnetic
and sensing properties.
The synthesis of transition metals [TM]-doped wide band gap semiconductors
has attracted scientific attention, because of their application in spintronic devices
with improved performance, less power requirement and increased speeds, than the
conventional charge-based devices. TM-doped ZnO [40–42] have recently attracted
great interest among many semiconductor host materials that have been investigated
for spintronic applications being ideal systems for spintronic and functional devices.
The structural, physical and chemical properties of TM-doped ZnO are influenced
by method of synthesis, synthesis conditions and TM dopant concentrations in host
ZnO that will influence the observed magnetic properties too. DOD printer can be
used for developing ZnO and TM-doped ZnO microstructure patterns like dots, lines,
junctions and films using solvent-based inks on different substrates like Si, plastic and
polyimide using inkjet printing technology, which are important for the applications
of spintronics-based devices. Magnetic and structural properties of inkjet printed
films have been studied by taking 2% Mn-doped ZnO film as a representative film
[39]. The printed 2% Mn-doped ZnO film showed fast UV sensing capability along
with ferromagnetism. Among all films, Zn0.97 Mn0.02 Al0.01 O showed the enhanced
ferromagnetism due to extra carriers generated from Al [43].
Figure 4.4 depicts schematic steps followed for inkjet printing and processing of
films and patterns of formulated ZnO, 2% Mn-doped ZnO and 2% Co-doped ZnO
inks on the preheated substrate. During the drying at ~200 °C followed by heating
at 400–500 °C for 30 min, the solvent escapes from the substrate leaving metal
oxide structure on the substrates. Figure 4.4 also depicts the photos of formulated
ZnO-based inks and their printed patterns.
The ZnO and doped ZnO inks were prepared by dissolving corresponding precur-
sors in low-cost solvents as reported by us elsewhere [39, 44]. However, inks of metal
nanoparticles were prepared by dispersing nanoparticles of Au, Cu and Ag (prepared
by a solvo-thermal method of heating acetate or chloride precursor in ethylene glycol
at 140 °C for 2 h followed by washing) in printable solvent after surface modification
of metal nanoparticles.
Crystalline films of oxide structures were inkjet printed on n-type Si (001) with
preferred c-axis (002) orientation (Fig. 4.5) by 3-pass printing of 0.25 M inks, with
intermittent heating at 400 °C for 30 min, 1-pass after another, after printing and
drying. No evidence for any impurities of manganese or cobalt oxides has been seen
by XRD [39, 44]. XRD analysis of (002) peaks, using the Scherer equation and also
SEM images, yields an average crystallite size of ~25 nm for ZnO-based samples.
Critical analysis of XRD patterns of doped ZnO exhibited peak position shift to lower
angles proving the volume increase of ZnO because of the substitution of Mn2+ /Co2+
in ZnO lattice [39, 44].
126 O. D. Jayakumar and A. K. Tyagi

Fig. 4.4 Typical schematic steps followed for developing different inkjet printed patterns of ZnO
base formulations. (Refs. [39, 44])

Fig. 4.5 XRD patterns of

ZnO, 2% Mn-doped ZnO and
2% Co-doped ZnO [39, 44]

Films with different thickness have been developed by printing different number
of passes, layer-by-layer, subsequent to drying and heating after each pass of printing.
For 1- and 2-pass inkjet printed films of all the three inks, the film thickness was 40
and 80 nm, respectively. The 3-pass inkjet printed films of these materials were of
130 nm film thickness.
4 Inkjet Printing of Nanomaterials and Nanoinks 127

Fig. 4.6 Inkjet printed structures (films and different patterns like dots, lines and junctions) of ZnO,
2% Mn-doped ZnO and 2% Co-doped ZnO. (Refs. [39, 44])

Figure 4.6 shows the 3-pass and 1-pass inkjet printed films and patterns developed
on silicon and polyimide substrates of ZnO, 2% Mn-doped ZnO and 2% Co-doped
ZnO, respectively. All films were annealed for 30 min at 400 °C after printing.
Figure 4.6B shows dots (~200 µm diameter), lines of ZnO, 2% Mn-doped ZnO and
2% Co-doped ZnO with width between 150 and 400 µm and junctions of widths 250
and 300 µm (Fig. 4.7).
Magnetic properties of inkjet printed films of ZnO, 2% Mn-doped ZnO and 2%
Co-doped ZnO are well explained elsewhere [39, 44]. Figure 4.8a and b depict the
magnetization (M) vs Field (H) for 6 lines of Zn0.98 Mn0.02 O and Zn0.97 Mn0.02 Al0.01 O,
respectively. It is clear from magnetic data that the doping of 1% Al in Zn0.98 Mn0.02 O
caused an increase in magnetic properties of Zn0.97 Mn0.02 Al0.01 O which may be due
to the extra charge carriers due to trivalent Al [43]. However, the magnetic moment
of 14 dots of Zn0.98 Mn0.02 O (Fig. 4.9) was found to be significantly higher than the
inkjet printed films of Zn0.98 Mn0.02 O (Fig. 4.6A). This is surprising and needs further
systematic studies.
128 O. D. Jayakumar and A. K. Tyagi

Fig. 4.7 Magnetization versus field plot of ZnO, 2% Mn-doped ZnO and 2% Co-doped ZnO films.
(Refs. [39, 44])

Fig. 4.8 a Image of printed lines (6 lines) of 2% Mn-doped ZnO and its MvsH curve. b Image of
6 lines of printed Zn0.97 Mn0.02 Al0.01 O and its MvsH curve

Fig. 4.9 Printed image of 14

dots of 2% Mn-doped ZnO
and its MvsH curve
4 Inkjet Printing of Nanomaterials and Nanoinks 129

Fig. 4.10 Inkjet printed electrodes using Au and Ag nano-particle inks

In our earlier studies [39] of 2% Mn-doped ZnO made by inkjet printing, we have
reported on the bifunctional properties of the same. The response of UV light on
3-pass inkjet printed ZnO and Zn0.98 Mn0.02 O films developed on Silicon by heating
in presence of air at 400 °C was measured using a Tektronix 7503 oscilloscope.
The UV response of these films with 130 nm thickness on Silicon substrate was
measured by keeping the film in UV light of 365 nm wavelength emitted by an LED.
We have observed a fast decay time of ~0.52 ms for the Zn0.98 Mn0.02 O film while
ZnO film decayed in 0.60 ms [39]. In addition, the Zn0.98 Mn0.02 O film showed more
photocurrent compared to pristine ZnO film. The short decay time and fast response
to UV light exhibited by ferromagnetic Zn0.98 Mn0.02 O film compared to diamagnetic
film of pristine ZnO needs detailed investigation.
The increased UV response of inkjet printed Zn0.98 Mn0.02 O film encouraged us to
develop a prototype of UV sensor using Zn0.98 Mn0.02 O film. The processing scheme
followed for the development of UV sensor is shown in Fig. 4.10. The inkjet printed
Zn0.98 Mn0.02 O film is printed over the Si substrate which was pre-printed with two
gold electrodes. The UV response of ZnO film is shown by an LED (indicator) as
well as the resistance change. When the ZnO film is irradiated by UV light (363 nm),
the photocurrent developed in the circuit lights up indicator. At the same time, the
resistance of ZnO film decreases from ~8 Mega Ohm to ~0.5 Mega Ohm as shown
in Fig. 4.10.

4.5 Conclusions

A brief introduction to 2D and 3D inkjet printing and its versatility of applications

is given in this chapter. DOD inkjet printed structures of ZnO, 2% Co-doped ZnO
and 2% Mn-doped ZnO were developed on Silicon and polyimide substrates, by
using their solvent-based inks. The 2% Mn-doped ZnO film on Si substrate showed
UV sensing ability along with enhanced ferromagnetism. This paves the way for
130 O. D. Jayakumar and A. K. Tyagi

Fig. 4.11 Magnetic and UV sensing properties of 2% Mn-doped ZnO (Refs. [39, 44])

multifunctional devices. The chapter ends with the introduction to 4D printing, the
future for new material synthesis Figs. 4.11 and 4.12.

4.6 Future Scope

The future and the demand of additive manufacturing process are very promising in
many fields ranging from food to medical. Future may see business centres, disaster
sites and even every home with the 3D printing device.
4D printing, the futuristic future
The process of self-transforming a 3D printed object into a new structure with new
functionality due to the external stimuli like temperature, light or environmental
change over a period of time is called 4D printing. Or simply 4D printing is creating
a material after 3D printing with time as 4th dimension. Hence, the breakthrough
about 4D Printing is its ability of changing the shape of a structure made by 3D
Printing technology over a time period. The shape of 4D printed object is obtained
from 3D printed shape. The difference between 3D printing and 4D printing is 4D
printing makes use of programmable software and parameters like temperature, light,
pressure, etc. This is similar to a non-living object in 3D shape change its 3D shape
over a period of time into a 4D shape with new structure.
4 Inkjet Printing of Nanomaterials and Nanoinks 131

Fig. 4.12 The scheme followed for the development of a UV sensor using ZnO film and a prototype
of UV sensor

Acknowledgements We place on record, our deepest gratitude to Prof. K. V. Rao, Department

of Materials Science and Engineering, KTH-Royal Institute of Technology, Stockholm SE10044,
Sweden for his invaluable support, guidance and motivation.

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Chapter 5
Particle Size and Shape Engineering
for Advanced Materials

R. S. Ningthoujam and A. K. Tyagi

Abstract Advanced Materials are the materials whose properties/characteristics are

superior over the traditional materials for a particular application. Materials can be
obtained by preparation of new methodology or modifications of existing materials.
Materials consist of many particles with varying size ranging from nanometer to
micron. On the basis of arrangement of atoms/ions in particles, materials can be
grouped into three: amorphous, liquid crystal, and crystalline materials. Particles
can be generated by three ways: natural, man-made industrial processes, and labora-
tory synthesis or modification of existing ones. Examples of natural particles include
sea spray, mineral composites, volcano ashes, etc. Examples of man-made indus-
trial processes include cooking smokes, diesel exhaust, welding fumes, industrial
effluents, sandblasting, etc. Laboratory synthesis or modification of existing ones
are performed for a particular purpose or many purposes, which include metal, non-
metals, alloys, semiconductors, insulators, composites, etc. Particle size and shape
are important parameters for a particular application. In this chapter, engineering
of particle size and shape will be discussed. The changes in chemical and physical
properties as a function of particle size and shape will also be discussed. Mechanisms
behind the formation of particles in solid, liquid, and gas phases are included.

Keywords Advanced materials · Crystalline · Amorphous · Liquid crystalline ·

Size and shape of particles · Chemical and physical properties · Mechanism

R. S. Ningthoujam (B) · A. K. Tyagi

Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
Homi Bhabha National Institute, Mumbai 400094, India
A. K. Tyagi
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 133
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_5
134 R. S. Ningthoujam and A. K. Tyagi

5.1 Introduction

Advanced Materials are the materials whose properties/characteristics are superior

over the traditional materials for a particular application. Advanced materials can
be obtained by preparation of new methodology or modifications of existing mate-
rials. Let us take an example. Gold is one of the inert materials as well as non-toxic
elements in environment. However, pure gold is difficult to be used as jewelry since
it is extremely soft in the as-cast and annealed states [1]. Thus, it is alloyed with a
little amount of Cu, Ag, Pd, or Ni as impurity to impart desired hardness. Depending
on the amount of above impurities, its color changes from reddish yellow (pure)
to greenish yellow (Ag) and red (Cu). Pure gold has particle size of micron, and
thus it could not be used for ultra-sensing in biological applications (biosensors,
diagnosis, biotechnological environmental monitoring, and wellness monitoring).
It requires changes in its particle size and shape up to nano-region (0D, 1D, or
2D). After preparation of such nanoparticles, post-processing, such as patterning
of nanoparticles in the form of films and surface modification or functionalization
with proper ligands/molecules/antibody, is necessary [2–4]. In case of catalysis,
catalytic properties of gold particle change with size, shape (spherical, nanorods,
nanowires, prism, star, and hollow structures), and dielectric medium [5–7]. Every
particle can have interesting properties, which are suitable for a particular application,
but every particle may not be useful in different areas of application. Engineering
aspects are necessary to make material for a particular application. The advanced
materials can be of following types: metals, semiconductors, insulators, compos-
ites, magnetic, ferroelectric, piezoelectric, shape memory, thermo-chromic, photo-
chromic, magneto-rheological, smart materials [8–10]. The interesting functional
property of material for a particular application can be brought by engineering shape,
size, hollowness, porosity, defects, or combination with other material through modi-
fication of synthesis procedure and post-processing after getting the initial material.
The technological advantages bring a strategy to revolutionize materials for indus-
trial and societal needs. Collaboration among R and D sectors and industrial part-
nership is need of the hour to design new materials for advanced applications. These
advanced materials may be used by a company for launching a new product, which
has many features or superior properties that satisfy many customers, so that company
achieves profitability goals. The company has to follow regulatory compliance and
sustainability [11].
Scientists, academicians, and engineers need to start innovative ideas, which are
required for present and future scopes in the areas of environmental friendliness,
sustainability, security, prevention of pathogenic microbes, energy, and high value-
added markets.
Existence of advanced materials is a result of demand for a particular application
in early stage and up to certain times, and it may become obsolete after sometime if
the new development arises due to conditions or environment or time. New develop-
ment may arise due to serendipity or rational modifications of existing materials or
technology. Let us discuss a few examples.
5 Particle Size and Shape Engineering for Advanced Materials 135

There are many allotropes of carbon. Diamond is one of the allotropes of carbon,
which is an electrical insulator, and it has high hardness and high thermal conduc-
tivity. It has been used for cutting and polishing tools and anvil-cells for high pressure
applications [12–14]. The chemical bond of C atom to surround 4 C atoms is cova-
lent bond (sp3 hybridization). Usually, diamonds are found naturally in earth’s crust.
Depending on the demand of users, its color needs to be modified. A fancy-colored
diamond is in high demand by purchasers. Only 0.01% of natural diamonds are
colored. This color can be introduced by incorporation of defects, addition of impu-
rities such as N, B, and other elements. This can be achieved by synthesis process.
Many synthesis methods have been developed in terms of economic viability or
industrial ways. So far, a large-scale production of artificial diamond is not achieved.
The cost of synthesis of diamond is exorbitant, but its demand in market is high. We
would like to bring to the notice of researchers that advanced synthesis method is
required to meet its demand or requirement in market. Concept of materials science
can bring a new synthesis procedure for diamond in economical ways.
Initially, the graphite was considered as the best material for electrical and thermal
conductivities as well as chemical and thermodynamic stabilities. Because of these
interesting properties, it is useful in electronic products such as batteries, solar panels,
and electrodes as well as refractories in high temperature material processing appli-
cations in absence of oxygen [15–17]. Carbon (C) atom in graphite has chemical
bonding with surrounding 3 C atoms in same layer by covalent bond (sp2 hybridiza-
tion) and has hexagonal closed packing structure. Between the layers, there are van
der Waals forces, which impart lubricant property to graphite. Each layer is known
as graphene, which was later isolated in 2004.
Two new types of hollow C molecules are a closed case (known as buckyballs, C60 ,
C70 ) and a cylinder (nanotubes). In 1985, C60 (fullerene) was prepared by vaporization
of the graphite rods using laser in an inert atmosphere of helium gas [18–21]. That
was the first report for preparation of nanosized carbon molecule. The fullerene
molecules range from C36 to C176 with respective diameter of 0.5–1.2 nm. The C60
has diameter of 0.7 nm. The C60 molecule has alternate single and double bonds
(=C–C=C–) to form hollow sphere with 20 hexagonal and 12 pentagonal faces just
like in soccer ball. This molecule can donate and accept electrons in the reaction.
Because of this, these are used in many applications such as batteries, catalysts,
and nanoelectronics [22]. The addition and substitution reactions can take place on
the surface of C60 sphere, and thereby, many derivatives have been prepared. These
derivatives are used in many applications including biosensors. With addition of
alkali metals (M = Li, K, Cs, Rb) to form M3 C60 , it exhibits superconductivity up
to 45 K [23].
In 1991, carbon nanotubes were prepared by carbon arc discharge, which was
similar to those used to prepare fullerene molecules [24–26]. There are two types
of carbon nanotubes. One type is considered as single-wall carbon nanotubes
(SWCNTs), which is composed of halves of fullerene cage attached to ends of a tube
or a hollow cylinder and flat graphene (2D), which is rolled up into nanometer-sized
hollow cylinder. SWCNTs exhibit the ballistic transport rather than conducting elec-
tricity via electron transport and fast ionic movement along hollow tube. Another
136 R. S. Ningthoujam and A. K. Tyagi

type of CNTs is multi-walls carbon nanotubes (MWCNTs), which have multiple

layers of carbons over inner layer. Among layers, there are van der Waals forces. C
atoms undergo a mixing of sp2 and sp3 hybridizations. Such carbon nanotubes show
the enhanced field emission properties and have been used as tips for STM (scan-
ning tunneling microscopes) and AFM (atomic force microscopy) [27]. It has high
thermal conductivity, high electrical conductivity, high tensile strength, and high
Young’s modulus of elasticity. Because of the above properties, it brings advance
scopes in different areas of materials science. Such small-size nanotubes are used in
medical sciences as nanosensor, nono-emitter, etc.
Many researchers were thinking to develop carbon fibers and single-layer
plane graphene without rolling since 1960s [28–30]. In the graphite intercalation
compounds, the graphene layers can function as either acceptor of electrons from
or donation of electrons to the intercalated species. Typical examples are mentioned
here. K-graphite (KC8 ) is a donor graphite compound, whereas Br-graphite is an
acceptor compound. With progress of materials science, new allotrope of carbon, say
graphene (atomic layers), was prepared by mechanical exfoliation of small mesas
of graphite in 2004. The graphene is a 2D material with a few layers of sp2 -sp2
chemical bonds. It has interesting properties such as high electric conductivity, high
thermal conductivity, like a metallic nature, and strong ambipolar electric field effect
(electron and hole concentrations of 1013 /cm2 ), and room temperature mobility of
10,000 cm2 /Vs. Now, graphene and their derivatives and nanocomposites have been
prepared by different synthesis routes or post-processing or modifications.
These are some of the new developments of materials for different applications.
Au nanostructures of spherical, rod, hollow, cage, star shapes, and various sizes,
and with combination with others (Ag, Fe3 O4 , SiO2 ) in the form of composite, and
core–shell nanostructures have been developed by different synthesis routes [31–38].
Magnetic nanoparticles have been used as catalysts, nanocarriers for drug, contrast
agents in magnetic resonance imaging (MRI), heat-generators in hyperthermia-based
treatment, magnetic-based separation for bacteria, toxic ions/compounds, etc. [39–
51]. For every device or application, specific synthesis strategies and post-processing
are required so that this can be utilized in economic and environmentally friendly
ways. Surface functionalization or modification of particles with suitable functional
group(s) is important in designing materials for specific purposes.
Ceramic materials such as glass fibers, Al2 O3 , YPO4 , YVO4 , lanthanide-doped
vanadates and phosphates, oxides, and intermetallic compounds as FePd, FePt,
NbTi, Cu-Zn, VN, MoN, SiC, TiN, BN, Fe6.3 Cr2.5 Co12 , FeCrAl, γ/ -Ni3 (Al, Ti),
Alx CoCrCuFeNi, and AlX Fe1.5 CrMnNi0.5 (x = 0.3, 0.5) are important in high temper-
ature and extreme environment, and used as crucibles, coating, tools, heating element,
and superconducting materials [52–63].
Preparation of different shapes of ceramics is one of the challenges to materials
scientists. Polymers are important in imparting durability, lightweight, and flexible
properties of materials. Composites/hybrids are important materials which can have
superior functionalities than individual ones. Biomaterials are materials, which are
used in health care. Laser-based synthesis, fabrication, fine tuning techniques, atomic
layer deposition, high purity single crystal preparation, and 3D/4D printings are
5 Particle Size and Shape Engineering for Advanced Materials 137

important areas in materials science. In addition to above materials, engineering of

size, shape, hollowness, and dimensionality of particles, and post-processing will be
required to design new materials. Advanced materials can be categorized into the
following on the basis of performance [11, 64–66]:
1. High performance materials (ceramics, alloys, carbon-based materials,
lightweight material having stability under high temperature, high pressure,
high radiation or extreme conditions)
2. Energy materials (fuel cells, batteries, solar photovoltaic)
3. Additive (additive manufacturing, 3D/4D printing)
4. Nano (Nanomaterials, nanostructures, nano-engineering)
5. Semiconductor-based integrated circuits (Computer, mobile, robotics)
6. Biomaterials (drug delivery and repairing of DNA/RNA through nanocarriers,
replacement of bones, teeth)
7. Smart materials (sensors, actuators, materials that sense and react to environ-
mental conditions or stimuli, say mechanical, chemical, electrical, or magnetic
signals)
8. Environmental materials (Materials for recovery, or reuse or substitutions,
environment friendly, harmless to environment, eco-friendly)
9. Surface coatings (surface coating, surface engineering over materials or
particles, thin films to enhance stability, multi-utilities)
10. Metalwork (metals processing technology)
11. Joints (welding, brazing)
12. Durability-Flexibility (polymers, rubber, resistance to any fatigue, thermal)
13. Multifunctional (hybrids, composites, core–shell materials)
14. Green materials (economic way of research, environmental friendly)
Light-amplification (Laser-related cutting, drilling, down and upconversion
photonics, laser-based devices in electro-optics, magneto-optics, health care,
industry, security, laser surface cleaning or treatment, chemical reactions, patterning,
fine tuning/marking, communication, printing, lithography, sensors, guiding, heat-
generation, melting, vaporization).

5.2 Different Types of Particles in Materials Science

Particle in materials science is an entity of atoms, and its size can range from
nanometer to micron. Its properties are generally different from individual atoms
or molecules. It can move in free space or liquid medium, but it is restricted inside
solid. It can have vibrations and rotations of molecules or chemical bonds of atoms
due to absorption of energy from surrounding. Particles can be generated by three
ways: natural, man-made industrial processes, and laboratory synthesis or modifica-
tion of existing ones. Examples of natural particles are sea spray, mineral composites,
volcano ashes, etc. Bioinspired synthesis of nanoparticles such as Fe3 O4 , Ag, and
naturally formed nanoparticles such as Fe3 O4 in living cells (magnetotactic bacteria)
138 R. S. Ningthoujam and A. K. Tyagi

are also reported [67, 68]. The bioinspired synthesis of particles is also considered
as green chemistry route. Examples of incidental particles are man-made industrial
processes, which include cooking smokes, diesel exhaust, welding fumes, indus-
trial effluents, sandblasting, etc. Engineering particles are the prepared particles for
a particular purpose or many purposes, which include metal, non-metals, alloys,
semiconductors, insulators, composites, etc. The particles in laboratory synthesis
or modification of existing ones can be generated by two approaches: Bottom-up
and Top-down approaches [51]. On the basis of arrangement of atoms in particles,
they can be grouped into three: Amorphous, liquid crystal, and crystalline mate-
rials (Figs. 5.1 and 5.2). Amorphous material does not have a long order of atoms
(isotropic in properties). Here, the diameter (d) of spherical particle is assumed as
size. Examples of amorphous materials are many plastic, polymers, papers, etc. A
liquid crystal is a state of matter having properties between those of conventional
liquid and those of solid crystal. They can be used as liquid in which molecules
have proper orientations. Examples of liquid crystals are solutions of soap and deter-
gents, biological membranes, and cell membranes. DNA and many polypeptides can
form liquid crystal. Crystalline materials can be grouped into two categories, namely,
single and polycrystalline materials. In single crystal, atoms are arranged in perfect
order. It means that there are no grain boundaries (Fig. 5.3). Grain boundary is space

Fig. 5.1 Types of particles on the basis of arrangement of atoms/ions

5 Particle Size and Shape Engineering for Advanced Materials 139

Fig. 5.2 Evolution of particle from atoms through cluster. Particles are of two types: Disordered
and ordered solid. In ordered solid: different layers of A, B, and C types can form A (simple
packing), AB (hexagonal closed packing), or ABC (face-centered cubic closed packing or cubic
closed packing) in a particular crystal structure

Fig. 5.3 In a single crystal,

arrangement of atoms/ions in
lattice is perfect (2D
representation). A schematic
part of single crystal having
length of 3 mm is shown

between grains or particles. In grain boundary, atomic density is less than the bulk or
grain [69]. In case of polycrystalline materials, there are grain boundaries between
grains. Polycrystalline materials can be further grouped into two: macrocrystalline
and nanocrystalline materials (Figs. 5.4 and 5.5). In case of macrocrystalline, size of
140 R. S. Ningthoujam and A. K. Tyagi

Fig. 5.4 In a
macrocrystaline,
arrangement of atoms/ions in
lattice forms grains (2D
representation). Between
grains (G), there is a grain
boundary (GB). Space of GB
is not much significant as
compared to that of G. The
orientation of a particular
grain is different from
neighboring ones. A
schematic part of
macrocrystaline having
length of 1 mm is shown

Fig. 5.5 In a nanocrystaline,

arrangement of atoms/ions in
lattice forms grains (2D
representation). Between
grains (G), there is a grain
boundary (GB). Space of GB
is significant as compared to
that of G. The orientation of
a particular grain is different
from neighboring ones. A
schematic part of
nanocrystaline having length
of 100 nm is shown

grain is from submicron to a few microns (d >> 100 nm). Examples of macrocrys-
talline materials are highly crystalline particles of ceramics, alloys, metals, compos-
ites, etc. In case of nanocrystalline, size of grain is in nanometer range (1–100 nm).
Depending on confinement of electrons or atoms, nanocrystalline can be grouped
into four categories, namely: 0D, 1D, 2D, and 3D. Examples of 0D, 1D, 2D, and 3D
materials are quantum dots, nanowires, nanosheets, and nanostars (or nanotetrapods),
respectively [70]. The atomic/ionic arrangement in lattice of a particular structure
5 Particle Size and Shape Engineering for Advanced Materials 141

can be of simple (A-type), hexagonal close packing (hcp, AB-type), or cubic closed
packing (ccp, ABC-type) (Fig. 5.2).
Four types of synthesis methods for materials are generally found: (1)
Dried powder-based synthesis, (2) Liquid/Solution-based synthesis, (3) Gas-based
synthesis, and (4) Thin film-based synthesis. In case of dried powder-based synthesis,
the precursors are ground or mixed without using any liquid (water or oil), and then
heated or pressurized or combined form of heat-treatment and pressure is used or
excitation is done using suitable light (UV, visible, and IR) or laser or irradiation
with γ-rays, β-rays, α-rays or neutron sources or any kind of external uncharged or
charged particles.
This includes the preparation of oxides by the solid-state reaction, the prepara-
tion of alloys by arc melting, polymerization of monomers under irradiation, light-
or laser-induced synthesis, etc. Now, how to change size and shape of particles? In
case of liquid-based synthesis, the precursors are generally dissolved in water or oil
or mixture of water and oil into molecular and ionic forms, and then compounds
or materials are precipitated out. It may be further carried out for post-processing,
say, heat-treatment. This includes the precipitation, co-precipitation, sol-gel route,
micro-emulsion route, hot-injection route, hydrothermal route, crystallization, etc.
Now, how to change size and shape of particles? In case of gas-based synthesis,
atoms or ions or molecules are brought to gaseous formation, and reaction among
them occurs in gaseous state to form cluster or particles. This includes the formation
of molecules of compounds or particles in stars, ionosphere, exosphere, magneto-
sphere, etc. Here, the roles of absorption of UV light, x-rays, γ-rays, electromagnetic
waves (electric and magnetic fields), or uncharged particles are important. Even in
laboratory, the particles are prepared in gaseous form using time of flight mass spec-
trometer, plasma synthesis, etc. The role of environment, such as inert gases, cooling
process, condensation, and presence of electromagnetic waves, can tune size and
shape of particles. In case of thin film-based synthesis, gaseous forms of atoms or
ions or molecules are condensed on a substrate, or molecules in liquid form are
deposited on substrate. This includes chemical and physical vapor deposition (CVD,
PVD) and molecular beam epitaxy (MBE), mono- or poly-layered deposition of long
chain fatty acids or surfactants on substrate from liquid medium, etc. In subsequent
sections, different methods to tailor the size and shape of particles of advanced mate-
rials will be discussed. Engineering of particles means the preparation of desired
particles followed by processing such as fabrication, surface modification, design,
or construction, so that properties/characteristics of products are superior over the
traditional materials for a particular/targeted application. Such engineered products
or advanced materials can have impact in different areas such as (i) Energy tech-
nologies, (ii) Conversion of greenhouse gases such as CO2 to methane or methanol
or ethanol or any derivative, (iii) Transportation, (iv) Information Technology, (v)
Catalysts including photocatalysts, (vi) Health care, (vii) Biomaterials, (viii) Biotech-
nology, (ix) Structural materials, (x) Robotics, (xi) Food processing, (xii) Material
science, (xiii) Sensors including biosensors, (xiv) Cosmetic technology, (xv) Nuclear
energy, (xvi) Alternative source of fuel (H2 ) produced from various processes such as
splitting of H2 O or fuels CH4 /C2 H6 /C3 H8 , (xvii) Production of energy or electricity
142 R. S. Ningthoujam and A. K. Tyagi

Fig. 5.6 Use of engineered products or advanced materials in different areas

through wind or tidal waves, (xviii) Space science and technology, (xix) Carrier in
drug delivery, (xx) Effective drug design, (xxi) Solar cells or photovoltaics or fuel
cells or batteries, (xxii) Efficient light emitter materials, (xxiii) High data storage
devices, (xxiv) Sustainable environment, (xxv) Surface and polymer sciences, (xxvi)
Processing of papers and inks, (xxvii) 3D/4D printing, and (xxviii) Mechanical, civil,
and metallurgical areas (Fig. 5.6). However, it is not possible to cover all areas in
this chapter.

5.3 Need for Different Sizes of Particles and Shapes

in Advanced Materials

This aspect can be emphasized by several examples. Suppose, the particles are useful
in drug carrier in living body, and then, shape of particles must be spherical and size
of particles should be 100–300 nm (micelles, liposomes, polymers) or smaller size
<50 nm (Fe3 O4 or SiO2 ). Micelles, liposomes, and many polymers are amorphous
in nature, whereas Fe3 O4 particles are crystalline and SiO2 is amorphous [71, 72].
Micelles or liposomes have water-soluble and oil-soluble structural components.
If drug molecules are water soluble, these can be conjugated with water-soluble
component, whereas if drug molecules are oil soluble, these are conjugated with
oil-soluble component. Drug release kinetic is based on temperature, pH of envi-
ronment, or other type of counter interaction (positive and negative polar groups). If
5 Particle Size and Shape Engineering for Advanced Materials 143

particles are useful in replacement of teeth, bone, shape of particles can vary from
spherical, nanowires, or nanorods. Even particle size can vary from nanometer to
micron. Particles can be amorphous or crystalline. Materials such as hydroxyap-
atite (HA = Ca10 (PO4 )6 (OH)2 ), titanium, alloys (Ti-Al-V, Ti-Al-V-Li), composites
of tri-calcium phosphate (TCP = Ca3 (PO4 )2 ), Al2 O3 , ZrO2 are used as biomaterials
for replacement of teeth or bone [73]. Porous scaffold biomaterials have been used
as templates for tissue regeneration, so that damaged tissues after surgical proce-
dures can be regenerated. This engineering is very important for application. HA
and TCP scaffolds have characteristic properties such as high mechanical stiffness
(Young’s modulus), hard brittle surface, and very low elasticity as well as highly
biocompatibility. These have chemical and structural similarity to the microenviron-
ment of native bone. Thus, these are used in dental and orthopedic surgery to coat
metallic implant surfaces to improve implant integration with host bone. Sometimes,
these have limitation in shaping for implantation, and even new bone formed in a
porous HA or TCP scaffold cannot sustain the mechanical loading needed for remod-
eling. Also, degradation of scaffold occurs with time or different pH medium (5–8).
Nowadays, synthetic polymers, such as poly-l-lactic acid (PLLA), poly-dl-lactic-co-
glycolic acid (PLGA), polystyrene, and polyglycolic acid (PGA), have been used
as scaffold materials for tissue engineering [74]. Many composites have been fabri-
cated with a tailored architecture. Naturally occurring biomaterials, such as collagen,
various proteoglycans, and chitosan, have been used in tissue engineering, such as
the regeneration of damaged tissue due to injury or surgery, with incorporation of
a proper antibacterial, anti-fungal, or anti-virus materials. Ag or TiO2 nanoparti-
cles have been used for protection from microbes such as bacteria, fungus, or virus
[75, 76]. For cartilage and cardiovascular repair, composites of naturally occurring
polymer with synthetic polymer have been used. It needs a purpose or any targeted
point for materials. Sometimes, porous carbon fibers have been used as scaffold in
tissue engineering to enhance mechanical strength. Hollow Au and Ag nanoparticles
with size less than 100 nm have been used as drug carrier as well as heat gener-
ator under NIR laser excitation (photothermal) or reactive oxygen generator under
NIR laser excitation (photodyanamics) [77]. The drug is loaded inside the core. This
concept has been used to cure tumor through blood–brain barrier.
In case of photocatalysts, a light absorber is necessary. In order to perform light
absorption in UV, visible, and NIR, materials are varied. This is based on band gap
engineering. The particles with appropriate size and shapes can have high absorption
cross-section. It also calls for designing different types of materials. Anatase TiO2
nanoparticles can absorb the UV light, and after N doping, it can absorb light in
the visible range [78]. Quantum dots (QDs) in general show absorption spectrum
from UV to visible, since it can have discrete absorption peaks along with lowest
energy absorption peak. Sometimes, QDs can absorb light from UV-to-Visible-NIR
range, which cover almost entire solar spectrum. PbS QDs can show absorption in
visible range, and PbSe QDs can show absorption in visible-NIR range. Bulk PbS and
PbSe have band gaps of 0.41and 0.26 eV, respectively [79]. When shape of particle
changes from the nanosized spherical to nanorod, a variation in absorption band is
observed. When heterostructures of metal–semconductor, semiconductor I (lower
144 R. S. Ningthoujam and A. K. Tyagi

band gap)–semiconductor II (higher band gap), semiconductor I (lower band gap)–

semiconductor II (higher band gap)–semiconductor I, semiconductor I (lower band
gap)–semiconductor II (higher band gap)–semiconductor III (different band gap from
I or II) are produced, improvement in absorption cross-section as well as band gap
tuning can be brought [80]. Multi-well heterostructures are essential for absorption
of light from UV-visible-NIR, in case of conversion of solar light to the electricity or
heat. Conservation of energy or production of H2 from water splitting and solar light
using proper photocatalysts is up most important for today and tomorrow society in
sustainable environment. Synthesis and fabrication of particles in powders and thin
films are important steps to achieve proper target or goal.
The possible sizes and shapes of particles from materials are shown (Fig. 5.7). In
spherical particles, particle size can be increased by heat-treatment, because diffusion
or chemical reaction is faster at higher temperature. Sizes 2–5 nm, 10 nm, 100 nm,
1 μm, 10 μm can be obtained. Particles with disc type can be converted into rod by
increasing length. Tube-type particles can be prepared by using template method.

Fig. 5.7 The regular size and shape of particles can be obtained from different materials. 1. In
spherical particles, particle size can be increased by heat-treatment because diffusion or chemical
reaction is faster at higher temperature. Size 2–5 nm, 10 nm, 100 nm, 1 μm, 10 μm can be obtained. 2
and 3. Particles with disc type can be converted into rod by increasing length. Tube-type particles can
be prepared by using template method. In this, template will be removed by heating or dissolution
after formation of material. Different shapes such as (4) needle, wire, (5) triangular, prism, (6)
cuboid, (7) fibrous, (8) oblate, (9) sheet, (10) star, etc., can be prepared by chemical or physical
methods
5 Particle Size and Shape Engineering for Advanced Materials 145

Fig. 5.8 Many particles having irregular shapes

Different shapes such as needle, wire, triangular, prism, star, cuboid, oblate, fibrous,
sheet, etc., can be prepared by chemical or physical methods. Those are highly regular.
However, many particles having irregular shapes are obtained (Fig. 5.8). In this,
determination of shape and size is very difficult. Sometimes, many nanostructures
of hollow, core–shell structure, dispersion of small-size particles in core surrounded
by shell or dispersion of particles in another phase or hybrid are obtained from
synthesized particles and nature (Fig. 5.9).

Fig. 5.9 Many nanostructures of hollow, core–shell structure, dispersion of small-size particles in
core surrounded by shell
146 R. S. Ningthoujam and A. K. Tyagi

5.4 The Role of Nanosized Particles in Advanced Materials

and Recent Advances in Nanoscience
and Nanotechnology

When atoms or ions come closer with or without external forces, they can form
molecule (Fig. 5.2). For example, H atoms prefer to form molecule, whereas He
atoms prefer to exist independently. Many atoms or ions prefer to form molecule
after gaining or loosing electrons or balancing with counter ions so that they stabilize
at lower energy. The group of molecules can form cluster. With further addition
of atoms or ions or molecules, cluster can exist as independent entity since size
increases. Generally, sizes of atoms or ions vary from 0.3 to 2.2 angstrom (10–10
m = 1 Å). Sizes of smaller clusters are in the range of 5–10 Å. The smaller-sized
clusters can be dissociated into atoms or ions or molecules if binding energy among
them is weak. The larger-sized cluster in the range of 20–100 Å can exist as solid,
in which their binding energy is strong. The binding energy is related to lattice
energy in case of solid. The solid means the rigid structure, in which movement of
atoms or ions is restricted, but only vibrations of chemical bonds can take place.
Usually, atoms or ions in solid are arranged in a highly ordered microscopy structure
(in x-, y-, and z-axes) forming lattice. In few cases, disorder in arrangement of
atoms or ions is found. They are divided into two groups: crystalline and amorphous
solids when atoms or ions are arranged in order and disorder, respectively. The
larger-sized clusters are known as nanosized particles. Nanosized particles exhibit
the different properties such as magnetic property, electrical resistivity, catalytic
property, hardness, thermal and chemical stabilities, etc., as compared to their bulk
counterpart. Here, bulk counterpart means micron-sized particle. 1 micron is equal
to 1000 nm. The chemical bonding among atoms or ions will be of ionic bonding
(electrostatic), covalent bonding (sharing of electrons), metallic bonding. Generally,
they are very stable in solid form. There are other solids, which are possible under
high pressure and low temperature. Molecules such as Ar, H2 , CCl4 , CO2 , N2 , I2 ,
HCl, H2 O, NH3 can form solids, and the chemical bonds are of London dispersion
forces, electric dipole–dipole interaction, and hydrogen bonding [81, 82].
Science dealing with nanosized particles (1–100 nm) is known as nanoscience.
Thus, all branches of science, such as biology, chemistry, physics, and engineering,
and their interface branches such as microbiology, biotechnology, environment, etc.,
are interrelated after evolution of nanoscience. This brought many interesting applica-
tions in different areas such as pharmaceutical (new design of drug, minerals, formu-
lation), health care (drug delivery, treatment and diagnosis), agriculture (control of
disease, crop protection, better seeds, livestock productivity), water treatment (safe
use, purification, removal of toxics), diseases (removal of bacteria, virus, and fungus,
early detection), energy storage (solar power, wind power), environment (preparation
of compounds using green chemistry route), data storage (a few terabytes), cosmetics
(protection from fungus in homes, cars, and bus using Ag-TiO2 , protection from UV
lights coming from sun), robotics, computer, information, ceramic industry, glass
industry, metal industry, day-to-day uses, etc. Technology dealing with application
5 Particle Size and Shape Engineering for Advanced Materials 147

Fig. 5.10 Schematic representation of aggregation and agglomeration of small-sized particles

of nanomaterials is known as nanotechnology. In view of this, we need to understand

basic concept of nanoscience, development, and its applications in society.
In case of structural materials, there are variations in physical properties with
decrease in particle size or dimension (3D to 2D to 1D to 0D). Many physical and
chemical observations of materials are observed with respect to particle size and
shape; and these are discussed here.

5.4.1 Aggregation and Agglomeration

When small-sized particles are prepared in aqueous medium, attractive forces, such as
dipole–dipole interaction, though electric or magnetic or both forces arise, and thus,
they get agglomerated and with longer time, get aggregated (Fig. 5.10). Agglom-
eration can be minimized by dispersion of particles in another medium having
capping agents and followed by ultrasonication. Agglomeration has weak bonds
between particles. In case of aggregation, it is difficult to separate particles. There
are many other ways to reduce aggregated particles using digestion method. Such
aggregated or agglomerated particles have different properties from those particles
having monodispersed nature.

5.4.2 Atomic Structure in Lattice

In single crystal, defects of atoms in lattice sites are negligible. Thus, it is perfect
lattice in 3D directions. In case of polycrystalline materials, there are two types of
lattice due to particle size [69]. One type of polycrystalline materials is microcrys-
talline, where particle size is of the order of microns. Here, one particle can have many
148 R. S. Ningthoujam and A. K. Tyagi

grains (G), and in between grains, there is a grain boundary (GB). Size of GB is so
small as compared to that of G (Fig. 5.4). Thus, effect of GB in properties is minimum.
Another type is nanocrystalline, where particle size is of the order of nanometers (d
= 1–100 nm) (Fig. 5.5). Here, effect of GB is high. In 1–2 nm size, effect of GB can
change chemical and physical properties. Even, density of GB is almost same as G
in 1 nm-sized particle. Atomic density in one site (A) is different from another (B)
or (C) site (Fig. 5.11). The grains or crystallites are arranged in different orientations
in neighbor. Many dangling bonds on the surface of particle arise if small-size parti-
cles are prepared in inert atmosphere. Number of dangling bonds can be minimized
using suitable surfactant/capping agent. Such dangling bonds can change chemical
and physical properties. In ambient or oxygen atmosphere, such dangling bonds are
very reactive to form oxide layer over particles (Fig. 5.12). If exposure is longer,
it can form core@shell particles (here shell is oxide layer). With further decrease
in particle size, stability decreases. At extreme decrease in particle size, it becomes
amorphous or disorder in atomic arrangement or cluster of atoms.
Porosity is also an important parameter to measure void or empty spaces in a mate-
rial (soils, particles prepared in lab, and natural particles). In prepared particles of
carbon and silica, size of pores can vary from 1–2 nm (microporous) to 50 nm (meso-
porous). Their atomic structures are different from single crystal lattice. Layered

Fig. 5.11 2D lattice of a particle of Ni (Nanocrystalline) having three crystallites and atomic
bonding structures in an inert environment. Magnetic properties of Ni will vary with decrease in
particle size due to effects from surface dangling, lattice defects, and grain boundary.
5 Particle Size and Shape Engineering for Advanced Materials 149

Fig. 5.12 2D lattice of a particle of Ni (Nanocrystalline) having three crystallites and atomic
bonding structures in an oxygen or ambient environment. Magnetic properties of Ni will vary with
decrease in particle size due to effects from surface dangling, surface oxide layer, lattice defects,
and grain boundary. Ni (ferromagnetic)@NiO (antiferromagnetic) heterostructure can be defined
after long exposure in an oxygen or ambient environment

structured compounds have different atomic structures as compared to their corre-

sponding other phase. These materials have potential applications such as removal
of toxic ions or gases, drug delivery, battery, catalysts, ion-exchange, etc.

5.4.3 Magnetic Properties

Types of magnetic materials include ferromagnetic or ferrimagnetic, antiferromag-

netic, paramagnetic, and diamagnetic materials [83]. In case of ferromagnetic or
ferrimagnetic material, they have spontaneous magnetization, Curie temperature
(ferromagnetic to paramagnetic transition, Tc ), coercivity (Hc ), retentivity (Mr ), and
saturation magnetization (Ms ). In case of antiferromagnetic material, they show the
magnetic transition known as Neel’s temperature (antiferromagnetic to paramag-
netic transition, TN ). In case of paramagnetic materials, magnetization value is very
small and magnetization decreases with increase of temperature following Curie law.
Magnetic field can influence magnetization of ferromagnetic and antiferromagnetic
materials, but its effect will be less in paramagnetic material. In diamagnetic mate-
rial, moment is negative and small; and under applied magnetic field, its spin tries
150 R. S. Ningthoujam and A. K. Tyagi

to oppose magnetic field. These types can be distinguished on the basis of ratio of
magnetization to applied magnetic field with temperature (χ = M/H vs. T) (Fig. 5.13).
Intrinsic magnetic properties of materials do not change in case of macrocrystalline
particles (size of 1–10 μm).
When size of particle reduces to nanometer range, their magnetic properties are
different from intrinsic properties. First, ferromagnetic material will be discussed.
In micron-sized particles, particles are considered as multi-domain, where magnetic
domains have spins and surrounded by domain walls (Fig. 5.14). Because of pres-
ence of domain walls, it has coercivity (Hc ) and magnetic retentivity (Mr ), saturation
magnetization; and it shows the hysteresis loop upon changing magnetic fields in
opposite directions (+ve and –ve directions) at large values of 2–3 T [83]. With
decrease in particle size, the saturation magnetization decreases, and on further
decrease in particle size, it does not achieve saturation magnetization, and even does
not have Hc or Mr . In such situation, particles are so small that without magnetic
field, it does not have magnetization just like paramagnetic nature. Such particles are
considered as superparamagnetic particles, in which individual particle is assumed
as a single domain (Fig. 5.14).
In an assembly of single-domain particles, there is a product of volume (V) and
anisotropic constant (K) (KV = particle energy or anisotropy energy), which is much
less than that of room temperature energy (kT). It changes the direction of magne-
tization of a particle from one easy direction to the opposite within 10–9 s [84–86].
Net moment becomes zero. In case of normal paramagnetic materials, such as (Na,
K), K is zero. In superparamagnetic particles, K is not zero, but the particles behave

Fig. 5.13 Schematic representation of magnetic susceptibility–temperature curves for different

types of magnetic materials: Paramagnetic, diamagnetic, ferromagnetic, and antiferromagnetic
behavior can be observed. Paramagnetic substance shows the decrease in susceptibility with temper-
ature, i.e., it follows the Curie Law. Diamagnetic substance has negative susceptibility. Ferromag-
netic substance shows the ferromagnetic to paramagnetic transition (Tc ), known as Curie temper-
ature. Inset shows the behavior of susceptibility above Tc . Antiferromagnetic substance shows
antiferromagnetic to paramagnetic transition (TN ), known as Neel’s temperature
5 Particle Size and Shape Engineering for Advanced Materials 151

Fig. 5.14 Schematic representation depicting a multi-domain, b single domain, and c Hc versus
particle size

as paramagnetic because anisotropic energy (KV) is dominated by the surrounding

energy. Every domain or particle can have high moment of 103 –105 μB on the basis of
chemical formula of atoms or molecule. Thus, the term ‘super’ is added to paramag-
netic as prefix. The relaxation time (τ) is the average time to decay the magnetization
value to 1/e of its initial one as given by

1
= f 0 e− kT
KV
(5.1)
τ
In case of high temperature T (kT >> KV), the time-scale of thermal relaxation is
much faster than the experimental time window (1–50 s), net moment becomes zero
and it becomes superparamagnetic (Fig. 5.15). In case of very low temperature T (kT
<< KV), the relaxation time is very slow as compared to experimental time window,
it shows magnetic moment, and thus, it can show the ferromagnetic behavior. The
temperature at which thermal relaxation is equal to experimental time window is
known as the blocking temperature (Tb ), and above this, it behaves as superparam-
agnetic, and below this, it behaves as ferromagnetic. The Tb value decreases with
decrease in particle size.
The coercivity (Hc ) of ferromagnetic materials decreases with decrease in particle
size. However, there are two different variations in Hc (Fig. 5.14) [83]. With decrease
in particle size in polycrystalline ferromagnetic materials (multi-domain region),
there is an increase of Hc , and it reaches the highest value when size of particle
becomes single domain or critical size (each particle acts as single domain), and
then decrease in Hc is found with further decrease in particle size. Hc becomes zero
when particles are so small. These particles are considered as superparamagnetic
particles, in which relaxation of magnetization is so fast (10–9 s). The direction of
magnetization varies from easy direction 0–180° within 10–9 s.
152 R. S. Ningthoujam and A. K. Tyagi

Fig. 5.15 Schematic diagram depicting change in easy direction of magnetic domain with decrease
in particle size in room temperature (kT, k is Boltzmann constant). K and V represent anisotropic
constant and volume of particle, respectively

There is a decrease in ferromagnetic to paramagnetic transition (Curie tempera-

ture, Tc ) with decrease of particle size. This is due to decrease in exchange interaction
in magnetic structure. E.g., Bulk MnFe2 O4 has Tc at 570 °C and saturation magneti-
zations (Ms ) at 110 and 80 emu/g at 10 and 300 K, respectively [87]. With decrease
in particle size down to 5 nm, their Ms and Tc are found to decrease. This is known
as finite size effect of nanoparticles on magnetic properties.
Apart from particle size effect on magnetic thermal relaxation of superparamag-
netic particles, contribution of surface dangling bonds in small-sized particles must
be considered. Even defects in lattice are also associated in small-size particles. Thus,
whenever magnetic properties of small-size particles are discussed, effect of small
size (KV), surface dangling bonds, and defects in lattices are required (Fig. 5.11).
The effect from surface oxidation or chemical-absorption of gases such as CO2 ,
H2 , H2 O, CO2− 3 is also required in small-size particles if experiment is performed
in ambient atmosphere (Fig. 5.12). Such ferromagnetic core will be surrounded by
antiferromagnetic oxide layer or paramagnetic spins arose from surface or lattice.
Sometimes, exchange bias behavior from ferromagnetic@antiferromagnetic inter-
face interaction may arise [88]. Also, cation distribution in ferrites, hexaferrites, and
garnet compound needs to be considered during interpretation of magnetic properties
[83, 89].
When shape of particles changes from spherical to rods or needle or any shape,
the coercivity of ferromagnetic materials increases. This is due to enhancement in
magnetocrystalline anisotropic constant (Keff ) [83].
There is a decrease of magnetization (emu/g) of ferromagnetic materials with
decrease in particle size. The bulk magnetization of Fe3 O4 at room temperature is
90 emu/g and particles of 8–30 nm size have 30–70 emu/g [90–93]. With change
in shape from spherical to rods or needle in particles, there is an enhancement of
magnetization in nanosized particles.
5 Particle Size and Shape Engineering for Advanced Materials 153

Fig. 5.16 Schematic diagram depicting change in spin structure in diamagnetic and antiferromag-
netic particle when size of particle decreases

Now, what behaviors can be seen in antiferromagnetic materials upon decreasing

particle size? It can show three types of behavior: (1) reduction in TN and amount
of paramagnetic character may be increased, (2) finite size effect on TN (in case of
antiferromagnetic material) or TC (in case of ferromagnetic material), and (3) change
from antiferromagnetic to ferromagnetic behavior (Fig. 5.16) [94, 95]. Diamagnetic
particles become a weak ferromagnetic character (bulk ZnO particles are diamagnetic
at room temperature and exhibit a weak ferromagnetic in case of small-sized particles
due to localized ordering of uncompensated spins which come from defects in lattice)
(Fig. 5.16) [51, 96]. In case of paramagnetic materials, the effect of particle size will
be less.

5.4.4 Electrical Resistivity Property

There is an increase of metallicity with reduction in dimension in case of 3D (graphite)

to 2D (graphene) in carbon allotropes. Diamond shows insulating behavior and has
the highest electrical resistivity as compared to carbon nanotubes, graphite, and
graphene in carbon allotropes.
The electrical resistivity (ρ) of elemental metals such as Ag, Au, Cu, Ni, Sn,
Gd increases with decrease in particle size [69, 97]. This is due to association of
grain boundaries (gb) and surface effect associated in nanocrystalline materials. The
electron mean free path decreases with decrease in particle size. It is to be noted that
one particle of nanocrystalline material composes of many small crystallites/grains
(g), and in between crystallites, there are grain boundaries. Different orientations
154 R. S. Ningthoujam and A. K. Tyagi

of crystallites or lattices are observed in a particle. The path of electrons is not

disturbed in crystallite region due to order of atoms/ions, but is disturbed by grain
boundaries. Thus, mean free path of electrons decreases in nanocrystalline materials
as compared to bulk or single crystal. Thus, electric resistivity follows the same trend.
The electron scattering is more in case of nanocrystalline materials as compared to
that of microcrystalline materials (Fig. 5.17).
At room temperature, additional resistivity in nanosize particles is related to
ρ0 × λ/d, where parameters such as ρ0, λ, and d are the room temperature resis-
tivity, mean free path of electron-phonon scattering, and length scale, respectively
[98]. Here, length scale is related to the wire width or grain size which can add surface
and grain boundary scattering. These are important in choosing suitable elemental
wire for downscaling of integrated circuits. 10 nm wide Cu interconnect lines have
higher resistivity than that of bulk.
Electron mean path values of Ag, Cu, Au, and Ni are 53.3, 39.9, 37.7, and 5.87 nm,
respectively, at room temperature [99]. The room temperature resistivity values of
Ag, Cu, Au, and Ni are 1.587, 1.678, 2.214, and 6.98 μ-cm, respectively. Thus,
Ag is the best conductor among these. In same length scale (d), the product of ρ0 ×
λ will have minimum value for Ni as compared to others. Thus, Ni will have good
conductor for downscaling of integrated circuits.
At low temperature, electrical resistivity (ρ T ) for clean metal is given by:

ρT = ρe + ρi (5.2)

where ρ e and ρ i represent the resistivity arising from the elastic and inelastic
scattering, respectively. The ρ e arises from impurities, defects, or disorder and is

Fig. 5.17 a A schematic view of simple understanding of the scattering of an electron when it
travels a fixed distance in a micron-size crystal and a nanocrystal. b Schematic representation of
electrical resistivity versus temperature at low temperature for clean and dirty elemental metals.
Curves are the simulated data representation
5 Particle Size and Shape Engineering for Advanced Materials 155

considered as the residual resistivity (ρ 0 ). The ρ i arises from the electron-electron (e-
e), electron-phonon (e-ph), and/or electron-magnon (e-m) effects and is proportional
to the term βT n (2 ≤ n ≥ 5 for T ≤ 0.25θ D, and the θ D is the Debye temperature of
metal [100–102]. Thus, electrical resistivity (ρ T ) for clean metal can be written as

ρT = ρ0 + βT n (5.3)

The ρ-T behavior is shown in (Fig. 5.17). Resistivity increases with temperature. It
shows the positive coefficient of resistivity. With increase in value of ρ0 , the behavior
in ρT -T curve is also shown. The curve is almost a straight line when system becomes
highly dirty due to the presence of impurities, defects, or disorder. Then, resistivity
decreases with increase in temperature. The nature of curve is like a semiconductor
behavior.

5.4.5 Optical Property

Only when particle size of semiconductor is less than exciton Bohr radius, its band
gap is found to be more than that of bulk. This is due to the quantum confinement
effect. Those particles below exciton Bohr radius show the enhancement of band
gap with decrease of particle size. Discrete peaks below the minimum absorption
energy peak (Emin ) are generally observed in QDs. The wavelength corresponding
to Emin increases with increase of size in QDs. It is to be noted that one emission
peak is observed at near to Emin . The wavelength corresponding to Emin in absorption
spectrum is slightly less than that corresponding to emission peak. The absorption
and emission peaks related to surface defect of semiconductor are generally broad.
Band gap of QDs can be explained by taking formation of molecule from
atoms/ions [55]. During formation of molecule, the bonding and anti-bonding orbitals
(BMO and AMO) are formed with a particular energy gap (E). With addition of
atoms/ions to the molecule, it forms a cluster by reduction of chemical potential
of system. With further addition of atoms/ions, formation of QDs in semiconductor
starts. Discrete energy levels arise in BMO and AMO. This discrete energy levels
come closer when particle size is reaching critical size, known as the exciton Bohr’s
radius. For particle size above Bohr’s radius, it behaves as normal semiconductor
(valence and conduction bands). Evolution of QDs from atoms/ions is shown in
Fig. 5.18. It is to be noted that the attractive and repulsive forces arise with addition
of atoms/ions to the system.
QDs are considered as 0D. In QDs, band gap increases with decrease of particle
size. In case of PbSe, bulk has the band gap of 0.26 eV, but QDs with sizes of 2,
4, and 6 nm have the band gaps of 2.06, 1.07, and 0.77 eV, respectively [103]. This
happens when crystalline particle size is less than the exciton Bohr radius of material.
It is to be noted that bulk PbSe has the exciton Bohr’s radius (46 nm). Those particle
sizes less than this 46 nm show the blue shift in band gap as compared with the
bulk value. Many discrete energy absorptions can be seen in addition to minimum
156 R. S. Ningthoujam and A. K. Tyagi

Fig. 5.18 Evolution of QDs from atoms/ions along with bulk semiconductor. AMO and BMO in
nanoparticles can be considered as conduction band and valence band of semiconductor, respectively

energy absorption. This is known as the quantum confinement effect in the solid-
state communities. TEM micrographs of PbSe particles prepared at 140 °C with
waiting time (Wt ) of (a) 0.5, (b) 2, (c) 5, (d) 10, and (e) 30 min, and (f) schematic
representation of monomers, cluster, and QDs of PbSe are shown in Fig. 5.19. Since
the particle size for Wt = 0.5 min is too small, its size could not be determined
exactly. The particle sizes for Wt = 2, 5, 10, and 30 min are found to be 4.1, 5.1, 5.4,
and 6.3 nm, respectively. The UV-Visible-NIR spectra of PbSe samples prepared
at (a) room temperature (22 °C), (b) 80 °C, and (c) 100 °C with different Wt are
shown in Fig. 5.20. PbSe QDs prepared at 180 °C with Wt = 15 min show the
absorption bands at 675, 1110, 1452, 1715, 2118, and 2397 nm. These are assigned
to the discrete levels due to quantum confinement. With increase in Wt at a particular
temperature or heating temperature, minimum absorption peak is found to shift to
longer wavelength suggesting increase in size of QDs. Magic-sized cluster is obtained
for sample prepared at room temperature. Samples prepared at 80, 100, and 180 °C
show the behavior of QDs. Figure 5.21 shows the photoluminescence (PL) of PbSe
sample prepared at (a) room temperature (22 °C), (b) 80 °C, and (c) 100 °C with
different Wt after excitation at 600 nm CW laser (HeNe), and (d) PL decay of PbSe
QDs having emission peak at 1300 nm and excitation wavelength at 600 nm. Data
are fitted with monoexponential equation. At room temperature, emission peak at
790 nm is obtained. With different waiting times, peak does not shift indicating
the presence of magic-size particles. PL spectra of sample prepared at 80 °C for
different Wt times show that there are shifts in emission peak at longer wavelength
with increase in Wt indicating particle size effect in QDs. Emission peaks at 1078,
1257, and 1360 nm for Wt = 45, 60, 120, and 180 min, respectively, are observed.
PL spectra of sample prepared at 100 °C for different Wt = 10, 15, 30, and 60 min
show peaks at 1127, 1215, 1363, and 1481 nm, respectively.
The lifetime values for QDs having emission peaks at 1300 and 1535 nm are
obtained to be 1.3 and 1.0 μs, respectively.
5 Particle Size and Shape Engineering for Advanced Materials 157

Fig. 5.19 TEM images of PbSe particles prepared at 140 °C with waiting time (Wt ) of a 0.5,
b 2, c 5, d 10, and e 30 min. f Schematic representation of monomers, cluster, and QDs of PbSe.
Reproduced with permission from PCCP Owner Societies and RSC Publications as a co-author of
this paper [103]

As compared to bulk, the quantum yield of emission from QDs can be increased
to 80–95%. Generally, luminescence intensity is improved with decrease of particle
size in QDs and peaks are sharp. This is opposite to bulk or micron-sized particles
because non-radiative from surface effect is associated.
QDs of PbSe nanoparticles are prepared by injecting Se-TOP into Pb-oleate in
1-Octacence, which was kept at 80–170 °C [103]. With different waiting time at a
particular temperature, size of QDs can be varied. Instead of Se-TOP, when Se-TDP
(TDP = tris(diethylamine)-phoshphine) is added to Pb-oleate in 1-Octacence, which
was kept at 170 °C, it forms PbSe of nanorods [104]. Depending on the ratio of Pb
and Se, the different lengths of nanorods are prepared. With increase of waiting time,
length of nanorods increases (Fig. 5.22), and also absorption peak shifts to longer
wavelength with increase in length (Fig. 5.23).
158 R. S. Ningthoujam and A. K. Tyagi

Fig. 5.20 The UV-Visible-NIR spectra of PbSe samples prepared at a room temperature (22 °C),
b 80 °C, and c 100 °C with different waiting times (Wt , minutes). d PbSe QDs prepared at 180 °C
with Wt = 15 min show the absorption bands at 675, 1110, 1452, 1715, 2118, and 2397 nm, which
are assigned to the discrete levels due to quantum confinement. Reproduced with permission from
PCCP Owner Societies and RSC Publications as a co-author of this paper [103]

Many shapes of PbSe nanoparticles can be prepared using noble metal nanopar-
ticles (Au, Ag, or Pd) as seed. Here, concentrations of the seed and precursors are
varied. Various shapes such as quantum dots, cubes and stars of nanostructures are
prepared. The yield is very high (Fig. 5.24) [105].
It is to be noted that excitons are the imaginary quasiparticles produced by pairing
of an electron (from the conduction band) and a hole (from the valence band), due to
Coulombic interaction [55]. It forms H-like atom states with diameter significantly
larger than the unit cell length. The exciton radius (Rb ) can be calculated from the
effective masses of electron (me *) and hole (mh *) and dielectric constant of medium
(ε), and their relation is given below:
 
h2 1 1
Rb = + (5.4)
e2 m ∗e m ∗h

As the band gap of nanoparticle semiconductor (Eg ) is more than the bulk
(Eg (R → ∝)) due to the quantum confinement effect (QCE), their relationship
5 Particle Size and Shape Engineering for Advanced Materials 159

Fig. 5.21 PL spectra of PbSe sample prepared at a room temperature (22 °C), b 80 °C, and c 100 °C
with different waiting times (Wt , minutes). d Luminescence decay of PbSe sample having emission
peak at 1300 nm. Data are fitted with monoexponential equation. Excitation wavelength is fixed
at 600 nm. Reproduced with permission from PCCP Owner Societies and RSC Publications as a
co-author of this paper [103]

is given below:
 
h2 1 1
E g = E g(R→∞) + + ∗ (5.5)
8R 2 m ∗e mh

where R is the radius of particle size assuming it to be a spherical particle.

Even particle size of material slightly greater than that of the exciton Bohr radius
can show the quantum confinement when particles are dispersed in another dielectric
medium or core–shell formation. For example, SnO2 has the exciton Bohr radius of
2.4 nm, which is too small. Thus, it is difficult to prepare QDs of SnO2 . But SnO2
having particle sizes of 3 and 5 nm can show quantum confinement when dispersed
in TiO2 , SiO2 , or Y2 O3 matrix [106–110].
There is a report on increase of band gap for MoS2 with reduction of dimension
from 3D (E = 1.23 eV, bulk) to 2D layers (E = 1.88 eV, monolayer) [111].
160 R. S. Ningthoujam and A. K. Tyagi

Fig. 5.22 TEM images of different growth times/waiting times: a Wt = 30 s, d = 3.9 nm; b Wt
= 2 min, d × L = 3.8 × 21 nm2 ; c Wt = 4 min, d × L = 4.1 × 44 nm2 ; and d Wt = 8 min, d
× L = 5.7 × 35 nm2 . (d is diameter of the rods and L is the length of the rods). Reproduced with
permission from ACS Publications [104]

Fig. 5.23 Absorption spectra of different growth times/waiting times: a 30 s, d = 3.9 nm; b Wt
= 2 min, d × L = 3.8 × 21 nm2 ; c Wt = 4 min, d × L = 4.1 × 44 nm2 ; and d Wt = 8 min, d
× L = 5.7 × 35 nm2 . (d is diameter of the rods and L is the length of the rods). Reproduced with
permission from ACS Publications [104]
5 Particle Size and Shape Engineering for Advanced Materials 161

Fig. 5.24 TEM images of and transmission electron diffraction from PbSe nanocrystals: a–d,
g Reactions carried out at 125–135 °C, e, f reaction carried out at 155 °C. a Final products as
a mixture of Au-Fe3 O4 seeds and PbSe nanorods. PbSe nanorods extracted at b 4, c 7, d 9 min
waiting time, e 30 s, and f 90 s waiting time after selenium injection. g TEM image of branched
PbSe nanocrystals produced after 8 min of reaction at 125–135 °C using ½ the quantity of seed
particles used for the samples shown in (a)–(f). h Electron diffraction pattern of the final products
in (a). Reproduced with permission from ACS Publications [105]

In case of carbon allotropes, graphite belongs to 3D type having semiconducting

property with narrow band gap of 40 meV, whereas graphene belongs to 2D having
semi-metallic property [112]. Their properties in 2D and 3D are largely different
even though chemical formula of molecule is same.
In metallic systems such as Ag, Au, and CuS nanoparticles, surface plasmon
resonance (SPR) spectrum is observed [113]. In case of nanorods, two SPR peaks
corresponding to diameter of rod (at lower wavelength, which is similar to spherical
nanoparticles) and length (at longer wavelength due to longitudinal polarization
effect) are observed.

5.4.6 Bulk Density of Materials

Nanocrystalline materials have lower temperature to achieve 95–99% theoretical

density as compared to coarse micron-sized particles [69]. The TiO2 nanocrystalline
12 nm shows enhanced densification as compared to 13 μm at same temperature of
heat-treatment, say at 900 °C. The pore or void density is less in case of nanocrys-
talline TiO2 as compared to that in micron particles. This is confirmed by enhanced
decrease of a positron annihilation lifetime in case of nanocrystalline sample (about
390 ps) as compared to that in micron particles (about 420 ps). Doping of Y in
nanocrystalline TiO2 enhances densification, but their grain size decreases.
162 R. S. Ningthoujam and A. K. Tyagi

With increase of consolidation pressure up to 3 GPa, nanocrystalline Fe particles

(6–10 nm) show additional broadening in sextet spectrum of Mossbauer recorded at
77 K [69]. One sextet is fitting with α-Fe in perfect lattice and broadening comes from
Fe atoms in grain boundary. This is due to increase in grain boundary percentage,
and simultaneously, percentage of pore or void present in lattice decreases. The
broadening in peak decreases after annealing nanocrystalline Fe at 500 °C for a few
hours in vacuum. In this way, size of particles increases to bulk. This is also proved
by positron annihilation data of nanocrystalline Ni (in which two lifetime data (183
and 291 ps) are observed and corresponding to the presence of vacancies or pores of
two different types).
Absorption of H2 occurs in case of Pd [69]. Nanocrystalline Pd has more storing
capacity of H2 as compared to single crystalline Pd. This is due to presence of grain
boundaries in nanocrystalline Pd. Usually, H2 molecules or atoms occupy interstitial
sites of Pd (tetrahedral and octahedral sites) in case of single crystal, and occupy
interstitial sites as well as grain boundaries in case of nanocrystalline.

5.4.7 Variation in Properties from Single Layer

to Multilayer/Heterstructures/Superlattice

With change from single layer to multilayer or heterostructure (–A/B/A/B/A–), lumi-

nescence intensity can be improved. This happened in LEDs such as GaN/InN or
GaN/AlN heterostructures as compared to pure GaN, InN, or AlN [100, 114]. In
heterostructures, photo-catalytic property can be improved due to tuning of band
bending at Fermi energy [78].
Even, giant magnetoresistance (GMR) is observed in such as multilayer or super-
lattice system of Fe/Cr/Fe or Fe/Mn/Fe, Co/Cr/Co, Co/Mn/Co, and enhancement in
GMR is observed with increase of multilayers [115–117]. Each layer has 5–20 Å
thickness. This provides higher data storage capacity. Schematic diagram show the
resistivity drop in the presence of a few Tesla (Fig. 5.25). Fe or Co is ferromagnetic
and Cr or Mn is antiferromagnetic in nature. Without magnetic field, antiferromag-
netic coupling between Fe and Cr occurs, and thus resistance is very high. In the
presence of magnetic field, all spins in Fe and Cr are parallel to each other, and thus,
resistance is dropped significantly.

5.4.8 Evolution of Multifunctional Materials

by the Formation of Core–Shell or Composite or Hybrid

In case of noble metals such as Ag and Au, these are often found in rocks, rivers,
ponds, muds, etc., and their intrinsic properties do not change much. However, in case
of Fe and Co, they do not exist freely in nature. They are highly oxidized and form
5 Particle Size and Shape Engineering for Advanced Materials 163

Fig. 5.25 Resistivity versus Magnetic field in Fe(001)/Cr(001)/Fe(001) layer: magnetic superlat-
tice. This is redrawn from Ref. [115–117]

oxides in ambient atmosphere. Even, some oxides such as Fe3 O4 are slightly stable
as compared to pure Fe, but they are less stable than that of α-Fe2 O3 [93, 118]. It
means that unstable phase can form core–shell formation in native oxygen or ambient
environment. With time, they are converted to stable phase. For example, Fe3 O4
particles are converted to α-Fe2 O3 with time or by heating. This can be represented
by core–shell model: Fe3 O4 (t = 0 s), Fe3 O4 @α-Fe2 O3 (t = 30 days), α-Fe2 O3
(1 year).
When there is a decrease of particle size down to nanometer, the chemical and
physical properties of materials change. The chemical stability is less than that of
bulk. Even in inert atmosphere, percentage of surface dangling bonds increases with
decrease in particle size, and thereby their magnetic properties are varied: decrease in
magnetization and Curie temperature. Increase of surface dangling bonds can form
ferromagnetic core@antiferromagnetic shell that is confirmed by exchange bias in
coercivity study [119].
With decrease of particle size in noble metals such as Ag and Au, electron density
of states at the surface of particles is different from their bulk. They result in the
surface plasmon resonance (SPR) effect [113].
Intentional addition of shell or conjugation of another material can change prop-
erties of particle. Even co-doping to host can improve properties in terms of lumi-
nescence and magnetic properties. Examples are SnO2 @SiO2 , SnO2 -SiO2 , SnO2 -
TiO2 , Au@UNPS (UCNP = unconversion nanoparticles), AVO4 :RE, APO4 :RE,
NaYF4 :RE, and their core shell (shell = same host material or another mate-
rial; RE = rare-earth) [106–110, 120–137]. Luminescence intensity is generally
improved in case of core@shell structures. AVO4 :RE@AVO4 , AVO4 :RE@SiO2 ,
NaYF4 :RE@NaYF4 have more luminescence intensity as compared to that
164 R. S. Ningthoujam and A. K. Tyagi

of core counterpart. The hybrid of magnetic and luminescence nanoparti-

cles such as CaF2 :Eu-Mn@Fe3 O4 , YVO4 :Eu @Fe3 O4 , UNPS@Au@Fe3 O4 ,
NaErF4 :Tm@NaYF4 :Yb, CaMoO4 :Tb@Fe3 O4 , Mn0.5 Fe2.5 @YVO4 :Eu3+ show
interesting properties as compared to individual materials [36, 120, 122, 123, 133,
134]. These materials have potential for bio-imaging and therapy under AC magnetic
field and under NIR laser excitation. This can bring multi-functional materials after
conjugation of two or more materials having different properties.

5.4.9 Change in Crystal Structure or Crystallinity

with Reduction in Particle Size

In general, crystallinity decreases with decrease in particle size in nanosized range.

With decrease of particle size, stability of a phase or crystal structure changes [138].
Metal bulk cobalt (Co) exits into two forms, HCP and FCC phases. With decrease of
particle size to 10 nm, a new phase ε-Co (structurally related to the β phase of Mn)
is formed.
In bulk form, insulator alumina (Al2 O3 ) exits in α-form. However, with decrease
of particles, another crystal structure of γ-form is formed [139–141]. This is due to
increase of surface area with decrease of particle size. This surface energy is taking
main role in formation of γ-form.

5.4.10 Induced Electric Field or Induced Magnetic Field

Study

MoS2 (bulk) and MoS2 nanosheets are semiconductors. Upon applying electric field,
bulk MoS2 can be brought to superconducting at 9.4 K [142].

5.4.11 Thermodynamic Properties (Excess Enthalpy, Melting

Point) with Decrease in Particle Size

Generally, surface energy is higher in case of small-sized particles as compared to

bulk particles. Because of this, their chemical and physical properties are different
from bulk. The excess enthalpy of SnO2 increases with decrease of particle size
[143]. The melting point decreases with decrease in particle size of material [69].
5 Particle Size and Shape Engineering for Advanced Materials 165

5.4.12 Surface Functionalization, Processing, and Finishing

for a Particular Application

Surface functionalization is necessary to get desired products. For biomedical appli-

cation, proper surface functionalization is required, so that particles become highly
dispersible in water, have longer stability in the blood flow, become specific to target,
have chemical stability, and are highly biocompatible. For ceramic application, mate-
rial should be highly stable at higher temperature [54]. For purpose of smart materials,
it should have high sensitivity at any change of pH, temperature or pressure or mois-
ture or gases. In this, proper fabrication and engineering aspect is necessary [144].
For coating materials, nitrides, carbides, borides, and oxides can be used [53, 100,
145]. For covering precious materials, light materials having carbon or aluminum
matrix can be used. Since carbon nitrides and boron nitrides are very light, stable,
and have high mechanical stability, they are used as bullet protecting materials [146].
They are usually inert to other materials. Dynamic impact resistance tests of these
nitrides exhibit that the wearable electronic textile (WET) absorbs all the impact
energy.
For coloring of materials with golden color, TiN can be coated over material [53,
100]. For making of drilling machine and ultra-hard materials, nitrides and carbides
are used [53, 100]. Carbon nitrides and WC are used for such purposes. LaB6 has been
used as electron emitter in electron microscopy [53, 100]. Silicon nitride and carbon
nitrides are used as tip in atomic force microscopy [53, 100]. For solder materials,
lead-free materials containing Sn, In, Zn, Cu, Bi, Ag have been used [147]. For
cosmetic purpose in paint or face makeup and skin protection, TiO2 , Ag, and ZnO
nanoparticles are added as additive [148]. For battery, many nanoparticles of carbon-
based materials, 2D materials, Li- and Na-based materials are used, and show the
better quality of battery in terms of capacity, reuse through recharge and discharge,
and longer life time [149].

5.5 Determination of Particle Size Distribution

The following statistical terms will be useful in consideration for particle size and
shape distribution.

5.5.1 Gaussian or Normal Distribution (Mean, Median,

and Mode)

Gaussian distribution is commonly considered as normal distribution and is a form of

continuous probability distribution for a real-values random variable. Its probability
density function (fx ) is defined by [150–152]:
166 R. S. Ningthoujam and A. K. Tyagi

Fig. 5.26 a The probability density function f(x) with variable (x) following normal distribution.
b Positions of mean, median, and mode in distribution. All the curves are the simulated data
representation

1
√ e− 2 ( σ )
1 x−μ 2
f (x) = (5.6)
σ 2π

where μ is the mean of expectation of the distribution and σ is the standard deviation
and its square value (σ2 ) is called the variance of the distribution. ‘x’ is variable
value.
Figure 5.26(a) shows the probability density function f(x) with variable (x)
following normal distribution. From this, it is observed that distribution function
is different for various variance values (σ2 ) even though mean value is same (μ = 0).
Figure 5.26b shows the positions of mean, median, and mode in distribution. Mean
is arithmetic average of the data. Median is a value in particle size, and it divides
the population accurately into two equal halves, and this value is in between 50%
above and 50% below distribution. Mode is the most common value of the frequency
distribution, and it is assigned to the highest point of the frequency curve.
Figure 5.27a shows the particle size distribution function f(x) or number of parti-
cles with variable (x) or particle size (D, nm), which follows the normal distribution.
Here, mean, median, and mode have same value, i. e., 10 nm. Figure 5.27b shows
bimodal distribution of particles and both (depicted as ‘1’ and ‘2’) follow normal
distribution. The variable x or change in particle size is exactly same (i.e., ‘1’ has
6–14 nm and difference is 8 nm; ‘2’ has 14–22 nm and difference is 8 nm). Mean is
average of ‘1’ and ‘2’ distributions and this is assigned with 14 nm. However, there
is no particle. Also, the particle size distributions in ‘1’ and ‘2’ are 49% and 51%,
respectively. After removing 1% from ‘2,’ median is obtained. The exact position is
not provided. The mode is assigned to ‘2’ since it has higher population as compared
to ‘1.’ In case of ‘1’ having 6–14 nm and ‘2’ having 14–26 nm, the mean is 16 nm,
and median is assigned above mean (not exact value); and mode is assigned to ‘2’
5 Particle Size and Shape Engineering for Advanced Materials 167

Fig. 5.27 a The particle size distribution function f(x) or number of particles with variable (x) or
particle size (D, nm), which follows the normal distribution. b bimodal distribution of particles and
both (depicted as ‘1’ and ‘2’) follow normal distribution. The variable x or change in particle size is
exactly same (i.e., ‘1’ has 6–14 nm and difference is 8 nm; ‘2’ has 14–22 nm and difference is 8 nm).
c bimodal distribution of particles and both (depicted as ‘1’ and ‘2’) follow normal distribution. The
variable x or change in particle size is exactly same (i.e., ‘1’ has 6–14 nm and difference is 8 nm;
‘2’ has 14–26 nm and difference is 12 nm). (d) bimodal distribution of particles and both. There is
overlapping of both curves. All the curves are the simulated data representation

(Fig. 5.27c). In both Fig. 5.27b and c, there is no overlapping in both ‘1’ and ‘2.’ In
Fig. 5.27d, there is overlapping, the mean is 12 nm, which has particle. From these,
it can be possible to have a number of particle size distributions, such as tri-modal,
etc.

5.5.2 Log-Normal Distribution

In general, particle size distribution is not exactly normal or Boltzmann. There is

randomization in distribution [150–154]. This is usually calculated using log-normal
distribution, and its probability density function (fx ) is defined by:
168 R. S. Ningthoujam and A. K. Tyagi

Fig. 5.28 The log-normal

distribution curves for
different values of mean and
variance

 2
1 − 21 ln(x/μ)
f (x) = √ e σ
(5.7)
xσ 2π

where μ is the mean or expectation of the distribution and σ is the standard deviation
and its square value (σ2 ) is called the variance of the distribution. ‘x’ is variable value.
Exact calculations of mean, median, variance, and mode are slightly different from
those of normal distribution. Figure 5.28 shows the log-normal distribution curves.

5.5.3 Other Distributions

In addition to normal or log-normal distribution, many equations are used to analyze

particle size and shape of particles of inorganic, organic, minerals, food, and
biomaterials. Details can be found in many literatures [152–159].

5.5.4 Aspect Ratio, Regular, and Irregular Shapes

The size and shape of particles prepared in laboratory may vary from spherical to
rod, hollow, star, prism, disc, needle, triangular, tube, fibrous, etc. [155–162]. It
is not so easy to calculate mean, median, and mode using normal or log-normal
distribution when shape changes from spherical to others. Many mineral particles
are available in nature and are used in various industries in catalysis, as fillers, in
coatings, as absorbers, etc. It is required to control particle size and shape for the
5 Particle Size and Shape Engineering for Advanced Materials 169

performance and properties of materials. Even after dispersion in liquid, the rheolog-
ical properties of dispersions depend on analysis of size and shape of particles. For
use of particles as biomaterials, it requires size and shape of particles, chemical and
photo-stability, biocompatibility, mechanical stability, microenvironment, etc. Many
techniques are used to see morphology of particles using sedimentation method
(Stoke’s law), Laser light scattering/projected area (Fraunhofer), Laser light scat-
tering/particle volume (Mie-theory), Photon correlation spectroscopy/translational
diffusion, surface area using BET technique, electron microscopy, DLS (Dynamic
light scatterings) techniques, etc. Still many variations in size and shape of particles
are obtained. Surface area measurement has limitations because even pores available
in particles can provide additional surface area apart from surface of particles.
In disc shape, there are diameter and thickness. With increase of thickness, it
becomes rod shape. In such cases, ratio of major length to minor length can provide
aspect ratio. This is an important parameter in mechanical, rheological, magnetic
properties, etc. Aspect ratio (AR):

L Ma jor
AR = (5.8)
L Minor

Regular-shaped particles are of spherical, disc, rod, sheet, hollow, core–shell,

needle, star, rigid fibrous, triangular, oblate, tube, etc. For rod-, needle-, or wire-
shaped particles, there are two axes such as minor and major axes. The volume
of spherical particle by taking minor length as diameter can be calculated. Then,
number of equivalent volumes of spherical particle with minor length as diameter
present in rod, needle, and wire can be approximately calculated. Even, when shape
becomes oblate, star, prism, or triangular, such equivalent volumes can be used, so
that approximate value of equivalent volume of a particular-shaped particle can be
compared with others. In case of hollow or tube, inner and outer volume calculations
can help in finding equivalent volume. However, when shapes do not have a proper
regular, it is difficult to use equivalent volumes. Instead, surface area measurement,
small angle neutron scattering, small angle x-rays scattering, and image software
will help in proper calculation of volume.

5.6 Mechanism

Mechanism behind the formation of nucleation and growth of particles in different

media [69, 163–171]:
(A) Solid State Phase
(B) Liquid State Phase
(C) Gas State Phase
(D) Single-crystal growth from S-L phases.
170 R. S. Ningthoujam and A. K. Tyagi

5.6.1 Solid State Phase

In solid state, the molecules or atoms in a particle are closely packed together and have
chemical bonding through ionic, covalent bond, or metallic bond [172]. Generally,
they are rigid, but atoms in solid are under constant vibration. They can undergo
chemical reaction either by heating or changing environment. For example, oxidation
of iron piece occurs in ambient atmosphere. In case of decomposition of CaCO3 , it
requires heat to produce CaO (solid) and CO2 (gas). Two types of chemical reactions
are observed: Homogeneous and Heterogeneous reactions. In homogenous, phase
transformation occurs from one solid to solid or liquid or gas (S-S, S-L, S-G). In case
of heterogeneous, different species (reactants or products) are involved. Mechanisms
involved in the solid-state reaction can include the following [163].
1. Phase Change, 2. Formation of Phase Boundaries or Interface, 3. Rate Process
Changes, 4. Nucleation, 5. Growth, 6. Diffusion.

5.6.1.1 Phase Change

In case of phase change, homogeneous and heterogeneous types of phase changes

occur. Homogeneous type of phase changes is S-S, S-L, and S-G phase transforma-
tions. Example of S-S phase transformation is polymorphic transformation (diamond
to graphite, graphite to graphene, graphite to carbon-nantube). Example of S-L phase
transformation is melting (diamond melts at 4000 °C in inert atmosphere). Example of
S-G phase transformation is sublimation (naphthalene sublimes at 80 °C at standard
atmospheric temperature, sublimations of ammonium chloride, camphor, iodine, and
anthracene). In case of heterogeneous transformation, different species of reactant
or product are associated. Table 5.1 will provide the possible ways of heterogeneous

Table 5.1 The possible ways of heterogeneous transformation [163]

Ways or types Reactants Products Reactions/examples
Decomposition or A→ B +C:S +S 3AuCl → 2Au + AuCl3
disproportionates S +G CaCO3 → CaO + CO2
NH4 Cl → NH3 + HCl
G +G
Combination or A + B→ C: S MgO + A12 O3 → MgAl2 O4
synthesis MgO + SiO2 → MgSiO3
Replacement or A + B→ C +D:S +S Cu + AgCI → CuCI + Ag
substitution S +G BaCO3 + TiO2 → BaTiO3 + CO2

Sequential or A→ B→C (i) La2 O3 + 11A12 O3 → 2 LaAlO3

consecutive + 10A12 O3
(ii) 2LaAlO3 + 10A12 O3 →
LaAl11 O18
5 Particle Size and Shape Engineering for Advanced Materials 171

transformation. Here, symbols such as A, B, C, D are used to represent reactants or

products. S, L, G stand for solid, liquid, and gas phase, respectively.

5.6.1.2 Formation of Phase Boundaries or Interface

When solid particles of different phases (A and B reactants) are mixed using pestle
mortar, it imparts close proximity. The possible interactions from mixing are: (1) no
reaction at room temperature or a slight higher temperature, i.e., it needs activation
energy (E) for formation of interface (C). (2) it starts the formation of interface
(C) due to fast diffusion of atoms or ions of A and B at room temperature or higher
temperature. With time at particular temperature (higher than that required for forma-
tion of interface), the size of interface increases. If amount of A is more in terms
of atomic percentage than that of B, some part of A remains as unreacted after
completion of reaction between A and B in case of AB chemical formula. In some
cases, it so happened that B atoms or ions are homogeneously or heterogeneously
mixing with A atoms depending on types of chemical compounds or stoichiometry
(AB, An B, ABn (n = 2–12)) formed. (3) In case, A site is highly stable in terms
of chemical bonding even at higher temperature (i.e., inert). It is difficult to react
with B atoms or ions. When there is a presence of vacancies in the lattice of A, the
chemical stability of A decreases. Atoms or ions of B site can enter the interstitial
sites or void or pores of A site, and reaction starts at small region of A site to form
interface inside A site. (4) Either of A or B site or both have very small-sized particles
(nanosized). The reaction for formation of interface occurs at lower temperature than
normal reaction temperature, because small-sized particles have large surface area
as well as less chemical and thermal stability. (5) In some case, if A is highly stable,
but B decomposes to other species (solid or gas or liquid or S-S, S-G, or S-L) at
slightly higher temperature, reaction for formation of interface can be enhanced if
one or more species after decomposition of B starts reaction with A site. This is due
to atomic level interaction between A and species at different environment. Interface
region of A and B to form new compound (C) at the first stage is known as nucleus
and the process is known as nucleation. (6) The presence of impurities in A or B site
or both may change the formation mechanism for interface. The size of interface can
be increased with extent increase of time under temperature or pressure or radiation
and this is considered as growth. The possible interactions from mixing of reactants
are represented by schematic diagram (Fig. 5.29). The density of compound (C)
can be increased by annealing compacted portion (pallet) of compound at higher
temperature (T = 0.7–0.8 Tm ; Tm = melting point of compound C). This process is
known as sintering. By changing partial pressure of reaction medium or by changing
environment through addition of alkaline or acidic material/gases or by variation of
pressure or temperature, the various reaction pathways for formation of compounds
including metastable phases can be produced.
172 R. S. Ningthoujam and A. K. Tyagi

Fig. 5.29 Schematic representation depicting the possible interactions from mixing of reactants or
particles. Details are provided in main text

5.6.1.3 Rate Process Changes

The rate equation for homogenous reaction in gaseous system can be expressed

As → Bs (5.9)

The rate equation is


r = −d[A] dt = k[A] (5.10)

[A] is concentration of reactant A. k is a reaction rate coefficient. The free energy

(GA ) of reactant is less than that of activation energy (G* ), and that of product (GB )
is less than that of reactant.

G = RTlnK∗ (5.11)

where K* is equilibrium constant.

In case of solid-state reaction, rate equation is defined by [163].
  
rate = dni dt 1 Vt (5.12)
5 Particle Size and Shape Engineering for Advanced Materials 173

where ni is initial moles and Vt is the volume of solid/interface/compound formation

at time t.
In case of heterogeneous reaction, rate equation is complicated depending on type
of reaction. It may associate various activation energies such as initial, intermediate
and final.

5.6.1.4 Nucleation and Growth

In solid-state reaction, nucleation starts at surface of particles where chemical reac-

tion between particles of reactants occurs. With time, growth of new particles starts
if sufficient reactants are present.

5.6.1.5 Diffusion

Diffusion in solid-state reaction involves one or more of the following: the inter-
change of atoms or ions, vacancy hopping, movement of interstitial sites, and
exchange due to decomposition or pressure and temperature gradient. The Fick’s
law can be applied in diffusion [163]:
1. First law:

J = −Ddc dx (5.13)

where J is total number of jumps and D is diffusion coefficient for a process.

Dc/dx is change in concentration with distance x.
2. Second law:

[dc/dt]x = d{Ddc/dx} (5.14)

(dc/dt}x = D(d2 c/dx2 ) (5.15)

The temperature-dependent diffusion coefficient (D) can be expressed using

Arrhenius equation:

D = Do exp(−E/kT) (5.16)

The diffusion rate in solid-state reaction can be related by the following:

Rate = ktn (5.17)

where n = 0.5, 1.0, 2.0, 3.0, or fraction.

174 R. S. Ningthoujam and A. K. Tyagi

Sometimes, the flux is used to make solid-state reaction at lower temperature. The
flux has a low temperature melting point, which is lower than solid-state reaction
temperature. The flux carries one or more of reactant components to reaction zone.
Final product does not react with flux added.
In solid-state reaction, nucleation, growth, coarsening, sintering, and the forma-
tion of grain boundaries between particles are associated.

5.6.2 Liquid State Phase

Evolution of particles from liquid state is generally known as solidification [169,

170]. Another term is precipitation, which is generally referred to ionic compounds.
The precipitation occurs when ionic product of opposite charged ions (anions and
cations) is more than that of solubility product. With further increase of ionic product,
it becomes supersaturated. Once supersaturation state is reached, the solid product
can be observed by our eye. The solubility product of ionic compound is fixed at a
particular temperature and it varies slightly with temperature.
Example, ‘C’ is compound formed by A+ (cation) and B− (anion). The dissolution
of C takes place in a solvent if its solvation enthalpy is greater than its lattice enthalpy.

C(s)  A+ (aq) + B − (aq) (5.18)

  
K sp = A+ B − (5.19)

Compounds such as NaCl, BaSO4 , CaMoO4 , Fe(OH)3 , Fe3 O4 , MFe2 O4 (M =

Zn, Mn), A2 O3 (A = Y, Y, Gd), APO4 (A = Y, La, Gd), NaYF4 , CdS, PbSe, ZnO,
SnO2 , TiO2 , AVO4 (A = Y, La, Gd), can be prepared from the corresponding sources
of positive and negative ions. Precipitation is faster if opposite charges have high
concentrations in solutions. Ag, Ni, Au, Pd, FePt, FePd particles can be prepared
from the respective ions in solution. This is a solidification process. Sometimes,
the term precipitation is used. The term precipitation belongs to solidification. The
condensation of atoms or ions or vapors into solid is also considered as solidification.
In air atmosphere, condensation of water vapor occurs due to gravitation forces or
cooling process, and finally, many types of precipitation such as ice pellets, drizzle,
sleet, snow, rain, hail, and graupel can occur. In sea, different types of precipitation
occur in different zones due to surrounding environment and depths.
Ionic compounds such as AgCl, AgBr, and AgI have the solubility products (Ksp )
of 1.77 × 10–10 , 5.35 × 10–13 , and 8.52 × 10–17 , respectively [173]. There is a
decrease in solubility product with change of negative counterpart Cl− to Br− to I− .
Thus AgI is sparingly soluble in water. In the same strength of solution of such ionic
compound, the precipitation of AgI will be faster. The Ksp can be calculated from
the electrochemical reduction potentials. For example, the Ksp of AgI at 25 °C can
be calculated from electrochemical reduction potentials:
5 Particle Size and Shape Engineering for Advanced Materials 175

Equations Reactions Reduction potential half-reaction (Eo , V)

i AgI(s) + e → Ag(s) + I− 0.15
ii I2(s) + 2e → 2I− 0.54
iii Ag+ + e → Ag(s) +0.80

The dissolution of AgI in water can take place:

AgI(s)  Ag+ −
(aq) + I(aq) (5.20)

Here,
  
Ksp = Ag+ I− (5.21)

From equations (i) and (ii), the complete reduction potential (Eo ) can be calculated
as:

Equations Reactions Reduction potential half-reaction (Eo , V)

iv AgI(s) + e → Ag(s) + I− 0.15
v Ag(s) → Ag+ + e 0.80
(iv) + (v) AgI(s) + e → Ag(s) + I− Eo = −0.95 V

Using the Nernst equation,

Ecell = Eo − (0.0591/n) logKsp (5.22)

Here n = 1.
Or, 0 = −0.95 − (0.0591/1)logKsp .
Or, logKsp = 0.95/(−0.0591).
Or, logKsp = −16.07.
Ksp = 8.52 × 10–17 .
The process of the precipitation can be explained by nucleation and growth of
particles. Mechanisms behind the formation of nuclei and growth of particles in
unprotected and protected systems in solution can be discussed here. The solution
comprises of solute dissolved in a solvent. The precipitation can occur when ionic
product is more than solubility product or monomers come closer in proximity to
make stable nuclei. E.g., precipitation of AgCl can occur in water when product
of Ag+ and Cl− pair ions is more than that of solubility product at a particular
temperature. The solubility product of AgCl at 300 K is 1.77 × 10–10 . Ag+ ion
and Cl− ion come closer to form AgCl molecule or monomer. These molecules or
monomers will form nucleus. If chemical potential of AgCl molecule or monomer is
higher in nucleus as compared to that in solution, nucleus will dissolve to solution.
On the other hand, if chemical potential of AgCl molecule or monomer is lower in
176 R. S. Ningthoujam and A. K. Tyagi

nucleus compared to that in solution, the nucleus is stable. With time, AgCl molecules
or monomers will come closer to nucleus, and subsequently, growth of particle starts.
Here, uncontrolled growth may take place. The size of nucleus will be in 2–5 nm.
After growing, size of particle may increase from a few nm to a few microns. The
agglomeration or aggregation can take place depending on electrostatic interaction
or H-bonding or electric or magnetic dipole–dipole interaction. Usually, particles
can be separated in agglomeration under ultrasonication or by changing polarity or
pH of medium. In case of aggregation, it is difficult to remove individual particles
using many techniques.
Various types of solidification will occur from different sources (Table 5.2). Many
attractive forces are associated during solidification. Force of attraction follows
Induced dipole–induced dipole attraction < dipole–dipole attraction < H-bonding
< ionic or covalent bonding [81, 82].
Broadly, three types of nucleation such as homogeneous, heterogeneous, and
unusual one (in which mixture of them depending on pH, temperature, and environ-
ment) are found in solution. In homogenous nucleation, nuclei are formed uniformly
in a liquid, whereas, heterogeneous nucleation takes place in the presence of foreign
substance (impurities, container, grain boundaries, etc.). Classical nucleation can be
valid in case of spherical particles. In case of formation of hollow, thin film, and
different shapes of particles, it did not follow classical nucleation theory.

Table 5.2 Various types of solidification [81, 82]

Sources Types of attractive forces/bonding Examples
among atoms or ions or molecules
Molecules with non-polar London dispersion force is a Ar, Xe, CO2 , I2 , N2 , Cl2
temporary attractive force, which
arises from induced
dipole–induced dipole attraction.
This is possible in non-polar
molecules coming closer in such a
way that the electrons in two
adjacent atoms get displaced and
make temporary dipole molecule
Molecules with polar Dipole–dipole interaction HCl, NH3 ,
Molecules with polar Hydrogen bonding H2 O, H2 S, HF,
Molecules with polar Ionic bonding [Ni(NH3 )6 ]Cl2 ,
Atoms Metallic bonding Ni, Co, Sc, Gd, Ag, Au, Pt,
Pd, FePt, metallic alloys
Atoms Covalent bonding Graphite, graphene, carbon
nanotubes, fullerenes, carbon
fibers, Sulfur (S6 , S8 ),
phosphorus (P4 )
Ions Ionic bonding NaCl, MgO, Al2 O3
5 Particle Size and Shape Engineering for Advanced Materials 177

Fig. 5.30 Schematic representation depicting different reaction pathways to prepare particles: path
1, 2, or 3 can form single phase in plot of free energy changes versus diameter of particles. Path 4
can form metastable phases along with final product

The various reaction pathways for formation of products and metastable phases
are shown in Fig. 5.30 [163–171]. Classical and non-classical types of nucleation
and growth of particles are available [169, 170]. Activation energy required to occur
a chemical reaction has higher than that of reactants or products. Product has lower
energy than that of reactants in general. In case of metastable formation, intermediate
activation energy is associated. In path 1, 2, or 3, particles of single phase are formed
from reactant molecules or ions or monomers in solution. Here, monomers come
closer and form cluster, and then finally nuclei are formed at critical diameter where
activation energy exists. When chemical potential of monomer is more in nuclei
as compared to that in the solution, nuclei will start dissolution. When chemical
potential of monomer is less in nuclei as compared to that in solution, nuclei will
start growing and finally product will be formed. Path 4 shows metastable phase
formation before the final product formation.
178 R. S. Ningthoujam and A. K. Tyagi

5.6.3 Gas State Phase

In gas state synthesis, target material is fixed in closed vacuum chamber [69, 168].
This was bombarded by high temperature Ar or plasma Ar+ gases, some atoms are
detached from target to form cluster. The cluster is carried by cold Ar gases to the
deposited place or the suitable substrate. Magnetron sputtering or vacuum chamber
deposition is a system for this. In this way, nanoparticles of Ag, Au, Pd, Pt, Co, Ni can
be prepared. If two more targeted sources are used, alloys, core@shell, composites
can be prepared. FePd, FeAl, FePt, CoPt, SmCo, YCo5 , can be prepared. Core-
shell, hybrid, oxides, nitrides, sulfides such as Pd@MgO, CuO, TiO2 , PbS, Fe3 N
can be prepared by using different atmospheres. Post-processing and finishing help
in designing materials for different applications. Different density of nanoparticles
can be prepared by pressure-induced cold condensation/compaction. These nanos-
tructures are useful in many applications in catalytic, photo-catalytic, plasmonic,
gas-sensing, bio-sensing, anti-corrosion areas, etc.

5.6.4 Single-Crystal Growth

Single crystals are crystals having high degree of perfect lattice. Dislocation or defects
are least in case of single crystals as compared to others such as polycrystals [69, 174].
To grow a crystal, it needs to attain a state of supersaturation, followed by process
of nucleation. The growth of crystals can be done from melt, vapor, and solution.
The growth of crystal from solid is difficult. Different techniques are reported to
produce single crystals. Every technique has advantages and disadvantages for the
preparation of a particular material. Single crystals can be prepared by different
methods (Fig. 5.31).
Crystal growth from the melt is the process of crystallization of fusion. Here,
polycrystalline material is melted, and crystallization starts from a melt on cooling
the liquid from its freezing point. The chance of contamination with impurities is
less and the rate of growth is generally more than that of other possible methods.
Different methods for crystal growth from melt include Bridgmann, Czochralski,
Vernuil, Zone melting, Kyropoulos, and Skull melting methods.
Crystal growth from vapor is performed by two routes: Chemical and physical
transport methods. In chemical transport method, chemical precursors in the form
of molecules of halide is transported, and it gets decomposed in the growth area and
deposition of particles on suitable substrate occurs. In physical transport method,
polycrystalline material (known as target material) gets converted into vapor or gas
using Plasma source of Ar+ or other heater; and gases of targeted atoms are trans-
ported to cooler area, where single crystal seed of a particular crystallographic direc-
tion (say, [100, 110, 111]) is kept. In this way, growth of single crystal takes place
on single crystal seed.
5 Particle Size and Shape Engineering for Advanced Materials 179

Fig. 5.31 Different methods to prepare single crystals of metallic, semiconductors, oxides and
sulfides, halides

Crystal growth from solution takes place from solution, where material required
for the growth dissolve in a particular solvent such as water or organic solvent, and
either evaporation of solvent takes place or slow cooling takes place or temperature
gradient takes place. This is considered as the low temperature solution growth.
There is a process of preparation of single crystals using high temperature solution
growth. In this, material or reactants are dissolved in water or a particular solvent
and transferred into a closed reaction chamber, which is non-reactive in reaction
process such as Teflon container. This Teflon container is closed and kept in stainless
steel container, which sustains a high pressure and temperature. When temperature is
provided, the vapor pressure is increased. When it reaches the critical point of solvent,
the dielectric constant changes. Water at normal condition has dielectric constant of
78 and decreases to 5–10, at or above critical point. Dissolution of compound having
ionic bonding decreases at higher temperature and pressure, since dielectric constant
is less than that at normal condition. Those compounds having covalent bonding did
not dissolve in water at normal condition and these can dissolve at critical point of
water. The supersaturation of ions for the formation of inorganic compound is faster
at critical point as compared to that at normal condition; and thus crystallization
process is different under high pressure and high temperature. This method is known
as solvothermal method. If water is used as solvent, this is considered as hydrothermal
method.
There are many difficulties to prepare single crystals of high Tc-compounds and
compounds having many different elements, because in melt technique, different
reactants/elements have different melting points. It is not easy to prepare single
crystals from solid. Recently, the preparation of single crystal from amorphous phase
of solid is reported [171]. Here, a suitable laser source is heated at the spot of
amorphous phase, and then crystallization starts below melting point. In this way,
many shapes of single crystals can be prepared.
180 R. S. Ningthoujam and A. K. Tyagi

5.7 Conclusions

Size and shape engineering of particles is important in order to get desired material so
that these can be useful for a particular application. Classification of particles in terms
of crystallinity or arrangement of atoms/ions is provided. Atomic structures in single
crystals, macro-crystalline, and nanocrystalline materials are shown. Atomic struc-
ture in nanocrystalline materials suggests the high contribution of grain boundaries
with respect to grain. The properties of materials changes with variation in size and
shapes of particles in nano-range. Higher bulk density material can be achieved by
using nanocrystalline material as compared to that using macro-crystalline material.
Band gap in QDs can be increased by decrease in particle size. Electrical resistivity
is more in case of nanocrystalline material as compared to that of macro-crystalline
material. This is due to the contribution of grain boundaries in nanocrystalline mate-
rial. In terms of magnetic property, superparamagnetic particles can be generated by
decrease of particle size in ferromagnetic material. Particle size distributions are asso-
ciated during preparation of particles or in natural available materials. Their fitting
equations are provided here. Lastly, mechanisms for the formation of polycrystalline
or single crystal particles in solid, liquid, gas media are discussed.

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bauer spectroscopy, microwave absorption and hyperthermia behavior of Ni-Zn-Co-ferrite
nanoparticles encapsulated in multi-walled carbon nanotubes. J Magn Magn Mater 460:12–27
126. Soni AK, Joshi R, Jangid K, Tewari R, Ningthoujam RS (2018) Low temperature synthesized
SrMoO4 :Eu3+ nanophosphors functionalized with ethylene glycol: a comparative study of
synthesize route, morphology, luminescence and annealing. Mater Res Bull 103:1–1
127. Mallick A, Mahapatra AS, Mitra A, Greneche JM, Ningthoujam RS, Chakrabarti PK (2018)
Magnetic properties and bio-medical applications in hyperthermia of lithium zinc ferrite
nanoparticles integrated with reduced graphene oxide. J Appl Phys 123:055103
128. Parchur AK, Ansari AA, Singh BP, Hasan TN, Syed NA, Rai SB, Ningthoujam RS (2014)
Enhanced luminescence of CaMoO4 : Eu by core@shell formation and its hyperthermia study
after hybrid formation with Fe 3O 4: cytotoxicity assessment on human liver cancer cells and
mesenchymal stem cells. Integr Biol 6:53–64
129. Ningombam GS, Singh NR, Ningthoujam RS (2017) Controlled synthesis of CaWO4:Sm3+
microsphere particles by a reverse-micelle method and their energy transfer rate in lumines-
cence. Colloids Surf A 518:249–262
130. Chakravarty R, Chakraborty S, Ningthoujam RS, Nair KVV, Sharma KS, Ballal A, Guleria
A, Kunwar A, Sarma HD, Vatsa RK, Dash A (2016) Industrial-scale synthesis of intrinsically
radiolabeled 64 CuS nanoparticles for use in positron emission tomography (PET) imaging of
cancer. Ind Eng Chem Res 55:12407–12419
131. Ningthoujam RS, Sharma A, Sharma KS, Barick KC, Hassan PA, Vatsa RK (2015) Roles of
solvent, annealing and Bi3+ co-doping on the crystal structure and luminescence properties of
YPO4 :Eu3+ nanoparticles. RSC Adv 5:68234–68242
132. Chakraborty S, Sharma KS, Rajeswari A, Vimalnath KV, Sarma HD, Pandey U, Ningthoujam
JRS, Vatsa RK, Dash A (2015) Radiolanthanide-loaded agglomerated Fe3 O4 nanoparticles
for possible use in the treatment of arthritis: formulation, characterization and evaluation in
rats. J Mater Chem B 3:5455–5466
133. Singh LP, Jadhav NV, Sharma S, Pandey BN, Srivastava SK, Ningthoujam RS (2015) Hybrid
nanomaterials YVO4 :Eu/Fe3 O4 for optical imaging and hyperthermia in cancer cells. J Mater
Chem C 3:1965–1975
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terials from water dispersible CaF2 :Eu3+ , Mn2+ and Fe3 O4 for luminescence and hyperthermia
application. J Phys Chem C 118:18087–18096
135. Phaomei G, Ningthoujam RS, Singh WR, Loitongbam RS, Singh NS, Rath A, Juluri RR,
Vatsa RK (2011) Luminescence switching behavior through redox reaction in Ce3+ co-doped
LaPO4 :Tb3+ nanorods: Re-dispersible and polymer film. Dalton Trans 40:11571
136. Phaomei G, Singh WR, Singh NS, Ningthoujam RS (2013) Luminescence properties of Ce3+
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light emission from Eu3+ co-activated LaPO4 :Dy3+ , Ce3+ . J Lumin 134:649–656
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Chapter 6
Synthesis of Porous Materials

Deepak Tyagi and K. Bhattacharyya

Abstract This chapter deals with the different types of porous materials, their
synthesis and their characterization of the pores. The different porous materials could
be broadly grouped into three types of artificially created pores. The microporous
and mesoporous materials are discussed in detail here with their synthesis strategies
and characterization techniques in this chapter along with the broad classification of
different types of porous materials and their generic properties.

Keywords Porous materials · Porous metals · Microporous materials ·

Mesoporous materials · Characterization techniques

6.1 Introduction

A porous medium or a porous material could be described as a material that possesses

pores (voids). The non-porous structural part of the material is often called the
“matrix” or “frame”. The pores are typically filled with a fluid (liquid or gas). The
skeletal material is generally solid, however foam structures also nicely depict porous
media. Right from the beginning of the earth the solids have their pores in them which
are useful for the different physical, biological and transport phenomena. A tree leaf
(with a stomata), a shell with pores, a bone joint, a honey comb, a pumice stone, a wall
made of stones/bricks, etc., all have pores of different sizes, shapes, magnitudes and
are used for different purposes [1, 2]. The materials without voids are termed as non-
porous materials and are better defined as the materials whose density is close to its
theoretical density calculated from its atomic structure. Examples for the nonporous

D. Tyagi (B) · K. Bhattacharyya (B)

Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
K. Bhattacharyya
e-mail: [email protected]
K. Bhattacharyya
Homi Bhabha National Institute, Mumbai 400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 189
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_6
190 D. Tyagi and K. Bhattacharyya

materials are forged metals, alloys, sintered carbide cutting tools, glass (without air
bubbles) silicon wafers and gem-quality diamonds, etc. However, all materials have
small holes about the size of an atom. It is impossible to remove them so we wouldn’t
call these small holes “pores” (though this may be debatable) however if the pores
are of lower than the atomistic size and they do not contribute to their theoretical
density they could be ignored. Therefore, essentially non-porous materials are denser
and do not absorb well and do not allow much air/liquid (fluid) to flow through. The
materials through which fluid can pass are called porous materials. The materials
through which fluid can’t pass are called non-porous materials.
Now the next question is could all the materials with pores be termed as porous
materials? Technically the answer is no. Usually the porous materials are those where
the pores usually add to the property enhancement for the designer, or they are
usually termed as defects. Therefore, the porous materials should have two essential
characteristics to be termed as porous materials: (a) they should have lot of voids
(pores); (b) the pores are intended explicitly to accomplish the desired index of the
material property under the research.

6.2 Types of Pores

In a porous material there can be different types of pores. The division of pores could
be made on different basis sets.

6.2.1 Accessibility and the Shape of the Pores

A porous material may contain pores like cavities, channels, interstices that are deeper
than they are wide. The porous materials can be described by pores, as well as the
cell/pore walls as seen in Fig. 6.1.
Accessibility:
A Closed pores
B, C, E, F, G Open pores
B, F Blind pores (dead-end or saccate)
E Through pores

Shape:
C Cylindrical open
F Cylindrical blind
G Roughness
B Ink-bottle-shaped
D Funnel shaped
6 Synthesis of Porous Materials 191

Fig. 6.1 Different types of Pores

6.2.2 Size of the Pores

Pore size is important for different applications. International Union of Pure and
Applied Chemistry (IUPAC) has designated three pore size regimes that could be
associated with the designated isotherm for the physisorption experiments (like N2
adsorption-desorption experiments) and their associated transport mechanisms:
(a) Microporous—The pore size is smaller than 2 nm, which is comparable to the
size of molecules. The transport phenomenon is dominated by mainly activated
transport.
(b) Mesoporous—The pore size is between 2 and 50 nm. The pore size is either
same order or smaller than the typical mean free path length of typical fluid.
Transport mechanisms that may be occurring are Knudsen diffusion and
surface diffusion. Multilayer adsorption and capillary condensation may also
contribute.
(c) Macroporous—The pore sizes are larger than 50 nm, i.e. the pores are larger
than the mean free path length of fluid. Transport phenomenon is dominated
by bulk diffusion and viscous flow.
192 D. Tyagi and K. Bhattacharyya

6.2.3 Ordering of the Pores

The pores that are formed in the solid matrix could be ordered with a specific ordering
or could be present randomly. The ordered mesoporous systems are like MCM-
41, SBA-15, etc. MCM-41 has one-dimensional hexagonal porous structure and
SBA-15 is hexagonal three-dimensional ordered structure. Anatase TiO2 has random
microporous structures.

6.2.4 Type of Pore Dimension

The pores present in the solid matrix could be one dimensional, two dimensional or
three dimensional which definitely affects the transport phenomena of the fluids
inside them. MCM-4 has one-dimensional hexagonal pore, SBA-15 has three-
dimensional hexagonal pores, MCM-48 has three-dimensional cubic pores, etc.
Several zeolites have two-dimensional pore systems.
i. Natural and artificial pores
Porous solids include two types of porous structures, i.e. natural and artificial
porous structures. Natural porous solid could be found universally such as in
bones of animal and human beings, plant leaves, wood, sponge, coral, etc. The
artificial porous materials are the materials that are synthesized intentionally
with the formation of a particular type of pore and could again be segmented
into three different divisions:
(a) Porous Metal: This is rather a new genre of scientific materials that is
used for its functional and structural properties [3–5]. The porous metals
are light weight and possess the properties both of metals like ductility,
conductivity (electrical), etc., in general along with the other properties
like low bulk density, greater surface area, lesser thermal conductivity,
better penetrability, mechanical damping, electromagnetic shielding, noise
attenuation, etc. There can be different types of porous metals that are
designated according to their synthesis methods like (a) Powder Sintering;
(b) Fibre Sintering; (c) Metal Casting; (d) Metal deposition; (e) Direct
Solidification; (f) Composite formation.
(b) (b)Porous Ceramic: These comprise of heat-resistant ceramic materials
ranging from metal oxides to chalcogenides to phosphates, aluminates,
etc. The pore size mostly ranges between angstrom to millimetre in units
and usually the materials are thermally stable [6, 7]. Usually the charac-
teristics of the ceramic porous materials are: (a) good chemical stability,
(b) rigidity and specific strength and (c) good thermal stability. At times
the hydrothermal stability is poor however that may vary from the way
they are synthesized and the shape of them. The porous ceramic could
be again divided broadly into two types upon the synthetic route: (a) Soft
6 Synthesis of Porous Materials 193

Templating: If the templates are utilized directly from long-chain micelles

and post synthesis these micellar medium are thermally removed to obtain
the desired pore size and the structure; (b) Hard Templating: Using the
soft templated porous ceramics as the basis of templates and removal of
the soft templates post synthesis usually with HF or NaOH depending on
the type of the soft template used. Here for the hard templating the walls
of the soft template would be used to form the pores and the pores of the
soft template will be utilized for the matrix of the hard-templated porous
ceramic. It could also be distributed in another two classes (c) honeycomb
ceramics and (d) ceramic foam [7–9].
(c) Porous Foam:These foams are usually polymer materials covered with
several large pores [10, 11] and made up of either resin (phenolic
formaldehyde resin, epoxy resin) or polystyrene materials (polyvinyl chlo-
ride, polyurethane, polyethylene, urea-formaldehyde, etc.).The large pores
present in the above materials are usually occupied with gaseous moiety.
The volume ratio of gas-filled pores to that of solid polymer defines its
density. They could be classified according to their density and rigidity.
(a) Density: According to density there are three different types viz.
low, moderate and high foaming materials. Density for low foamed (high
density) polymers is more than 0.4 g/cc, moderate foamed in between
(0.1–0.4) gm/cc and high foamed (low density) less than 0.1gm/cc. The
expansion ratio for low (<1.5), medium (1.5–9.0) and high (>9.0) foaming
materials. (b) Rigidity: According to rigidity, there are three different
categories rigid, semi-rigid and flexible foams [11] which are classified
according to their glass transition temperature (GTT) [defined as the
temperature required for melting the polymeric crystal foam]. The rigid
foam is crystalline and rigid at room temperature (RT) and has high GTT
(>RT). The flexible foam has low GTT (<RT) and the semi-rigid has GTT
in between these two. Usually resins (phenol-formaldehyde resin, epoxy
resin) polystyrene, polycarbonate rigid polymers whereas porous rubber,
elastic polyurethane are flexible ones. Polyvinyl Chlorides and polyolefin
can have both. The general features of polymer foams are: (a) low relative
density; (b) very good heat insulation; (c) good sound insulation; (d) and
sound specific strength.

6.3 Synthesis of Porous Metallic Materials

Porous materials including porous metals require certain degree of porosity in them
and certain degree of strength in the matrix.
194 D. Tyagi and K. Bhattacharyya

6.3.1 Sintering

One of the processes commonly utilized is the sintering to form the porous materials.
The sintering process for the porous powder ingredients is displayed by the following
mechanism: The atoms in the connecting area of the different powders will diffuse
from their parent crystal lattice (~0.4Tm ) (Melting Temperature) and form prelim-
inary bonding between each other. Next at (~0.5Tm ) is signified by the migration
of the surface atoms in the adjoining convex area of powders nearby to produce a
sintering neck. The different methods for synthesis of diverse porous materials via
sintering could be accounted as follows:
(a) Sintering of Powders: The powder sintering is signified by sintering of a mixture
of metal powders and pore-forming organic materials. The sintering process is
emphasized by the disintegration of the pore-forming organics followed by the
atomistic diffusion of metallic materials producing spongy and porous metal.
Different metallic powders utilized are Aluminium, Molybdenum, Mo-alloy,
Tungsten, W-alloys, etc., and their combinations.
(b) Loose Sintering: This process is exemplified by using powders without pelleti-
zation (i.e. without applying pressure to them). The surface tension and the
capillary effect between the different powder materials is the source of contact
between them whilst sintering. The major caution for this process is the mould
materials so utilized should possess higher thermal strength and should not
take part in the reaction or react with the powders. Further higher porosity
could be attained via utilizing pore former organics. Examples are Cu-Sn alloy
and Ni-diaphragm (utilized in Alkaline Batteries/Fuel cell).
(c) Activated Sintering: Usually for synthesizing porous metals possessing higher
melting point requires either higher temperature or higher sintering time. These
metals usually require certain type of activation to reduce either the energy for
sintering or time of sintering. An activator so employed for an activated treat-
ment however could lower the sintering temperature or time. Fundamentally
the activator lowers down the thermodynamic activation energy of the process
and improves the kinetics of the system by enhancing the reaction rate. The
proposed activation could be achieved using physical or chemical methods.
The physical means that could be employed would be using and additional
force field which would thereby lower the activation energy by supplying
extra energy like (a) Magnetic Field, (b) Vibrational Energy (c) Radiation
(High energy Radiation), etc. The Chemical activation may be achieved by
using a supplement material that produces an intermediate step whose oxida-
tion/reduction releases high energy and mass which could be then subsequently
utilized to lower the final activation barrier and formation of porous material by
the loss of the additional mass. Hydrides, reactive gases, certain trace elements,
peroxides, etc., are often utilized as these activating materials. Mechanistically
the activated sintering phenomenon is largely centered around the volume
diffusion of the activator and the defects created by the activators leading to
porosity. However, around the grain boundary the surface diffusion could not
6 Synthesis of Porous Materials 195

be completely ruled out. The alteration in diffusion coefficient for the defect
sites/ vacancies and metal atoms could lead to faster migration of the metal
atoms thereby enhancing the kinetics of the system.
(d) Electric Flash Sintering: The metal powders with high melting point could
be allowed before a high frequency A/C (alternating current) or D/C (direct
current) flash or spark discharge. The small discharge emanating from the A/C
or D/C source is for a very small time (15–30 s) however produces a very
high energy instantaneously and thereby the metals do not get enough time to
quench thoroughly leading to formation of pores inside and thereby a porous
material. Usually, porous refractory materials are made by this technique.
(e) Sintering in Liquid Phase: The diffusion of the metal atoms/defects in a
liquid phase is usually faster if equated with the respective solid phase. This
simple technique could be utilized as the basis to form porous alloy materials
with one of the metal with lower melting point. The surface tension and the
tension in boundary of the solidus-liquidus eutectic mixture could be used as a
common driving force. Porous Cu-Sn alloys are usually subjected to this type
of treatment.
(f) Sintering of Slurry Using Foaming Agents: The metal in powder form, required
foaming agents, organic chemicals (leading to formation of gaseous material
upon degradation) are mixed together to form a semi-solid slurry. Subsequently
upon sintering the slurry leads to formation of high porous metals. Metals with
lower melting points are usually utilized like Be, Ni, Fe, Cu, Al, etc. Alloys
like stainless steel or bronze, etc., are subjected to such treatment to obtain
good degree of porosity.
The physico-chemical properties, agglomeration rate (particle size), surface entity
and the phase property of the composition are directly dependent on the sintering
temperature. Ideally 0.5Tm is taken a good sintering temperature as rule of thumb,
though it varies from system to system. However, depending on the different physical
properties like malleability, strength, and porosity of the metal required along with
the required mechanical strength of the metal in question sintering temperature could
be varied from 0.6 to 0.8Tm . Utmost care should be taken for sintering the metals that
are prone to oxidation. They should be sintered in either an inert atmosphere or in
a reducing atmosphere. Usually the sintering time should be optimized considering
into fact the properties that are required and holding time should be determined
experimentally. For porosity factor, the shape of the pore and the type of the pore
also depend on the sintering time. The different sintering atmospheres could be
differentiated in the following ways:
(a) Oxidizing Conditions (O2 (high purity), H2 O (steam), Air (usually where pure
O2 is not required).
(b) Reducing Conditions (H2 (high purity), NH3 (decomposed), CO (lower
reducing atmosphere), H2 and CO combination
(c) Neutral/Inert Conditions (N2 , Ar, He, vacuum)
(d) Carburizing Conditions (Carbon Monoxide, Methane and other hydrocarbons)
(e) Nitriding Conditions (Ammonia and Nitrogen).
196 D. Tyagi and K. Bhattacharyya

The reductive, oxidative or neutral conditions are relative and vary from system
to system. One should understand that a sintering atmosphere oxidative for a system
could be neutral or different for other systems. Usually for the porous materials the
condition (reductive, oxidative, etc.) are done in presence of a gaseous entity which
enhances pore formation. Equivalently certain pore-forming agents are also added
during the sintering process which releases good amount of gases in the reducing or
oxidizing conditions leading to formation or pores of certain type and ensuring high
degree of porosity in the metals.
The addition of pore-forming agents (PFAs) is usually utilized for metals with
high porosity. These PFA’s should neither react with the concerned metal nor should
absorb water or decompose at room temperature or reaction conditions. The PFAs
are decomposable when heated and should not leave any residue in the metals that
could act as impurity. Inorganic salts possessing lower melting point are employed
as PFA viz. camphor, urea, acid carbonates and ammonium chloride. Pore enhancers
and natural cellulose may also be used additionally.

6.3.2 Fibre Sintering

The general process to synthesize porous metals via fibre sintering process are
threading, felting and sintering [4]. Metallic fibres with particular known dimen-
sions (length, diameter, and length-diameter ratio) are aligned to the felt and further
calcined under reducing conditions resulting in porous fibres. Different alloys like
Ni–Cr alloy, stainless steel, Cu, Ni, etc., with a broad range of porous structure
are prepared by this method. Porous metals obtained from fibre sintering possesses
certain gains in the form of higher compression resistance, better elasticity and better
toughness.

6.3.2.1 Electrode Plating with Porous Metal Fibres

The Ni-base plate commonly utilized in the battery industry are porous metallic fibre
electrodes. It is manufactured using different approaches like:
(a) A uniform mixture of metal fibres and fibre felt is prepared (diameter to length
ratio) and thereby calcined in reducing medium to acquire a porous matrix.
Metallic plated organic fibre is calcined, cut and drawn to manufacture the
fibres.
(b) The reductive sintering of metal plated fibres is attained through thermally
decomposing the organic or via direct thermal decomposition of metallic plated
fibres.
(c) The metallic carbonyl compounds are decomposed thermally for the contin-
uous production metallic fibre base plate.
6 Synthesis of Porous Materials 197

Fig. 6.2 Representation of Metallic Melt Foaming using hydride PFA for porous metal foam

(d) PFA along with binder Ni powder and Ni-slurry are employed in a simple
technique.

6.3.3 Metallic Melt Foaming

Pore foaming agent (PFA) which releases gaseous material (Fig. 6.2) on thermal
decomposition is added to the metallic melt after optimization of the viscosity. The
foaming of the melt is caused by the thermal decomposition of the added foaming
agent which expands and is cooled thereby [12, 13].
Metal hydrides powders that decompose at low temperature(~400–500 °C) like—
hydrides of Ca, Mg, Ti, Zr and Er are essentially employed as PFA. Different metals
and alloys formed by this method possess lower melting point viz. Al-alloys, Al, Pb,
Sn and Zn.

6.3.4 Introduction of Gases to Metallic Melt

Stream of gas bubbles of air, CO2 or inert gases are introduced from the bottom
molten metal with an optimized viscosity as shown in Fig. 6.3. The metallic foam
formed should be stable and non-brittle in the course of this process. The solid
stabiliser particles along with the metal forms are heated to a melting temperature
above the metal liquidus and then gas is introduced from bottom to form cell bubbles.
On cooling down from the liquidus to solidus of the metal foam with required pores
is acquired [12, 13].
198 D. Tyagi and K. Bhattacharyya

Fig. 6.3 Gas introduction

into the metal liquidus from
below to produce porous
metal foam

6.3.5 Infiltration Casting

The pores or interfaces which are created by the inorganic/organic materials or hollow
spheres with lower density are loaded up in the mould. The infiltration of the metal in
the molten state occurs through the interspaces. On dissolution of these pileups by the
thermal process porous metals are produced. Heat resistance and soluble inorganic
materials could be used as the pileup like aluminium hollow balls, NaCl, puffing clay
particles, fired clay balls, sand balls, glass ball foams. Depending on the kinetics of
the infiltration and solidification certain polymers could be accepted as the substrate
and subsequently be pressurized with required pressure. The synthesis of metals like
Al, Mg, Zn, Pb, Sn and cast iron with high porosity in spongy form is established by
this method.

6.3.6 Metal Deposition

The metal deposition could be achieved through Physical or Chemical means or

by Electrode position to attain porous metal. One of the physico-chemical method
is vapour deposition depending on the way it is performed. In the physical vapour
deposition method, the materials are usually heated under strong vacuum to the
vapour state by using either Electric Arc, Electron Beam or Resistance heating and
subsequently are dispersed over a porous substrate. The evaporized metal in vapour
state is deposited over a polymer surface forming a film of metal few multilayer
thick. The film thickness is proportional to that of the vapour density and time of
deposition. Finally, the porosity in the metal film would be obtained by degenerating
6 Synthesis of Porous Materials 199

the polymeric porous substrate in the required atmosphere (reductive/oxidative) at

a particular temperature. Organic materials, polymers like polyester, polyurethane,
etc,. could be used as the polymeric base discussed above. The metals that could be
used in the vapour deposition technique are Cu, Ni, Zn, Al, Mo, Ti, Fe, etc. The alloy
of the different metals could also be made depending on the precursors used and the
time of alloying. Another way of deposition is evaporating the metal vapour under
inert atmosphere in lieu of vacuum. The porous structure formed by the deposited
vapour formed mainly by resistive heating. The presence of the inert atmosphere
leads to the collision between the metal atoms and that of the inert gas molecules
as they lose kinetic energy differentially and reassemble in the form of a cluster,
subsequently the growth mechanism is followed as cluster growth to produce a film
of metal. Thereby growth of porous metal film is dependent on the gravitational force
of the metal vapour atoms carried by the inert carrier gas. The rate of migration and
diffusion in the lower temperature also plays a role in the formation of the porosity in
this technique. Usually, highly porous metal thin films are produced in this fashion.

6.3.6.1 Electrodeposition

This is a method of electrodeposition of metal ions present in the electrolyte over

a foam polymer substrate and thereby decomposition of the polymer leads forma-
tion of porous metal. Electrodeposition method leads to formation of highly uniform
porous metal surfaces. The substrate used could be organic foams like polyurethane,
polyester, vinyl polymer and styrene polymers and polyamides. An initial pre-
treatment to eradicate the surface impurities, oil and closed pores is accomplished
using an alkali/acid solution. The materials/substrate not electrically conductive are
made conductive using techniques like evaporation plating, ion plating, chemical
plating, conductive gluing, conductive resin coating and slurry coating. Then elec-
troplating is conducted either by the traditional methods, pulse current method to
lower polarization. Different porous metals like Cu, Sn, Pb, Fe, Au, Ni, Pt, Pd, Al,
Cd Cr, Zn, Ag, Hg, Tl, Ga, Co, In and several metallic alloys are produced.

6.3.7 New Methods for Directional Porous Metals

GASAR (A Russian word meaning- Gas Reinforced): Solid gas eutectic solidification
is a new improved technique for synthesis of porous metals using their eutectic point.
Generically, it is more of a casting method in which a metal in liquid state with some
dissolved gas (like H2 -gas dissolved in the liquid metal) is solidified near its eutectic
temperature (possessing a lower co-melting point). The differential solubility of
dissolved gas moiety H2 in the solid metal as compared to the liquid metal plays a
pivotal role. Therefore, it serves the dual purpose that the metal solidification and
the pores introduction at the eutectic temperature. The eutectic point of a metal is its
state property and mainly depends on the total pressure of the system. The porosity
200 D. Tyagi and K. Bhattacharyya

in the system can be tuned by altering the hydrogen pressure in required cavity.
The temperature of the liquid metal has a great effect on the solubility of hydrogen.
Therefore, melting temperature of the metal should be tuned so that it can be utilized
for the eutectic point of the metal. If not regulated properly it could lead to certain
different phases of the metal with undesirable properties. The pore size is controlled
by the cooling rate, GASAR is applied for the production of metals with high porosity
like Co, Cr, W, Cu, Mg, Al, Ni, Mo, Be and alloys like stainless steel, steel, bronze,
etc., with a desired pore [14].

6.4 Synthesis of Porous Ceramic Materials

The term “Molecular sieves” was suggested by McBain (1932) for the materials
demonstrating specific adsorption characteristics. He proposed that for a material
to be a molecular sieve, it must have separate components of a mixture based on
molecular sizes and shape differences. We have walked a long way where the porous
materials are synthesized with required properties performing specific tasks which
could be well correlated with their structural attributions. Due to various properties
of zeolite molecular sieves such as Lewis and Bronsted acidity, shape selectivity,
etc., these materials find a broad range of applications different industrial processes.
Zeolites have now become a synonymous name in petrochemical and fine chemical
industries. A lot of research has been invested to understand their structure, forma-
tion, and their effective properties. This chapter will describe the generic viewpoints
required in their synthesis, the characterization techniques required to study their
characteristics and their utilization both in the research domain and industry. The
ability of the molecular sieves to separate various molecules based on their pore size,
hydrophobic and hydrophilic nature has been utilized extensively. For example, a
number of zeolites are now used routinely as drying agents, in gas purification and
in separation processes involving hydrocarbons [15]. Zeolites are also utilized on
large scale in detergent industries as additives where they act as ion exchangers and
adsorbents [16]. Zeolites and zeo-type materials because of their high acidity, shape
selectivity, regenerability and thermal stability are used in petrochemical industry,
olefin oligomerization and select to forming, dewaxing and MTG (methane to gaso-
line) processes[17, 18]. For example, Zeolite-A is used in separation process of n-
paraffins from branched paraffins, Zeolite–X and Zeolite–Y are employed as cracking
catalysts in petrochemical industries [8], and TS-1 is used in oxidation reactions of
paraffins, olefins, alcohols, etc. [19] They also serve as large surface area and porous
support to load certain active species. The zeolite-type materials, with their definite
pore structure act as a perfect host, to encapsulate a number of nanosized materials,
like nanosized metals, metal oxides, semiconducting materials, complexes and dyes,
etc. [20–23] These materials are also employed in treatment of waste water, in nuclear
effluent treatment and in soil enrichment [15, 24]. Classification for the molecular
sieves is represented below (Fig. 6.4).
6 Synthesis of Porous Materials 201

Molecular Sieves

Macroporous Microporous Mesoporous

> 50 nm < 2 nm 2-50 nm

Silicates Metallo Silicates Metallo aluminates Alumino phosphates Zeotypes

Alumino Chromo Germanium ALPO SAPO ZrO2 Nb2O5

silicates Silicates Aluminates

Gallo Vanado MAPO MSAPO GeO2 TiO2

Silicates Silicates

Boro Titano
Silicates Silicates

Ferri
Silicates

Fig. 6.4 Classification of molecular sieves based on chemical ingredients

6.4.1 Microporous Materials

6.4.1.1 Zeolites and Zeotypes

(a) Zeolite

Alex Fredrik Cronstedt, a Swedish geologist, discovered Zeolite (1756) as a rock.

The zeolitic material was gathered from a copper mine and was detected to discharge
heavy amount of steam on heating. The steam came from the adsorbed water inside the
mineral structure. The zeolite term was coined from the Greek word “boiling stone”.
Synthesis of zeolites was first performed in 1930s and was found to have substantial
demand in large scale petroleum industries for catalytic cracking purpose in 1960s.
These zeolitic materials were also found to be very important in the laundry industry
and have exchanged the phosphate compounds which incremented their importance
in 1970s. Zeolites are classically produced with crystals and crystal aggregates in
the micron range. Lately there have been number of approaches for the synthesis of
nanocrystalline zeolites with crystal sizes ranging from few nm to 100 nm such as
silicalite, ZSM-5, beta-mordenite and faujasite by different groups.
The basic structure for all zeolites generally involves an Alumino-silicate frame-
work which includes a tetrahedral arrangement of silicon cations (Si4+ ) along with
that of aluminium cations (Al3+ ) where each metal ion is bonded to four oxygen
anions (O2− ). Every O2− ion of the Si-O and Al-O bonds is connected to the two
cations (Si4+ and Al3+ ) and is shared between the two tetrahedra. The resultant
macromolecular three-dimensional structure is made up of SiO2 and AlO4 tetrahe-
dral building blocks. A three-dimensional structure of silicate or aluminate tetra-
hedra with a Si:O ratio of 1:2 was formed where every tetrahedron comprises a Si/Al
cation bonded with four O2− anions [25]. Certain Si4+ ions are exchanged with Al3+
202 D. Tyagi and K. Bhattacharyya

ions, which results in total negative charge in the tetrasilicate framework, present
over the O2− anion bonded to Al3+ cation. The counter ions like metals from group
IA and IIA (Na+ , K+ or Ca2+ , Sr2+ , Ba2+ , Li+ , Mg2+ ) balance the negative charge
of the zeolitic network [25]. Mostly these ions are present on the zeolitic external
surface bounded in the alumina-silicate structure with weak electrostatic bonds [26,
27]. These replaceable mobile counter ions/molecules present in the non-framework
structure are present in the three-dimensional pores and the cavities resulting from
the three-dimensional tetrahedral framework. Such molecules like water molecules
found in these cavities make the zeolites hydrated at room and lower temperatures.
The generic stoichiometric formulation of zeolites is [(Li, Na, K)a (Mg, Ca, Sr, Ba)d
(Al(a+2d) Sin-(a+2d) O2n )]·mH2 O [25, 28].
Zeolitic crystal structure could be differentiated mainly into “two types of motifs”-
primary building motif (PBM) and secondary building motif (SBM) (Fig. 6.5).
The main and the primary building motif are the (SiO4 )4− and (AlO4 )5− tetrahedra
(Fig. 6.5). A spatial arrangement of two- and three-dimensional simple geometric
forms are produced by sharing oxygens of the primary motifs with adjacent tetra-
hedra to form the secondary building motif. These secondary building motifs could
be present in diverse shape like single rings, double rings, polyhedral, etc., or may
even be present in more complex units formed by different ways of cross linking to
yield various distinctive channels and cage structures. Unit cell of a Zeolite definitely
contains definite number of secondary building motifs which could then be extended
in the three-dimensional regime. The non-chiral secondary building motifs could
comprise almost 16 terminal atoms. The number of atoms of the SBM are calcu-
lated with the primary assumption that a unit cell should possess integer atoms and

Fig. 6.5 Different moieties used for making the framework structure of a Zeolite (1) PBM—the
(SiO4 )4− or (AlO4 )5− tetrahedra (2) SBMs and (3) TBMs and (4) the representative zeolitic assembly
6 Synthesis of Porous Materials 203

same single framework (Fig. 6.5). Along with the above-defined PBMs and SBMs,
double rings, can crinite cages and alpha cavities may also be present in the zeolites.
These are called tertiary building motifs TBMs (Fig. 6.5). The TBM’s are found in
diverse framework structures and can be a potent tool for understanding interrelations
between the different frameworks. They can definitely be chiral in nature and are not
used to build the complete framework [29]. The PBMs are defined by the rings that
can accommodate the required number of tetrahedrons. A ring is designated after the
number of tetrahedrons that are present in the ring. Therefore, n-tetrahedrons will be
representing as a ring of n. Zeoliticnetwork is commonly made of tetrahedrons (4,
5, 6, 8, 10, or 12) whereas rings consisting of higher tetrahedrons (like 14–20) are
also found in literature [30, 31]. A zeolitic network with odd-numbered ring (3, 7, or
9) are quite unusual [32, 33]. The pore size in a zeolite is governed by the particular
framework ring size. The pore entrance known as a window.
(b) Zeotypes

The basic (primary) building blocks of zeotypes are tetrahedral made of either SiO4
or AlO4 , and all the tetrahedra share corners. The arrangement of the building
blocks is periodic (crystalline) and therefore possess particular symmetry. There
are primary or basic building motifs which are mainly Tetrahedron and then present
are the secondary or composite building motifs having polymeric structures which
are mainly interconnection of the tetrahedral shared corners with the O-atoms, like
(rings, prisms, etc.) and finally tertiary building units like larger cages. Different types
of soft templated methods are applied for synthesis of hollow zeolitic superstructures.
They include pickering stabilized colloids, interfacial techniques with non-miscible
solvents and fast crystallization from droplets. Literature report established on single-
step emulsion-based technique mainly stabilized using micellar materials like Fe-
based metal-organic frameworks (MOFs) cubic crystals into a three-dimensional
hollow superstructure. However, hollow zeotypes are rare and synthesis of them
are really tough. Other than MOFs, hollow SAPO-34 and APO-34 materials exhibit
macroporous internal structures. Chabazite zeolite, a very good catalyst for methanol
to olefins and for separation of CO2 and H2 from other gases, also shows similar
macroporous hollow porous structure.

6.4.2 Formation of Zeolites

Zeolites can be of two types: (i) Naturally occurring in form of minerals and (ii)
Synthetic that are produced commercially for specific uses for research purpose.
204 D. Tyagi and K. Bhattacharyya

6.4.2.1 Natural Zeolites

Most of the natural zeolites are found in the craters formed after the volcanic eruption
and have to mined to extract them. These are formed when the volcanic ash produced
by lava from volcanic eruptions come in contact with sea or lake water. The chemical
reaction between these aluminosilicates and the salts present in water leads to natural
zeolite formation.
Therefore, the principal factors determining the formation of natural zeolite are:
(i) Type of volcanic matter (lava or ash) reaching water.
(ii) Type of contact water (sea water or lake/ground water).
(iii) Ratio and concentration of the various salts.
(iv) pH of water.
These factors involved in the formation of a zeolite are the reason that each
natural zeolite has unique properties. It was further established by researchers that
formation of zeolite may take place under any of combinations of the following
conditions: hydro-geo thermal systems, waterbody or soil alkaline/saline in nature,
exposed water bodies with low-temperature, sediments under the deep-sea, burial
diagenesis. The formation of reasonably pure deposit of zeolite are obtained from
the rapid cooling of the volcanic ashes in the saline, alkaline lakes [34]. There
are about 40 naturally occurring zeolites forming in both volcanic and sedimen-
tary rocks. As per US Geological survey, the most mined zeolites are Chabazite
[Al2 S14 O12 ·6H2 O], Clinoptilolite [(Na, K, Ca)2-3 Al3 (Al, Si)2Si13 O36 ·12H2 O] and
mordenite [Al2 Si10 O24 ·7H2 O].

6.4.2.2 Synthetic Zeolites

In addition to the naturally occurring zeolites, many synthetic zeolites were synthe-
sized by different methods for specific applications. The best known are zeolite A
(used as laundry detergent), zeolite X and Y (Faujasites, used for cracking) and
ZSM-5 (Pentasil zeolite used as petroleum catalyst).
The first synthetic zeolite was reported by St Claire Deville (1862) as production
of levynite [35]. However, modern zeolite synthesis has its origin from the works
of Richard Barrer and Robert Milton (1940s). Research study of Barrer consisted of
transformation of existing minerals at elevated temperature (~300 °C) using highly
concentrated salt solutions [36] whereas Milton utilized highly reactive synthons
(aluminosilicate gels), enabling the reactions to be carried out under relatively mild
conditions. This led to discovery of zeolite A and B along with 20 other Zeolites
by Milton and his co-workers [37]. In the sixties, the range of reactants was further
broadened and quaternary ammonium cations were included. Another breakthrough
was the introduction of organic constituents, which led to discovery of many new
phases like zeolite beta, ZSM-5, etc.
6 Synthesis of Porous Materials 205

General route of zeolite synthesis includes sluggish crystallization of silica-

alumina gel with alkali and organic templates. In addition to the variation in struc-
ture, the zeolites can also be synthesized by incorporating variety of other atoms
(heteroatoms like Ge, Fe, Ga, B, Zn, Ti and Sn, etc.) which gives rise to interesting
properties. A brief account of the two most commonly used methods for zeolite
synthesis, i.e. Sol-Gel method and Hydrothermal method is given below.

6.4.2.3 Sol-Gel Process

Exceedingly condensed and branched polymers are synthesized by hydrolysis and

condensation of metal alkoxides which could be termed as prevalent precursors for
sol-gel processing. The functionality of the metal usually guides interconnection in
the polymers like Si, having coordination number 4 could result in many branched
framework structure.
The sol to gel conversion is guided by hydrolysis and condensation reactions for
the precursors. A typical hydrolysis reaction may be exemplified below (with Si-OR):

Si (OR)4 + n H2 O = (HO)n − Si (OR)4−n + ROH.

Where R is Alkyl Group for metal alkoxide precursors. The metal is completely
hydrolysed when n = 4. Partial hydrolysis is observed if n = 4. The condensation
is signified by liberation of a H2 O/ROH from partially hydrolysed molecule. The
general reaction is represented as:

(OR)4−n Si(OH)n + (HO)n Si(OR)4−n = (OR)4−n (OH)n−1 Si − O − Si(HO)n−1 (OR)4−n + H2 O.

The maximization of metal-metal linkage through oxygen (M-O-M) bonds occurs

through condensation and thereby minimises the terminal –OH group by internal
condensation. These monomers bind together forming rings, and thereby generating
required three-dimensional structures. The dense structural network is formed by
condensation of the hydroxyl groups outside.
The product properties are mainly governed by the composition of reaction
mixture, overall pH, reaction temperature, seeding time, time taken for reaction and
the type of templates used. The beauty of the sol-gel process is the easy incorporation
of other elements like metals and metal oxides.

6.4.2.4 Hydrothermal Process

Hydrothermal synthesis of zeolite can be presented by following simple steps:

1. Silica and alumina-containing reactants (amorphous in nature) are mixed with
a cation source, usually in a basic medium.
2. Heating reaction mixture (>100 °C) in a hydrothermal autoclave.
206 D. Tyagi and K. Bhattacharyya

3. The reactants continue to be in amorphous form (induction period) post that the
crystallization starts.
4. Slowly all the amorphous material is replaced by an approximately equal mass
of zeolite crystals.
5. These zeolite crystals are recovered by filtration, followed by washing and
drying [38].
Silicon and aluminium which make the microporous framework are introduced in
their amorphous oxide forms. The amorphous oxides possess Si-O and Al-O bonds
and these bonds are converted to Si-O-Al bonds in the hydrothermal reaction with a
mineralizing agent (commonly an alkali metal hydroxide). As only few new bonds
are formed for the zeolite from their precursor oxides the free energy change for
production of zeolite is pretty less. Various detailed mechanisms have been proposed
for the synthesis, e.g. Condensation polymerization of polygonal and polyhedral
anions, linkage of polyhedral, etc.

6.4.3 Mesoporous Materials

The 1990s saw the development of an innovative field in porous materials post the
advent of new plethora of materials possessing ordered mesoporous structures which
were designed using soft templated surfactants along with silicates and alumino-
silicates to obtain the desired size of mesopores and its properties. Utilizing the
surfactant route not only gave larger mesopores but also the control to engineer them
along with the amorphous framework structure which being distinctly different from
the crystalline zeolitic framework It was for the first time that Kuroda et al. informed
Kanemite mesoporous material (FSM-16) formed through the hydrothermal method
for synthesis of silicates [39]. An ordered material possessing pores diameter (2–
4 nm) with very high surface area (~900 m2 g−1 ) was reported by this research group
with the optimized reaction conditions [40]. However, by the same time, Mobil
scientists reported a new group of mesoporous materials, labelled M41S [41], which
had 1-D hexagonal pores (MCM-41) and showed several similarities with FSM-16.
The M41S family consists of three members viz. one dimensional hexagonal MCM-
41, 3-D cubic MCM-48, and thermally unstable MCM-50. Thereafter various silica
and alumino-phosphate based mesoporous materials such as, HMS [42], MSU-1
[43], KIT-1 [44], LUM-1 [45], SBA-n [46], HMA [47], UHM-1 [48], etc., have
been reported in the literature (Table 6.1) and the field has been of intense research
from the point of view of fundamental and as well as applied work. The extensive
work and growing importance on these mesoporous materials have been reported in
several review articles. These mesoporous materials have several advantages, which
make them superior to the microporous molecular sieves and the main features are
as follows:
1 Tunable pore sizes (2–10 nm).
2 Large number of internal hydroxyl groups, 30–50% (surface).
6 Synthesis of Porous Materials 207

Table 6.1 Overview of mesoporous molecular sieves

Mesophase Silica Template Reaction Medium Pore Pore
name source conditions size dimension
(nm)
MCM-41 Fumed Alkyltrimethylammonium Hydrothermal Basic 2–10 1D
silica halides synthesis
FSM-16 Layered Alkyltrimethylammonium Ambient Basic 2–10 1D
silicate halides temperature
HMS TEOS Primary amines Ambient Neutral 2–10 1D
temperature
MSU-1 TEOS Poly(ethylene oxides) Ambient Neutral 2–15 1D
temperature
LMU-1 TEOS Alkyltrimethylammonium Hydrothermal Basic 2–10 1D
halides synthesis
SBA-15 TEOS Ethylene oxide Block Thermal Acidic 5–30 1D
copolymers synthesis
HMA – Alkyltrimethylammonium Hydrothermal Basic 2–10 1D
halides synthesis
MCM-48 TEOS Alkyltrimethylammonium Hydrothermal Basic 2–10 3D
halides synthesis
KIT-1 Colloidal Alkyltrimethylammonium Hydrothermal Basic 2–10 3D
Silica halides synthesis
SBA-1 TEOS Alkyltriethylammonium Lower Acidic 2–10 3D
halides temperature
(273 K)
SBA-16 TEOS Ethylene oxide Ambient Acidic 5–10 3D
Block copolymers temperature
MCM = Mobil Composition Material; FSM-16 = Folded Sheet Mechanism number 16; HMS =
Hexagonal Mesoporous Silica; MSU-1 = Michigan State University number 1; SBA-n = Santa
Barbara University (n = 1, 2, 3, 6, 11, 12, 15, 16); LMU-1 = Ludwing-Maximilians-Universitat
# 1; HMA = Hexagonal Mesoporous Aluminophosphate; KIT-1 = Korea Advanced Institute of
Science and Technology number 1 (Reference taken from Thesis of Kaustava Bhattacharyya)

3 High internal surface area (600–1500 m2 g−1 ).

4 Hydrophilic and hydrophobic nature.
5 Good thermal stability (~1200 K).
6 Different pore geometry.
Owing to these characteristics, the mesoporous materials could generate several
promising new prospects in catalysis, particularly for conversion of bulkier molecules
in several processes, for instance as a cracking catalyst in petrochemical refineries, as
well as in the area of advanced materials, where they are used as hosts to accommodate
various semiconducting materials, dyes and complex nanoparticles. The importance
of these materials can simply be realized from the large number of research papers
and review articles [37–51], that appeared on this subject during the late 90s.
208 D. Tyagi and K. Bhattacharyya

6.4.3.1 Formation Mechanism

Generally, the hydrothermal synthesis of zeolites involves mixing of the silica,

alumina, alkali/alkaline earth metal ions and an organic template molecule, followed
by crystallization in an autoclave for several hours. The most outstanding feature
and the novel idea of replacing the organic (single molecule) template by assemblies
of cationic surfactant molecules was first demonstrated and reported systematically
by the Mobil scientists [41]. Depending on the gel composition and synthesis condi-
tions, the material achieved may consist of a hexagonal MCM-41, cubic MCM-48
or a thermally unstable MCM-50 structure. Mainly three ingredients are required
for synthesizing these mesoporous materials. These are, silica source, a structure-
directing agent in the form of surfactant and a solvent which is generally water. The
final product is obtained after ageing of the gel at about 383 K or by continuously stir-
ring the gel at room temperature for several hours or days. The solid material obtained
is thoroughly washed with distilled water, dried and finally calcined at 823 K first in
nitrogen and then in oxygen to remove the surfactant. These mesostructured materials
thus obtained can be synthesized from various sources of silica such as fumed silica,
tetraethyl orthosilicate, sodium silicate, colloidal silica and also by using different
kinds of surfactants, viz. cationic, anionic, neutral, gemini [49].

6.4.3.2 Various Mechanisms Proposed

Quite a series of synthesis mechanisms are projected to demonstrate the evolution

of the mesoporous materials viz. liquid crystal templating (LTC) mechanism, coop-
erative templating (CT) mechanism, neutral templating (NT) mechanism and folded
sheet (FS) mechanism.
In these mesoporous materials formation, surfactant has major role and depending
upon the water to surfactant ratio, temperature, etc., the surfactant molecules tend to
organize themselves into aggregates with different shapes, basically called micelles.
The scientists from the Mobil group were the first to propose the formation mech-
anism, (Liquid Crystal Templating (LTC) mechanism) [41]. It was assumed that
a liquid crystalline hexagonal mesophase is formed through self-organization of
the surfactant molecules (cationic head groups, S+ ) followed by surrounding and
condensation of the silicate anions (I− ) present in the reaction mixture. It results into
inorganic polymer formation, which attains the surfactant mesophase shape.
The surfactant is removed by burning off through calcination, and the resultant is
hollow inorganic silicate cylinders which are present in a hexagonal arrangement.
This mechanism was not accepted by many groups and subsequently another
mechanism was suggested by the Mobil group. According to this mechanism, when
anionic silicate is added to the cationic surfactant it initiates the formation of hexag-
onal liquid crystalline phase and the subsequent steps were the same as depicted in
the first path. This mechanism got support from a number of research groups [50].
Furthermore, Chen et al. suggested that initially micelles are formed in rod shape
and a random manner. These micelles interact with anionic silicates via electrostatic
6 Synthesis of Porous Materials 209

interaction to give polymerized silica monolayers over the micellar surface [51,
52]. The silica-coated micelles then spontaneously arrange themselves into long
hexagonal arrays. The driving force for the process was believed to cause further
condensation of the silicate species.
Stucky and coworkers proposed the Cooperative Templating (CT) mechanism
which was closely related to their earlier proposed lamellar-hexagonal phase trans-
formation mechanism [53, 54]. This mechanism involves the following three steps:
(i) Strong interaction of Silicate polyanions with surfactant cationic groups at silica-
surfactant interface. (ii) Silicate polymerization takes place at the interface. (iii)
Lamellar phase is transformed into cubic or hexagonal material. The generally
accepted scheme for synthesis of MCM-41 is presented in Fig. 6.6 which matches
with the different propositions proposed by different groups.
Tanev and Pinnavaia suggested a neutral templating (NT) mechanism. These
neutral surfactants include polyethylene oxides and primary amines, where both the
head and the tail groups of the surfactant are neutral [55]. The mesoporous silicates
prepared using this method were designated as HMS and MSU. The NT mecha-
nism is governed by hydrogen bonding due to the neutral surfactants present in this
case, While LCT and CT mechanisms are governed by electrostatic interaction. The
silicate source in this case is tetraethyl orthosilicate (TEOS).

Fig. 6.6 Suggested mechanism for synthesis of MCM-41; CTAB (cationic surfactant), CMC signi-
fies critical micelle concentration where the spherical micelle forms rod-shaped TEOS (tetra ethyl
ortho silicate)
210 D. Tyagi and K. Bhattacharyya

TEOS interacts with head group of the surfactant amine through H-bonding. This
silica-surfactant complex is amphiphilic in nature and contains bulky head groups.
The presence of these bulky moieties enhances the chances of formation micelles in
the form of rods. These rods tend to organize themselves into hexagonal packing.
Following which, the silanol groups undergo condensation and form rigid silica walls.

6.4.3.3 Mesoporous MCM-48 and MCM-41

The advancement of mesoporous M41S materials can be recalled as a very strong

innovation in the field of zeolite and materials science. Three subgroups of the M41S
family have been reported: (i) MCM-41, (ii) MCM-48 and (iii) MCM-50 as described
earlier [41].
Though most of the studies and the research work in the field have been concen-
trated and related to MCM-41, the reason being ease in the preparation of MCM-41
[56, 57]. However, the MCM-48 with three-dimensional pore structure has a number
of advantages over the one-dimensional MCM-41 and this has been well demon-
strated in studies relating to loading of various guest species, catalytic activity, etc.
[58, 59].

6.4.3.4 Synthesis Parameters

Following are some of the important parameters which govern the formation of high
quality MCM-48 and MCM-41 samples: (i) the nature of surfactants, (ii) surfactant-
silica ratio, (iii) duration of synthesis, (iv) pH, (v) crystallization time and (vi)
temperature, etc. A brief discussion of some of these parameters is given below.
(a) Nature of Surfactant
The pore size of the mesoporous material can be tuned by using a suitable
surfactant of a particular chain length. It has been reported that each additional
–(CH2 )– unit increase the pore size by around 0.3 nm. For example, pore size
of MCM-41 increased from 3.16 to 4.80 nm by increasing the chain length of
the surfactant from C12 (C12 H25 (CH3 )3 N+ Br− ) to C22 (C22 H45 (CH3 )3 N+ Br− )
[60]. Furthermore, additional swelling agents like trimethyl benzene also help
to increase the size of the pores [41].
(b) Silica Source and Surfactant-Silica Ratio
The variation in the surfactant to silica ratio also yields mesoporous materials
of different structures. Thus, the change in the surfactant to silica ratio results in
the formation of MCM-41 (≤0.5), MCM-48 (>0.5–1.5) and MCM-50 (≥1.5)
structures [61]. For MCM-41 the silica source which is generally used is fume
silica whereas for MCM-48 tetraethyl orthosilicate (TEOS) is used as a silica
source.
6 Synthesis of Porous Materials 211

(c) Crystallization Conditions

The crystallization of MCM-48/MCM-41 has been studied at different temper-
atures ranging from ambient temperature to 423 K. Generally, it is found that
for an optimized gel composition at a pH of about 11.0–11.5, a well-ordered
structure is formed from 373 to 383 K. For temperatures below or above limit,
disordering in the structure along with presence of other phases is detected.
For MCM-48 and MCM-41 crystallization time of about 24 and 72 h are found
to give an ordered structure. Increase in the crystallization time particularly for
MCM-48 samples leads to transformation of its structure to mixed structure of
(MCM-48 and MCM-50) and finally into a lamellar structure.
(d) Removal of Surfactants
As discussed earlier, the surfactants are removed from the pores by the calci-
nation step. This step affects the crystallinity and ordering of the mesoporous
material prepared. The process of calcination is done in a controlled manner
where the sample is first heated in nitrogen and then in oxygen. In order to avoid
or reduce the loss in crystallinity, alternative template removal processes have
been developed, where the sample is washed thoroughly before calcination
with mixture of HCl/ethanol or various heptane/ethanol mixtures containing
dil. HNO3 so as to remove a part of the surfactant in the process [62, 63].

6.4.4 Application of Mesoporous Molecular Sieves

Mesoporous molecular sieves have applications very much similar to zeolites and
zeo-type materials. Some of the applications of mesoporous materials are discussed
below.

6.4.4.1 Acid Catalyst

All siliceous mesoporous materials have rather poor catalytic activity because of the
surface silanol groups present. Therefore, the substitution of silica by trivalent atoms
like Aluminium, Iron, Gallium, etc., in the mesoporous molecular sieves frame-
work is widely attempted to generate the acidic sites within these materials and
detailed study of which has been presented in an article by Tuel et al. [64]. Thus the
mild acidity of mesoporous materials with large pores due to incorporation of such
heteroatom has increased their catalytic applications, such as acetylation, [65] alkyla-
tion [66], esterification [67], Diels-Alder reactions [68], hydrogenation [69], hydro-
sulfurization and hydrodesulfurization [70], isomerization [71], polymerization [72],
coupling [73] and in petrochemical reactions such as cracking/hydroprocessing of
cumene and hydrocracking of vacuum gas oil [74]. For example, Pt/Al-MCM-41
helped for isomerization of n-paraffin’s to is paraffin’s [75]. Al-MCM-41 was utilized
for Friedel-Crafts alkylation of paraffins, benzene, napthanlene, toluene, etc., using
olefins and alcohols as alkylating agents and their activity was found to be better
212 D. Tyagi and K. Bhattacharyya

than their microporous counterparts [66]. NiMo-MCM-41 showed very good results
for mild hydrocracking of vacuum gas oil leading to high yields of mild distillates
of diesel, kerosene, naptha and C1 -C4 gases. B-MCM-41 homologue has been used
in Prins reaction [66]. MCM-41 bearing large pores have also been found suitable
as acidic catalyst for a number of reactions involving bulky molecules for example,
alkoxylation of tetraphydropyran, acylation of 2-methoxynaphthalene, etc. [76–79].

6.4.4.2 Base Catalyst

The mesoporous materials especially those containing a trivalent heteroatom have

applications as base catalyst also. In this case, an alkali ion or an organic molecule
like amine, etc, compensate the trivalent atom’s negative charge. The process of
imparting basicity can be implemented by cation exchange [80, 81], impregnation
[81], or organic molecules functionalization as a part of treatment after the synthesis
[82, 83], or alternatively by direct incorporation in the gel during the hydrothermal
synthesis [84, 85]. Following are few examples of these approaches: Na+ and Cs+
ion-exchanged Al-MCM-41 samples have been reported by Kloetstra and co-workers
[80, 81]. Temperature programmed desorption of CO2 was used to evaluate the
basic strength of these materials and the material exhibited good activity as well as
selectivity for the Knoevenagel condensation of benzyladehyde with ethyl acetoac-
etate and o-methylation to form napthol. Brunel et al. reported functionalization of
MMS surfaces by alkoxysilanes using the process of grafting [83] and these mate-
rials exhibited strong basicity, which is required for certain reactions like Michael
reactions and transesterification. Introduction of such organic amines during gel
synthesis was reported by Macauaric [84]. Recently, Jaenicke et al. have grafted
organic amine on MCM-41 and used it for formation of monoglycerides from lauric
acid and glycidol [82]. Miller and coworkers reported basic heterogenous meso-
porous materials synthesized through cross-linking of lyotropic liquid crystals [86].
It was found to be good catalyst for Knoevengel condensation of ethyl cynoacetate
with benzaldehyde. Besides this, MCM-41 supported sulfated zirconia, mono and
dimetallic catalysts have also been reported [87, 88].

6.4.4.3 Redox Catalyst

Electro neutrality of the silica framework is maintained by introducing tetravalent

cations in it and therefore it can be used as a redox catalyst. Thus, a number of
transition metal ions such as Sn4+ , Zr4+ , Ti4+ , V4+ , etc., have been introduced in the
silicate framework and are used as redox catalysts [42, 89]. The redox behaviour of
these mesoporous molecular sieves has enabled the process of larger bulky molecules
of various paraffins, olefins and alcohols, etc., for selective oxidation. For example,
Ti-MCM-41 and Ti-MCM-48 catalysts had been utilized for epoxidation of 1-hexene
by H2 O2 [90, 91]. Ti-HMS showed good catalytic properties for oxidation of 2, 6
di-t-butylphenol to the corresponding quinone and for the hydroxylation of benzene
6 Synthesis of Porous Materials 213

to phenol. Zr-MS was used for aniline to azoxibenzene oxidation and epoxidation
of cyclohexene in presence of H2 O2 by Tuel and Gontier [92]. V-MCM-41 was
extensively used for oxidation of organics such as cyclodecane, 1-napthol, phenol,
cyclohexene and other bulky aliphatic and aromatic compounds [93]. Sn-MCM-41
showed selective oxidation and hydroxylation for aromatics [89]. Abdel and Pinnavia
used Sn substituted mesoporous molecular sieves for lactide ring-opening reactions
and to produce poly (l-lactic acid) [94]. Mo and Ni MCM-41 catalysts were used
for hydrosulfurization of thiophene [95]. Cr containing mesoporous silica is used to
catalyse reactions involving various organic substrates. Recently a few lanthanides
and actinides ions have been incorporated in the siliceous framework and found to
be active for oxidation of certain organic substrates.

6.4.4.4 Molecular Host

The mesoporous materials have larger pores as equated to microporous zeolitic mate-
rials and the pore size distribution is narrow and tuneable in this case. Therefore, these
materials have found a wider application in intrapore chemistry as compared to the
previously used microporous materials [96]. Active research in the areas that include
fundamental studies of sorption and phase transition of water, gases and organics in
confined spaces has been studied by many research groups [97, 98]. Recently, adsorp-
tion behaviour studies for benzene and cyclohexene have been carried out and have
been compared with the microporous zeolites [99, 100]. Mesoporous materials have
been ion exchanged with various metal ions and complexes and these hybrid mate-
rials have been used for various catalytic and photocatalytic reactions [101–103].
Another area where these mesoporous materials have been employed extensively is
as host to accommodate nano-scale metal, metal oxides, semiconductor clusters etc.
[104, 105]. The mesoporous materials have also been extensively used to encapsulate
various other guest molecules such as complexes, heteropolyacids, dyes, enzymes,
polymers, fullerenes, carbon nanotubes, carbon wires and polyaniline filaments, etc.,
and such hybrid materials have been used for various fundamental and industrial
research studies [106, 107]. Thus, discovery of mesoporous materials has led to a
new era in the field of inclusion chemistry.

6.4.4.5 Adsorption and Separation

These materials have the potential to be used as a very good adsorbent owing to their
hydrophobic/hydrophilic nature and at the same time a large-sized pore structure. For
example, it has been possible to entrap bulkier molecules like fullerenes in MCM-41
[108]. Thus, these materials can be used as selective adsorbents in separation tech-
niques such as high-performance chromatography and critical fluid chromatography
[109]. They are also used for removing VOCs (volatile organic compounds) from
the gaseous emissions from the industries [110]. Mesoporous solids are also used
for separation of biological molecules. Further, these mesoporous solids can also be
214 D. Tyagi and K. Bhattacharyya

used for heavy metal ions (Ag, Hg, Pb U, etc.) recovery from wastewater. There-
fore, these materials can be effectively utilized for various environment or pollution
control-related reactions [111, 112].

6.4.5 Hard Templating Method (Nano-Casting)

In this strategy of preparation of porous materials, hard templates, e.g. silica, etc.,
are used as the structure-directing agents. This method is used for synthesis of mate-
rials that are cannot be synthesized or difficult to be synthesized by soft templating
methods, e.g. porous carbon and metal oxides.
The basic steps involved here are similar to soft template synthesis, i.e.
a. Preparation of the template
b. Synthesis of the desired material by using template
c. Template removal.
This method is analogous to the metallurgical process of “casting”, only the scale
is minimized to nanometric scale, therefore it is also called as “Nanocasting” [113].
Here the template act as mould and after removal of the mould we get a replica of
the desired material.
The main advantage of this method is better shape and size control, pore regularity
and crystallinity [114–116]. However, the removal of template is often difficult as
compared to the soft templates. Mesoporous carbon [117, 118] and mixed oxides
[114, 115] have been prepared by this method using mesoporous silica templates.
The hard template pores are filled with the precursor and the precursor is thermally
converted to the desired product within the pores. Commonly used precursors are:
sucrose for carbon and metal salts for MOX. In the final step, the desired porous
material is obtained by removal of the template.
Mesoporous silica is one of the most widely used and attractive material as hard
template due to its superior properties like well-defined structure and even pore distri-
bution, large surface area, low toxicity, high thermal stability and good compatibility
with other materials [119]. As discussed in the earlier part of this chapter, these
properties of the mesoporous silica can be tuned by its synthesis conditions (pH
of the synthesis conditions, temperature, nature of structure-directing agents, etc.).
Thermal and chemical stability is another advantage of silica which leads to better
crystallinity of the end product as compared to the soft template method. The basic
ideology of casting and that of nano-casting are portrayed in Fig. 6.7.
The limitation associated with these templates is their removal, since it involves
leaching with reactive chemicals like HF and NaOH which are not environment
friendly and sometime they may react with the end product as well. Another disad-
vantage is that it is a very time-consuming method as the preparation of the template
itself takes a lot of time.
6 Synthesis of Porous Materials 215

Fig. 6.7 Schematic representation of casting and nanocasting

6.4.5.1 Mesoporous Carbon Preparation by Hard Templating Method

Carbon-based materials have a wide range of applications due to their unique prop-
erties like high surface area and tunable porosity. Some of the possible applications
include energy conversion and storage, sensors gas separation, water purification,
biomedical and as catalyst support for production of various bulk and fine chemicals.
Porous carbon-based materials which are suitable for application in various impor-
tant technologies can be divided into many categories, e.g. activated carbon-based
(granules/fibers), graphene-based, CNT-based, ordered porous carbon, etc.
Activated carbon is the major fraction of porous carbon used in different technolo-
gies, which is generally microporous in nature. It has pores consisting of graphene
layers (hydrophobic in nature) and surface functional groups (generally hydrophilic
in nature). It can be prepared by methods like physical activation, chemical acti-
vation, or combination of both chemical and physical activation, carbonization of
polymeric materials and carbonization of carbon precursors using metal salts. All
these methods have been conventionally used to prepare porous carbon. In general,
the inherent advantage of activated carbon as porous carbon lies in low cost of
production as compared to other types of porous carbon.
However, preparation of ordered porous carbon and porous carbon with uniform
pores is difficult as compared to silica because the structure evolution in carbon is
more complicated as compared to silica. Therefore, soft templating methods that
are used for preparation of porous silica, cannot be used for preparation of porous
carbon. For carbon, hard templating route or nanocasting route is employed.
Three basic steps involved in the process are:
216 D. Tyagi and K. Bhattacharyya

Fig. 6.8 Synthetic Strategy for the porous carbon support by Nanocasting

(i) Impregnation of template with carbon precursor, i.e. formation of precursor

template composite.
(ii) Carbonization of precursor by heating in inert atmosphere.
(iii) Removal of the template.
This can be presented in Fig. 6.8.

6.4.5.2 Preparation of Metal Oxides (MOX ) Using Hard Templating

Method

Ordered mesoporous transition metal oxides have numerous advantages over their
bulk and nano-sized counterparts. The superior properties like high surface area, open
pores, tuneable pore size and morphology, stability make them a suitable candidate
for several applications in catalysis, adsorption, drug delivery, sensors, lithium ion
batteries and supercapacitors [119–123].
The three basic steps involved in this case are:
(i) Introduction of metal oxide precursor in the template
(ii) Conversion of precursor to oxide by decomposition or reduction.
(iii) Removal of the template.
For preparation of porous metal oxides, mesoporous silica is the most frequently
used as hard template due to its superior properties as discussed earlier. Furthermore,
the surface silanol (Si-OH) groups lead to better interaction between silica and metal
precursors which results into better replication of the porous structure. However,
the silica-based templates need to be removed by using hydrofluoric acid or sodium
hydroxide, which limits their applicability for preparation of oxides that react with
either solution, e.g. ZnO, MgO, Al2 O3 . For example, hard template synthesis of
mesoporous ZnO using silica can be attained only when the pH of the potassium
hydroxide solution used to remove silica is adjusted to 12 [124].
Other templates like mesoporous carbon, etc., have also been employed for porous
metal oxide synthesis. The limitation in case of carbon materials arise due to poor
surface wetting properties [120, 125, 126]. This issue can be overcome by surface
functionalization of carbon using oxidizing agents. Another issue in this case is
mesoporous structure retention during template removal since high temperature
combustion is required to remove carbon.
6 Synthesis of Porous Materials 217

6.5 Characterization for Different Types of Pores

The use of porous materials in form of charcoal, clay and mortar, etc., and their
properties can be dated back to various ancient civilizations. However, the related
general principles of capillarity, diffusion, and fluid flow were developed much later
in the nineteenth century. Several methods were proposed or developed for quanti-
fying porosity, most common being by the adsorption of different fluids or gases.
Porosity can be simply defined as the faction of empty (void) volume over the total
volume. However, measurement of porosity is not as simple as its definition, as the
empty space can be of different length scales in different materials (few nanometres
to centimetres). Therefore, it is impossible to have a single method that covers this
range. The different techniques that are used could be broadly be divided into four
types as represented in the below Table 6.2 and are classified in the order of the pores
sizes that they can characterize. Also, it is to be mentioned that different techniques
have their own fundamental assumptions and hence may give different results. There-
fore, a combination of different techniques may give a better understanding of the
pore structure of the porous materials.

6.5.1 Adsorption Techniques

6.5.1.1 Surface Area Analysis

The surface area possessed by solid oxide catalyst is important not only for adsorption
process but also for catalytic activity. The gas adsorption-desorption techniques are
generally used to measure the surface area and pore size distribution of solid mate-
rials. BET (Brunauer-Emmett-Teller) method [127] is the most common method for
determination of surface area, involves the following equation:

p 1 C−1 p
= + ( ) (6.1)
ν ( p0 − p) νmC νm C p0

where
p Adsorption equilibrium pressure
po Saturation vapour pressure of adsorbate at the adsorption temperature
vm Volume of adsorbate required for monolayer coverage
v Volume of adsorbate adsorbed at p
C Constant related exponentially to the heat of adsorption in the first layer (q1 )
and heat of liquefaction of adsorbate (qL ) ; C = e(q 1 −q L )/RT
The constant C determines the shape of the isotherm. The higher the value of C,
the more the isotherm tends to type-II, which is desirable for accurate determination
of surface area. A plot of p/(po − p) versus v relative pressure p/po yields a straight
218 D. Tyagi and K. Bhattacharyya

Table 6.2 Showing the different techniques to detect the different types of pores. Macroporous—
>50 nm, Mesoporous—(2–50) nm, Microporous—<2 nm; All Micro + Meso + Macro;
Capillaries—>1000 nm
Sl. no. Characterization tool Techniques Pore range
1 Optical and electromagnetic Optical microscopy Macroporous
radiation Scanning electron Mesoporous and
microscope (SEM) macroporus
Transmission electron Microporous and
microscope (TEM)/high mesoporous
resolution TEM
Atomic force microscope Mesoporous and
macroporus
Scanning tunnelling Microporous and
microscope (STM) mesoporous
Small angle X-ray All
scattering (SAXS)
X-ray tomography Capillaries
2 Fluid and adsorption based N2 , He, Xe-adsorption All
CO2 -adsoprtion All
Hg-porosimetry Mesoporous and
macroporus
He-pycnometry All
Water porosimetry All
3 Nuclear techniques NMR microscopy Capillaries
NMR relaxation Mesoporous and
macroporus
Small angle neutron All
scattering (SANS)
Positron annihilation Microporous and
spectroscopy (PAS) mesoporous
4 Others Thermal porometry Mesoporous and
macroporus
Mechanical tracing Capillaries

line, where the slope S = (C − 1)/vm C and intercept I = 1/vm C. From this, vm can
be calculated as follows.
1
vm = (6.2)
S+1

Using the volume of adsorbate required for monolayer coverage (vm ) and cross-
sectional area of the adsorbates molecule, we can calculate the specific surface area
of the sample by following equation:
6 Synthesis of Porous Materials 219

vm N A Am
S= × 10−20 (m2 /g) (6.3)
W × 22414

where
S Specific Surface Area.
NA Avogadro’s number
vm Monolayer volume in ml at STP
W Weight of the sample (g).
Am Mean cross-sectional area occupied by adsorbate molecule which is 16.2 Å2
for nitrogen at 77 K.
For many practical purposes, the BET equation is generally fitted to the data
over a range p/po = 0.05−0.3 as at higher p/po values complexity arising due to the
adsorption of multilayer and/or due to condensation within the pores. Prior to surface
area determination, samples are subjected to a pre-treatment at 300 °C for nearly 5 h
under vacuum, this step removes impurities such as moisture. An adsorption isotherm
gives better understanding of the surface area and porosity of a material. Adsorption
isotherm is constructed by plotting adsorbate quantity versus relative pressures at
a constant temperature, it is obtained by successive addition of the adsorbate and
subsequent measurement of the equilibrium pressure. In the same manner, desorption
isotherms are acquired by calculating the removed gas quantities from the sample
upon lowering of relative pressure. The adsorption isotherms can be categorized
into five types viz. Type I or Langmuir isotherms show concave curve to the P/P0
axis and the amount of adsorbate approaches a limiting value as P/P0 approaches
1. Type I isotherms are characteristic of microporous materials which have small
external surfaces, some examples are molecular sieve zeolites and activated carbons.
In this type of materials, accessible micropore volume governs the limiting uptake
of adsorbate.
Type II isotherms are characteristic of a nonporous or macroporous material. In
this type of isotherm, we get unhindered monolayer as well as multilayer adsorption.
There is a point on this isotherm where the linear central part of the isotherm starts,
this point usually indicates the completion of monolayer coverage.
Type III isotherms are convex to the P/Po axis. Type III isotherms are very rarely
obtained (example is adsorption of water vapor on nonporous carbons). The absence
of a distinct point (as in case of type II) on type III isotherm is due to strong adsorbate-
adsorbate interactions (Fig. 6.9).
Type IV isotherms are characteristic of mesoporous materials. The initial part of
the isotherm is similar to that of type II and it has a steep slope at higher relative
pressures. The adsorption and desorption isotherms don’t follow the same path in
this case and thus give a hysteresis loop due to capillary condensation in mesopores.
The shape of this hysteresis curve gives idea about the shape of the pores.
Type V isotherms are rare, like that of type III. The only difference is that pores
in this case are in the range of mesopore.
220 D. Tyagi and K. Bhattacharyya

Fig. 6.9 Different adsorption Isotherms

6.5.1.2 Pore Volume and Pore Radii

The total pore volume is measured when quantity of vapour adsorbed when relative
pressure is near to unity and thereby the pores are filled with liquid adsorbate. With the
approximation of absence of macropores in the solid the isotherm remains horizontal
in the range of P/P0 = 1 where the measurement of pore volume could be well
accepted. In the event of the occurrence of macropores there is a steep increment of
the isotherm close to P/P0 = 1 and in the limiting presence of macropores it exhibits
a complete vertical rise in the isotherm. However, once there is a reliable acceptance
of limiting adsorption the total pore volume could be measured under the sample kept
under isothermal conditions. It is considered to be a complete equilibrium between
the formation of the gaseous N2 (Vads ) and liquid N2 (V1iq) and Vliq is calculated using
the Eq. (6.4).

Pa Vads Vm
Vliq = (6.4)
RT

where, respectively Pa and T denotes ambient Pressure and temperature, and Vm

represents molar volume of the liquid adsorbate (34.7 cm3 /mol for nitrogen).
The total pore volume and surface area has very less contribution from the pores
that are filled below a relative pressure of 1, thereby average pore size could also be
estimated from the pore volume. For example, taking into consideration a cylindrical
pore geometry (type A hysteresis), the average pore radius rp can be represented as

2Vliq
rP = (6.5)
S
6 Synthesis of Porous Materials 221

6.5.1.3 Pore Size Distribution

Statistical plot for pore volume distribution versus pore size is called a pore size
distribution plot. The desorption isotherm is given more importance as compared to
that of the adsorption isotherm for the distribution plot as the desorption isotherm
for equivalent amount of gas volume shows lower relative pressure, consequently
possessing lower free energy state. The thermodynamic stability is established via
the desorption branch isotherm. However, in typical cases possessing the hysteresis
in the type -IV- IUPAC the adsorption branch accepted for pore size distribution.
Primarily N2 gas is utilized as the adsorbate gas, however along with it, He and
Xe are also known as adsorbate gases. The Eq. (6.6) is derived with N2 taken as a
adsorbate. Pore size calculation of a mesoporous material is made by assuming a
cylindrical pore structure using the Kelvin Eq. (6.6)

−2γ Vm
rk = (6.6)
RT lh(P/P0 )

where
y the surface tension of nitrogen at its boiling point (8.85 ergs/cm2 at 77 K).
Vm the molar volume of liquid nitrogen (34.7 cm3 /mol).
R gas constant (8.314 × I07 ergs/deg/mol).
T boiling point of nitrogen (77 K).
P/Po relative pressure of nitrogen.
rK the Kelvin radius of the pore.
Using the appropriate constants for nitrogen, Eq. (6.6) reduces to
o 4.15
rk A =    (6.7)
log P0 P

rk = Kelvin pore radius for condensation at relative pressure of P/Po. There is a

definite adsorption that occurs before condensation Since, prior to condensation, rk
is not the genuine pore radius. Some additional term is added to it. The actual pore
radius rp is given by

r p = rk + t (6.8)

◦
 1/2
13.99
t (A ) = (6.9)
log(P0 /P)

where t is the thickness of the adsorbed layer. This statistical t can be considered as
3.54 (Vads Nm ) in which 3.54 Å is the thickness of one nitrogen molecular layer and
222 D. Tyagi and K. Bhattacharyya

Vad /Vmis the ratio of the volume of nitrogen adsorbed at a given relative pressure to
the volume adsorbed at the completion of a monolayer for a nonporous solid of the
same composition as the porous sample. A more convenient method for estimating
t was proposed by de Boer in the form of Eq. (6.9) and is accessible for pore size
distribution calculations. The pore size calculation is basically done by the BJH
(Barrett-Joyner-Halenda) method.

6.5.2 Small Angle X-Ray Scattering (SAXS)

The numerical nanoscale density variance is measured by a low (below 5° θ) angle

X-Ray scattering technique namely Small-angle X-ray scattering (SAXS). Average
particle size distribution, ascertaining pore size, resolving pore shape and size for
monodispersed macromolecules, determine space between partially ordered mate-
rials, etc., are obtained by SAXS instrument. This could be understood effectively by
inspecting the elastic scattering behaviour of X-Rays when passed through a mate-
rial and recording the scattering phenomena a small X-Ray angles. The scattering
intensity could be signified by the spatial Fourier transform of the electron density
fluctuation in a sample where the assumed microstructures may be nearly estimated
as constant electron density. The particle morphology would be obtained indirectly
with a required fitting with certain models. The finely divided solids show definitive
interference effects in certain cases whilst are negligible in others as shown previ-
ously in the literature. The alteration in the packing type leads to different scattering
patterns which may be represented by the radial distribution function as compared to
that of polydispersity. However, within the limit of prod, if absence of oscillations is
detected in scattered intensity, the systematic lowering of intensity is accredited to the
effect of polydispersity in nano-particle size distribution. In SAXS scattered intensity
is represented as a function of the magnitude of scattering vector “q” where q = 4 π
sin (θ)/λ (2 θ is the angle between the incident beam and the detector measuring the
scattered intensity, and λ is the wavelength of the radiation). In the intermediate and
the high region, the scattering intensity is proportional to q−4 . The assumptions for
that are taken into consideration are: (a) Scattering is from equi-axial materials (like
sphere, cube or disc with aspect ratio ~1); (b) nanoparticles are assumed to possess
polydispersity in size, but not in shape. The scattering intensity I (q) can be expressed

Rmax
I (q) = C P (q, R) N (R) (V (R)) 2 d R (6.10)
Rmin

where, P(q, R)—structure factor of the particle; R—Characteristic length, R; N(R)—

size distribution.
However, for spherical nano-particles. A modified Debye-Bueche function is
adapted in order to optimise the structure factor as shown below in (6.11)
6 Synthesis of Porous Materials 223

⎡ ⎤((Ds −6)/2)
1
2 /2
P(q, R) = ⎣1 + q 2 R2⎦ (6.11)
3

The constant in Eq. (6.11) was chosen with an assumption of the structure factor
of a perfect sphere, where R- radius of sphere and D- surface fractal dimension of
the sphere. V(R) is volume of the sphere; and N(R) represents pore radii distribution.
The N(R) can be expressed as
 
1 [(R − R0 )]2
N (R) = √ exp − (6.12)
2π σ 2 2σ 2

R0 and σ are two parameters of the distribution which are related to the mean.

6.5.3 Mercury Porosimetry

Porosimetry is another analytical technique used for quantification of a porous mate-

rial in terms of pore diameter, total pore volume, etc. It involves the introduction of
a non-wetting liquid into the pores of the material to be examined by applying posi-
tive excess hydrostatic pressure. The applied pressure has an inverse relation with
the radius of the pore. Therefore, the pore size can be determined by external pres-
sure needed to force the liquid into a pore against the opposing force of the liquid’s
surface tension. This behaviour of a non-wetting liquid was first described by E.
W. Washburn in 1921 and therefore the equation governing is known as Washburn
equation.
Mercury is most commonly used because it is not wetting, non-reactive for most
of the surfaces and it does not penetrate pores by capillary action. The surface tension
of liquid mercury is very high therefore it tends to contract its volume into a form
with the least surface area. Therefore, the entry of mercury into the pores is facilitated
by application of pressure and this pressure has inverse relation with the opening of
the pore [128].

6.5.3.1 Calculation of the Pore Size Distribution

It is assumed that as the pressure is increased, mercury enters pores in decreasing

order of size. Thus, if V is the volume intruded between P and P+P, it will equal
the volume of pores with radii between r and r-r,
2σ cos θ
r= P
(Washburnequation) (6.13)
224 D. Tyagi and K. Bhattacharyya

where σ is the surface tension and  is the contact angle. This gives a volumetric
distribution of pore sizes.

6.6 Conclusion

This chapter includes an intense description of the synthesis and the characterization
of the different microporous and the mesoporous materials. This will act as a good
guideline for the students and the researchers to understand the different strategies
for synthesis and understanding the properties of the different microporous and the
mesoporous substances.

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NIST Publication
Chapter 7
Synthesis of Highly Ordered Nanoporous
Anodic Aluminium Oxide Templates
and Template-Based Nanomaterials

S. Boominatha sellarajan and Subir Kumar Ghosh

Abstract Fabrication of ordered arrays of nanodots, nano-pillars and nanotubes

require a suitable mould before-hand to mimic the pattern. Nanoporous anodic
aluminium oxide (AAO) templates having pores with long-range order are ideal
fabrication tool for the synthesis of such nanostructures for applications in high-end
technological and biomedical devices. In this chapter, various synthetic routes for
the fabrication of barrier-type oxide layer to nanoporous to ultra-nanoporous ordered
AAO templates having pore dimensions of 10–50 nm with porosity 3–45% have been
discussed. Depending on the type of electrolytes used, temperature and anodizing
voltage, the evolution of pore diameter and cell structure have been covered in detail.
Extensive discussions on the synthesis of self-ordered nanoporous AAO membrane,
effect of anodization conditions on pore parameters was limited to H2 SO4 electrolyte.
Special attention was given on the synthesis strategies of fabrication of self-ordered
ultra-nanoporous AAO membrane with pore sizes <20 nm. Efforts have also been
made to cover the viable synthetic route for large-scale production of self-supporting
porous AAO (PAAO) templates to mitigate future technological demands. Various
techniques that have been adopted to synthesize various nanomaterials (nanorod,
nanodot, nanotube, etc.) using PAAO template as mould and diverse applications of
these nanostructures have also been covered.

Keywords Porous anodic aluminium oxide (PAAO) template · Ultra-nanoporous

AAO · Hard anodization · Pulse anodization · Nanomaterials synthesis ·
Bio-applications

S. Boominatha sellarajan
Department of Mechanical Engineering, Indian Institute of Technology Madras, Chennai 600036,
India
S. K. Ghosh (B)
Materials Processing and Corrosion Engineering Division, Bhabha Atomic Research Centre,
Mumbai 400 085, India
e-mail: [email protected]
Homi Bhabha National Institute, Mumbai 400 094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 229
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_7
230 S. Boominatha sellarajan and S. K. Ghosh

7.1 Introduction

Porous anodic aluminium oxide (PAAO) membrane is unique because of its highly
ordered honeycomb-like structure consisting of a close-packed array of columnar
hexagonal cells/pores. Such novel structures have attracted tremendous attention
to both scientific as well as a technological community because of their capability
to synthesize self-sustained micrometre to nanometer dimensions materials [1–9].
Utilizing bottom-up approach, a simple PAAO template-assisted synthesis technique
allows one to grow nanostructured materials such as nanowires [10, 11], nanorods
[12], nanotubes [13, 14], nanodots [15–20], anti-dot arrays [18, 21–23] easily. Several
porous materials have been considered as templates for synthesizing the nomate-
rials such as polymer track membranes [24–27], self-organized anodized nanoporous
membranes of Al [1, 15, 28–39], Ti [34, 40–46], Si [47, 48], Zr [49] and Hf [50],
zeolites [51, 52], porous mica [53, 54], nanoporous polymer glasses [55, 56] and
other materials. Among these, polymer track and PAAO membranes are considered
to be commercially viable because of ease of fabrication and tunable porous struc-
ture formation. However, the PAAO membrane is superior to the polymer membranes
due to the following advantages: (i) high chemical resistance, (ii) high thermal resis-
tance up to 1000 °C (i.e., polymer membrane can be stable up to ~200 °C), (iii)
tuneable pore parameters such as diameter, interpore distances and density via elec-
trochemical anodization process conditions and (iv) stable pore parameters during
the post anodization process unlike deformation of pore sizes may occur in polymer
membrane during the post-processes such as nanostructure growth, etc. Moreover,
PAAO membranes are rather inexpensive and template-based synthesis of nanoma-
terials is rather faster in comparison to lithographic (photo, X-ray, ion-beam and
interference) techniques (a top-down approach) in fabricating highly ordered nano-
materials since the later process is highly time-consuming and requires very expen-
sive sophisticated equipment’s. On the other hand, the electrochemical anodiza-
tion process is a simple, cost-effective, easy to scale-up and capable of producing
highly ordered long-range nanoporous structures even in the scale of centimetres.
It is believed that the sensitivity of the nano-size effect on materials properties is
strongly influenced by the membranes with uniform/regular cylindrical pore struc-
tures. For this reason, the commercial PAAO membranes obtained by traditional
methods that exhibit a three-dimensional pore structure with a large pore size distri-
bution, i.e., it does not have near-monodisperse pore sizes along the length, are
not desirable to fabricate high-quality nanomaterials. Therefore, the optimization of
process parameters to obtain PAAO membranes with monodisperse pore diameters
along the length of the pores with uniform physical and chemical properties on the
surface and walls of the pores is very important. Due to these reasons, the last couple
of decades, extensive investigations have been done and still, the research is contin-
uing on the synthesis of structurally advanced PAAO membranes, understanding the
porous structure formation mechanism [39, 57–60], tuning the pore diameters while
retaining the ordered structure [30, 32, 33, 38, 57, 61], scaling up of technology [3,
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 231

5, 61–65], etc. These PAAO membranes and template-based fabricated nanomate-

rials find application in technologically efficient [15] for a compact, high density and
highly sensitive magnetic [10] and electronic devices [3, 8, 39, 61, 62, 64], biosensors
[64], gas sensors [66], bio-filtration [67, 68] and also in photonics[69] devices.
In general, two typical methods are followed for the synthesis of PAAO
membranes: (i) a pretreatment or pre-texturing techniques via imprint or electron
beam lithography, optical diffraction grating, atomic force microscope scanning
probe, focused ion beam and polystyrene beads followed by anodization process [15,
70–73] and (ii) two-step anodization process for the self-organized porous alumina
membranes [28, 38, 73–75]. The pre-texturing processes are very expensive, time-
consuming and are only responsible for controlling the initial sites of pore formation
to achieve the ordered AAO membranes. However, the critical factors of controlling
the growth of pores and arrangements with respect to each other are controlled by the
anodization process itself, i.e., the collective anodizing parameters such as electrolyte
solution, pH, concentration, temperature and applied potential or current density.
Due to these constraints, the synthesis of self-ordered nanoporous AAO membrane
using the self-organized two-step method has become very popular. Details of AAO
template fabrication, mechanism and several parameters dependent pore structure
variations, template-based several nanomaterials fabrication and their applications
have been reviewed previously [4, 5, 16, 39, 62, 76–82]. However, these reviews
mostly covered AAO template fabrication from three major acids such as sulfuric
acid (H2 SO4 ) [38, 83, 84], oxalic acid (H2 C2 O4 ) [28, 75, 85, 86], and phosphoric
acid (H3 PO4 ) [28, 60, 87, 88] covering pore diameters in the range 30–500 nm. In the
recent past, in addition to these three acids, several other acids have been explored to
produce porous alumina templates with a wide variety of pore structures [5, 28, 75].
However, in industries, sulfuric acid has been chosen as the most common electrolyte
for the synthesis of the highly ordered PAAO membranes with various structures due
to its low-cost, relative ease of handling and capability to synthesize very small pore
diameter [29, 32, 36, 38, 61]. This has led to the investigation of synthesis of ultra-
small nanoporous(≤20 nm) AAO membranes and thereby fabrication of ultrafine
nanoarrays which ultimately assisted to investigate the quantum confinement effect
and other size-dependent properties [6, 39, 64, 65, 67, 72, 79, 80]. In this chapter, a
brief summary of different strategies adopted to synthesize PAAO membranes with
self-ordered pore patterns, pore formation mechanism, highly ordered ultra-small
PAAO membrane formation with large porosity and template-based strategies of
formation of different nanomaterials will be covered.

7.2 Anodic Aluminium Oxide (AAO)

Formation of a passive oxide layer on the metal surface is very common which
is sometimes dense and tightly bound that prevents further oxidation under ambient
conditions. For example, a thin oxide layer forms spontaneously on the Al surface, so-
called “alumina (Al2 O3 ) layer” under the service environment. This layer thickness
232 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.1 Experimental set-up for anodizing with DC (left) and AC (right). Source Connected to
electrodes inside the electrolyte medium

depends directly on the humidity of the air or the composition of the water/electrolyte.
However, many years ago in 1857, Buff [89] realized artificial growth of compact and
thick soluble porous oxide or insoluble non-porous oxide layer on Al by an anodizing
process in which Al metal was oxidized by immersing in the electrolyte (e.g., acid for
porous and base for nonporous layers) and connected anodically with a current source
either DC or AC as shown in Fig. 7.1. In most cases, a DC source was used and oxide
layers were formed due to the movement of the anions of the electrolyte to the anode
in the presence of an electric field. This led to the formation of one to two-thousandths
of a millimetre-thick oxide layer on Al via “anodization process” for better corrosion
resistance behaviour of Al and its alloys in diverse service environments. Since then,
this kind of thick anodic oxide layers on Al eventually are used as protection against
corrosion and wear, dielectrics in Al capacitors, decorative purposes and the ability
of colouring after incorporation of organic or metallic pigments, electrical insulation,
thermal resistance, and biocompatible coatings, etc. [1, 90].

7.2.1 Types of AAO

With the progressive development of both anodic oxide layer growth on Al surface
from a variety of electrolytes and with the advent of the electron microscopy, Keller
and his co-workers in the year 1953 [91] first reported the formation of self-organized
hexagonal nanoporous and barrier types of alumina layer attached to Al substrates
in acidic medium. Later in the 1990s, Masuda et al. [92] for the first time was
successful in fabricating self-sustained, highly ordered anodic aluminium oxide
(AAO) membrane/template by anodization process from a simple acidic solution.
With subsequent extensive research work in this field [15, 70–75, 92] led to the
conclusion that during anodization process, Al tends to form two kinds of AAO
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 233

layer: (a) the nonporous or barrier-type and (b) the porous oxide layer depending
upon the anodizing condition and parameters [74].

7.2.1.1 Nonporous AAO

A flat, nonporous insulating barrier oxide layer is formed, when Al is anodized in

near neutral (pH > 5) or basic and non-aggressive electrolytes at ambient tempera-
tures under high current efficiency conditions. This thin oxide layer is highly uniform
in thickness and relatively compact, hard and wear-resistant and behaves as an elec-
trical insulator; such layers are called barrier-type AAOs (named as BAAO). These
layers can be grown as either amorphous or crystalline structures depending upon
anodizing electrolyte used or anodization conditions [93]. Table 7.1 summarizes
various anodizing electrolytes and their conditions used for the synthesis of BAAOs.
Amorphous type BAAO is reported when Al is directly anodized in electrolyte solu-
tions such as ammonium adipate [94, 95] and borate [96]. Whereas, the crystalline
type of AAO is formed when the Al surface first reacts with hot water to deposit a
hydrous oxide layer and subsequent anodization to deposit a barrier oxide layer under
the hydrous layer [93]. The resulting amorphous BAAO layer density is reported to
be 3.2 g cm−3 which is relatively lower in comparison to the density of crystalline

Table 7.1 Summary of anodization conditions for the non-porous barrier aluminium oxide layer
Non-acids Concentration pH Anodization current References
density/formation
voltage/electrolyte temp
Ammonium 150 g L−1 6.44 140 V, 65 °C Oh et al. [94],
adipate Chang et al. [95]
Ammonium 5 wt% – 20 A m−2 /300 V, 23 °C Shimizu et al.
borate [96]
Sodium borate 2.2 M 7 5 mA cm−2 Thompson [1],
Uchi et al. [93]
Sodium 0.1 M 10 50 A.m−2 /125 V Wood et al. [97]
chromate
Sodium 0.01, 0.03 and – 3–100 mA cm−2 /20–200 V Moon et al. [98]
hydroxide 0.1 M
Sodium 0.1 M 9.4 175 V Thompson et al.
molybate [90]
Sodium 0.1 M 9.4 50 A m−2 /168 V Thompson [1],
phosphate Wood et al. [97]
Sodium 0.1 M 5.8 50 A m−2 /44 V Wood et al. [97]
sulphate
Sodium 0.1–0.00001 M 7.5 5 mA cm−2 /285–860 V Thompson [1],
tungstate Thompson et al.
[90]
234 S. Boominatha sellarajan and S. K. Ghosh

BAAO of ~3.5–3.8 g cm−3 . It may be noted that the density of crystalline BAAO
is very close to bulk γ-alumina and is reported to have a significant fraction of void
volume [90].

7.2.1.2 Porous AAO (PAAO)

Unlike BAAOs, the porous-type AAO (named as PAAO) layers are formed in acidic
and aggressive electrolytes at low temperature and the growth of pore formation
is rather complex. Structurally the porous alumina consists of 10–100 nm thick
nonporous oxide (i.e., barrier layer) over the Al surface that forms during the initial
stages of the anodization process in an acidic electrolyte. Further, with progress in
anodization duration, it exhibits deep pores with diameters varying between 5 and
700 nm and lengths up to several microns. On microscopic observation, it is now
clear that a very thin barrier-type oxide layer is first formed underneath each verti-
cally grown pores on top of Al surface during anodization process, i.e., a barrier-type
oxide layer is sandwiched between the pores and the Al surface. This kind of porous
oxides can have highly disordered to a long-range self-organized nanoporous struc-
ture having a wide range of aspect (length/pore diameter) ratios. It is also established
that irrespective of the formation of a type of AAO layer, the typical oxide growth
kinetics are mainly initiated due to commensurate egress of Al3+ ions from the Al
matrix and ingress of the O2− or OH− ions from electrolyte solutions into the elec-
trolyte/oxide/metal interfaces under potentiostatic or galvanostatic anodizing condi-
tions. It is now established that BAAO type layer formation is a prerequisite at the
initial stages of PAAO growth [90], hence, we will limit our discussion on BAAO
to the extent needed. However, the growth mechanisms of these two different oxide
layers are quite different and are discussed below.

7.2.2 Growth Mechanism of AAO

Let us consider the case of BAAO layer growth under potentiostatic conditions. Upon
switching on the cell voltage, the resultant current density (j) decreases exponentially
with time (t) because of the progressive growth of insulating oxide layer thickness
as shown in the schematic representation in Fig. 7.2. This j versus t plot dictates the
oxide layer growth behaviour with time and ultimately limits the maximum BAAO
layer thickness. Similarly, under galvanostatic growth of BAAO layers, the voltage
across the cell is increased linearly with time, resulting in the formation of uniform
and thick oxide layer. Once oxide films thicken further, rise in voltage stops and show
plateau behaviour with time. At this high voltage region, the oxide thickening ceases
with the occurrence of a dielectric breakdown associated with visible sparking on the
anode surface. In the linear region of the voltage–time curve, the Faradic efficiency
is 100% [90] and with the progress of oxide film thickness, the current efficiency
decreases because of the limited supply of oxidizing ions (O2− and OH− ). It is
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 235

Fig. 7.2 Schematic diagram of barrier-type alumina formation in a galvanostatic conditions,

b potentiostatic conditions and c BAAO film on Al surface. Reprinted with permission from Ref.
[5]. Copyright 2014, American Chemical Society

now established that the thickness of the BAAO layer grown under potentiostatic
or galvanostatic conditions, is proportional to the applied voltage or the resultant
voltage attained to maintain the current density. However, in all these anodization
processes, the basic mechanism of BAAO growth lies in the migration of Al3+ ions
outwards from the aluminium/oxide (Al/O) interface and the inward motion of O2−
and OH− ions from the oxide/electrolyte (O/E) interface [90] as shown in Fig. 7.2c.
The outward migrated Al3+ ions get oxidised at the O/E interface [74].
Higher current efficiency in case of BAAO formation could be attributed to the
contributions from oxidation at Al/O and O/E interfaces simultaneously [76]. It is
to mention here that the current efficiency, greater than 60% is necessary to form
BAAO type layer formation even when partial current is in the utilization of PAAO
type layer formation [90]. In general, the PAAO layers are synthesized in acidic
medium either by potentiostatic (Fig. 7.3a) or galvanostatic (Fig. 7.3b) conditions.
A thin barrier oxide, BAAO is formed on top of the Al surface during the initial
anodization process. As a result, anodizing current density demonstrates a forma-
tion of high electrical resistance via oxide growth by indicating a steep drop to a
low value after the initial surge (Fig. 7.3a) and simultaneous increase of voltage
(Fig. 7.3b) with time is shown in Fig. 7.3 of region “I”. However, within no time,
BAAO starts dissolving in the electrolyte at O/E interface, hence, decreasing the rate
of fall (increase) of current density (voltage). This leads to the non-uniform dissolu-
tion of BAAO layer and causes minor cracks/flaws at O/E interface as shown in the
schematic representation of Fig. 7.3 in region “II”. These cracks/flaws provide an
electric path, i.e., pore initiates and high current density flows which allows further
oxide growth/dissolution kinetics. On the other hand, the non-uniform thickening of
the BAAO layer may cause the local concentration variation of anions, i.e., a local
increase in the electric field, E, at a relatively thin layer region. In region III, a steady-
state pore formation is recognized, however, the descending pore density due to the
superimposing of pores with the neighbouring one attributes the small reduction in
the resultant current density versus time in Fig. 7.3a. Moreover, the barrier oxide layer
thickness is determined by the dynamic rate balance between oxide formation (i.e., at
the Al/O interface) and oxide dissolution (at O/E interface). Hereto, the oxide layer
236 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.3 Schematic diagram of the kinetics of porous AAO growth in a potentiostatic and b galvano-
static conditions: a Current (j) − time (t) curves for potentiostatic anodization (i.e., V = constant)
and b Potential (V ) − time (t) curve for galvanostatic anodization (i.e., j = constant). Inset: Repre-
sents I: formation of thin BAAO layer on Al; II: initiation of pore nucleation; III: the growth of
regular pore pattern; and IV: formation of the PAAO structure on Al. Reprinted with permission
from Ref. [5]. Copyright 2014, American Chemical Society

formation at the pore bottom is similar to BAAO formation assisted by the inward
migration of O2− and OH− ions. However, the dissolution of the previously grown
oxide layer at the pore base (O/E interface) is mainly governed by the applied electric
field-assisted distribution of reacting ions associated with outward migration of Al3+
ions. This process is called field-assisted dissolution (FAD) of BAAO at the O/E
interface [74] which nucleates a regular pattern of pores as can be seen in the region
“III” (inset of Fig. 7.3). With further progress in time, the porous layer consisting of
uniform pores grows perpendicular to the Al surface as shown in Fig. 7.3 region IV.
The thickness of the porous alumina layer depends on the anodization time and the
chemical reactions involved at the two interfaces for the formation of PAAO layers
are written as [74]:
At the Al/O interface:
−
(ox) + 3e
Al → Al3+ (7.1)

(ox) + 3O(ox) → Al2 O3

2Al3+ 2−
(7.2)

At the O/E interface:

(ox) + 3O(ox) → Al2 O3

2Al3+ 2−
(7.3)
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 237

− +
2H2 O(l) → O2−
(ox) + OH(ox) + H(aq) (7.4)

−
(ox) → O2(g) + 4e
2O2− (7.5)

4OH−
(ox) → O2(g) + 2H2 O + 4e
−
(7.6)

Al2 O3 + 6H+
(aq) → 2Al(ox) + 3H2 O(l)
3+
(7.7)

(ox) → Al(aq)
Al3+ 3+
(7.8)

It is now understood that the pore deepening process is determined by the steady-
state equilibrium between the rate of nonporous oxide formation on Al and the rate of
dissolution of aluminium oxide at discrete points. The chemical reactions Eqs. 7.2 and
7.3 correspond to the anodic oxide formation at Al/O and O/E interfaces respectively
and the reaction Eq. 7.7 represents hydrogen ion-assisted previously formed oxide
dissolution catalyzed by local Joule heating [5, 74, 75, 90–99] and applied potential.
This FAD mechanism favours a direct ejection of Al3+ ions from the Al/O interface
to the electrolyte through the oxide layer as described in reaction Eq. 7.8 [74].
Therefore, the net current efficiency (ηj ) associated with the AAO growth is decreased
by reactions Eqs. 7.5–7.8 for porous-type AAO. The current efficiency for the PAAO
forming layer is ~53% [1, 90, 96] which is much lower in comparison to BAAO layer
formation. This can be explained by the Pilling-Bedworth ratio (PBR) [100], i.e., the
ratio of the molar volume of the grown oxide to molar volume of the consumed metal
in the oxide formation process. The PBR for BAAO type layer formation is reported
to be ~1.7, for the growth of highly uniform oxides on Al surface, keeping Al/O and
O/E interfaces flat.
On the other hand, in the case of PAAO type layer formation, PBR ~0.9 is
reported at the initial stage, and this value rises to 1.22–1.45 for highly ordered
PAAO formation [74] irrespective of the electrolyte. The resultant structure becomes
porous consisting of pores perpendicular to the Al surface as shown in Fig. 7.3 region
IV. Based on [34] these mechanisms, the overall BAAO layer dissolution reaction at
O/E interface is written as:

− +
Al2 O3 + nH2 O(l) → 2Al3+ 2−
(aq) + (3 − n − x)O(ox) + xOH(ox) + (2n − x)3H(aq) (7.9)

In the case of disordered pore formation, the rate of oxygen evolution is thought
to depend on the applied voltage and dictates the pore parameters. However, the
attainment of long-range regular porous structure and the control over the pore size
and the cell size is determined by the anodizing parameters, such as pH, nature of
the electrolyte, applied voltage or current density and bath temperature that will
be discussed in the next few sections of this Chapter. The overall comparison of
238 S. Boominatha sellarajan and S. K. Ghosh

Table 7.2 Comparison of BAAO and PAAO type layer formation, property and applications
Parameters/conditions BAAO PAAO
Electrolytes used Near-neutral and Acidic and aggressive
non-aggressive
Maximum layer thickness Directly proportional to the Current density (j) (i.e., the
under potentiostatic condition applied potential (V) total amount of charge)
involved in the electrochemical
reaction
Oxide layer growth rate Decreases almost Decreases linearly with time
exponentially with time
Current efficiency (ηj ) Nearly 100% Less than BAAO, typically
60%
Pilling–Bedworth Ratio ≈1.7 for the highly uniform <1 at the initial barrier oxide
oxide layer formation, which facilitates the
pore initiation either by FAD or
H+ assisted at O/E interface
~1.22–1.45 for self-ordered
PAAO
Layer property Highly uniform in thickness A porous structure consisting
and relatively compact of vertically/slanting aligned
pores grown on top of thin and
compact BAAO layer attached
to Al base
Applications Corrosion, wear resistance in Catalytic, optical and
the automobile industry, etc. template-based
nanomaterials/nanostructured
fabrication and their related
nanotechnology

BAAO and PAAO type layer formation, properties of AAO layers and applications
are summarized in Table 7.2.

7.3 Synthesis of Self-ordered Nanoporous AAO Structure

Formation of PAAO structure followed by anodization of Al is of one kind but the size
of pores and their distribution across the surface and orientation is very important for
scientific investigations and device fabrication. Therefore, synthesis of AAO structure
with self-ordered pore patterns with uniform pore structure is desirable unlike the
staggered distribution of pores with different sizes and pattern. The properties of
PAAO layers such as the oxide film thickness, porosity, other structural parameters
(pore size, interpore distance) and hardness are strongly influenced by the anodization
process parameters (i.e., electrolyte type and concentration, applied voltage/current
density, temperature and time). Based on the film growth rate (thickness per unit
time) and its hardness property, the traditional anodization process in the industry
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 239

was technically classified as mild or soft and hard anodization. Both techniques were
used for obtaining the PAAO layer on Al [89, 91, 101, 102]. These two anodization
processes of Al are defined as follows:
(i) Hard Anodization: When Al is anodized at high current density/potential at
low temperature (−1 to 10 °C) in concentrated acids yielding a porous/semi-
porous, thick (10–110 μm) and harder oxide coating (hardness ~65 HRC) is
called as “hard-anodization (HA) process” [101, 102]. The low electrolyte
temperature promotes a reduction in chemical dissolution rate of the oxide
layer and pore nucleation sites during surface reconstruction and the applied
high current density/voltage increases the overall alumina thickness as well as
the pore-wall thickness between the neighbouring pores (low porosity). This
type of oxide films has been practiced as corrosion and wear-resistant coatings
in manufacturing industry applications (pistons, cylinders and hydraulic gears)
for several decades. It provides black plating services to military standard spec
Mil-A-8625 [103]. Industrially, the HA process is superior to mild anodiza-
tion due to its performance level and versatility, producing heavy and durable
coatings for abrasive wear applications requiring a larger build-up.
(ii) Mild Anodization: AAO coatings with moderate porosity when prepared at
relatively low current density/potential under high or near room temperature
(≥20 °C) and mild acid contents for a long anodization time is called as “mild-
anodization (MA) process”. Typical industry-based anodization (MA) condi-
tions are 15% H2 SO4 at 20 °C and 12 A/sq. ft. for different anodization time
based on the requirement of the alumina thickness (0.5–7 μm) [89, 104–107].
This kind of oxide coating has smaller pore-wall thickness than the HA AAO
porous layer and the resultant pores are used as a base for primers, bonding
agents and organic coatings for excellent colour dyeing applications.
These two processes are differentiated by the anodic layer thickness and their hard-
ness parameters. Since the pores formed in the porous alumina membrane prepared
either by classical HA or classical MA processes possess non-uniform distribution
of pores along with several micro-cracks on top of the surface that are not suitable
for the synthesis of nanostructures. It should be mentioned here that since decades
researchers avoid chromic acid anodization due to its carcinogenic effect, i.e., the
usage of Cr(VI) ions [107–109] and have not been considered here for discussion.

7.3.1 Modified Mild Anodization (MMA) Process

Mild anodization (MA) has become famous since 1953 because of PAAO structure
formation due to Kellers et al. [91] revolutionary work. However, the MA process had
some inherent shortcomings due to very poor reproducibility in forming long-range
self-ordered pore patterns and in growing high aspect ratio channels. Later in 1995,
Masuda and Fukuda pioneered an advanced “two-step anodization technique” more
suitable for synthesizing PAAO templates with highly long-range ordered hexagonal
240 S. Boominatha sellarajan and S. K. Ghosh

pore arrangements with uniform pore diameters [92]. The first step involves porous
pattern formation in an electrolyte under applied potential/current density and at
low temperature followed by the controlled dissolution of the AAO layer formed
retaining the initial defects on the surface. In the second step, anodization is carried
out under identical conditions of the first step for the growth of pores starting from the
previous step defects sites to inside AAO/Al layer. Post second anodization, a suitable
chemical etching reveals nice long-range self-ordered porous pattern on the surface
of the AAO layer attached to Al substrate. This process is called “modified mild
anodization” (MMA). The typical growth rate of PAAO under MMA condition is ~2–
10 μm h−1 which is rather low in comparison to conventional MA and HA processes.
Furthermore, this process is also found to be simple and cost-effective to produce an
ordered pore formation compared to the one fabricated by the pre-patterned texture
formation on Al surface using the focused ion beam milling, scanning probe scraping,
or hard SiC moulding followed by a single-step anodization process.
Self-ordering of such porous structure is normally estimated from pore param-
eters (a) pore size/diameter (DP ); (b) interpore spacing/periodicity (Dint ) and or
(c) the porosity (P ~ (DP /Dint )2 ) values which are controlled by careful selection
of the anodizing electrolyte (type and concentration) and the operating parame-
ters (applied current density/potential, electrolyte temperature, anodization time)
employed. Therefore, this self-assembled pore formation occurs only in a narrow
anodizing condition, i.e., more specific to acidic electrolytes called, “self-ordering
regime”. Typically, the following acids were extensively used for the fabrication of
highly ordered porous alumina membrane via two-step anodization of aluminium
and typical self-ordered regimes are:
(a) Sulfuric [19–25 V; Dint = 50–65 nm at 1–3 °C]
(b) Oxalic [30–60 V; Dint = 105 nm at 1–15 °C]
(c) Phosphoric [195 V; Dint = 500 nm at 1 °C]
In recent years, several other inorganic/organic acids such as malonic [58],
selenic [110, 111], acetylene di-carboxylic [112], glutaric [113], α-ketoglutaric [113],
acetonedicarboxylic (β-ketoglutaric acid) [113], squaric [114], etidronic [115, 116],
phosphonic [117] and phosphonoacetic acids [118] have also been explored to synthe-
size the self-ordered PAAO membranes. Among these, etidronic acid was found as
one of the self-ordering electrolytes which extends the Dint [530–670 nm] under
anodization conditions of applied potential [145–310 V] and temperature [0–60 °C]
[115, 116].
Figure 7.4 shows the schematic view (a–b) and SEM images of long-range ordered
porous AAO, (c) top surface, (d) cross-section view of AAO with narrow pore chan-
nels, and (e) bottom surface, respectively. Figure 7.5a, b schematically defines various
pore parameters such as growth rate (Rox = AAO layer thickness/anodization time),
barrier layer thickness (t b ), pore wall thickness (t w ), pore diameter (Dp ), interpore
distance (Dint = Dp + 2t w ) for a perfect hexagonal pore arrangement. It should be
mentioned here that there are other pore parameters involved in estimating the regu-
larity and higher orderings such as porosity (P), pore density (n) which are derived
from Dp and Dint . As mentioned earlier, the magnitude of these pore parameters
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 241

Fig. 7.4 Schematic structure of a porous anodic aluminium oxide (AAO) on Al foil and b cross-
sectional view. c–e SEM images of porous AAO, showing top surface, barrier layer, and bottom
surface, respectively. Scale bars are 1 μm. Reprinted with permission from Ref. [5]. Copyright
2014, American Chemical Society. Panels (c-e) were reprinted with permission from Ref. [31].
Copyright 2006 Springer Nature

is extremely influenced by the anodization conditions, such as the anodic poten-

tial/current density, nature of acid, concentration and temperature of electrolyte and
the first anodization time.
Figure 7.5 shows a schematic representation of the two-step anodization process
followed for the synthesis of long-range ordered PAAO membrane. For a two-step
anodization process, a high purity Al (99.999%) passes through an initial anodization
process under a potentiostatic or galvanostatic conditions followed by a chemical
etching step (typically with 1.8 wt% chromic acid / 7.0 wt% phosphoric acid at 60
ºC) that selectively etch the freshly grown yet irregularly shape porous patterned
alumina layer without damaging the Al substrate, ensuring a hexagonally ordered
and textured surface obtained for a 2nd anodization process. This textured surface is
acting as nucleation sites for the pore growth positions during the 2nd anodization
process since pore nucleation favourably occurs at these defect sites. Generally, the
2nd anodization process is carried out under identical conditions similar to the first
anodization process. The final thickness /required pore-channel length of the AAO
membrane could be achieved by suitably controlling the 2nd anodization process
duration. It should be mentioned here that the pore parameters are strongly influenced
242 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.5 Schematic representation of the preparation steps of PAAOs by using a two-step
anodization process

by the applied potential/current density and electrolyte temperature. However, the

pore size can further be adjustable by post-anodization processing while immersing
the AAO membrane in dilute phosphoric acid at room temperature without changing
its interpore distance (Dint ). Based upon the thickness and substrate used for the AAO
membrane, further, it is classified as free-standing or ultra-thin alumina membrane
and connected/attached alumina membrane, as mentioned in Fig. 7.5. The fabrication
of PAAO membranes with a long-range self-ordered nanoporous structure and high
pore regularity depends on the following factors such as:
(i) Sample purity, i.e., typically Al of 99.999% whereas aluminium alloys are used
for industrial MA and HA processes for automobile and other applications. It
should be mentioned here that the alloying element causes different dissolution
rates and diverge the oxide formation mechanism which causes non-uniform
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 243

pore formation and micro-cracks. Therefore, it is necessary to use high purity

Al for long-range ordered PAAO fabrication for nanotechnology applications.
(ii) Pretreatment processes such as annealing and electropolishing/NaOH etching
of Al, which helps to reduce the mechanical stress and grain growth for long-
range ordering and to generate a smoother surface with small etch pits which
act as pore nucleation sites, respectively, and
(iii) A very longer first anodization duration (~5–48 h) leads to achieving a larger
domain size with uniform pore distribution at the pore bottom due to the
coalescence of neighbouring smaller pores and reduces the final pore density
(~1010 –1012 cm−2 ).
In the next few Sections, as a case study, the self-ordered PAAOs formation
in H2 SO4 electrolyte under different anodizing parametric conditions is discussed
to demonstrate mechanistic aspects of controlling pore parameters to obtain a self-
ordered regime zone. It is the H2 SO4 electrolyte that is reported so far PAAO structure
with the smallest pore sizes [32, 36, 61, 119] among all the acids considered for
synthesizing self-ordered porous pattern.

7.3.2 Synthesis of Self-ordered PAAOs with Small Pore Sizes

It is now understood that there are two important anodizing parameters that govern
predominantly the pore parameters while self-ordered pore formation in AAO
membranes. These are anodizing potential and electrolyte temperature. Therefore, a
special emphasis is given here on the anodization conditions as a function of anodiza-
tion potential as well as electrolyte temperature for synthesizing self-ordered small
and ultra-small PAAOs via two-step anodization of Al in H2 SO4 based electrolytes.
A simple two-step anodization procedure was employed on Al (99.99%) to obtain
a self-organized PAAO membrane in 0.3 M H2 SO4 electrolyte. The spatial features
of pore ordering and hexagonal arrangements of the AAO membranes are intensively
characterized by 2D or 3D Fast Fourier Transform (FFT) of the FESEM images of
top-surface PAAO membranes/attached oxide layer. It converts the FESEM surface
images to the resultant lattice points obtained for the structural periodicity in the
inverse space. The FFT images are produced using the image processing software
WSxM (http://www.wsxm.es) [120]. The FFT patterns such as disc, ring and six-
distinct points (six-fold symmetry) strongly depend on the arrangements of pore
periodicity/pore regularity, i.e., pore distribution across the plane of the PAAO layers.
The resultant FFT pattern signifies about the pore arrangements and shapes in XY-
plane as:
(a) Disc shape FFT pattern corresponds to a disordered pore structure (both size
and periodicity)
(b) Ring shape FFT pattern represents ordered periodicity with non-uniform pore
size, and
244 S. Boominatha sellarajan and S. K. Ghosh

(c) Six distinct points or six-fold symmetry FFT pattern indicates the highly
ordered arrangements of pores.
Therefore, the top surface FESEM images of PAAOs for a selected area (~1.16
μm2 ) and its 3D-FFT images are considered here for the discussion to elucidate
the influence of anodization potential and electrolyte temperature on the regularity
of self-ordered pore formation. Moreover, the estimated average pore size and the
interpore distance values are also discussed in the below Sects. 3.3 and 3.4.

7.3.3 Effect of Anodizing Potential on Pore Regularity

The top surface morphology of PAAO membranes fabricated under second anodiza-
tion at three different anodization potentials (15, 19 and 25 V) at a constant electrolyte
temperature (3 °C) is shown on the left side of Fig. 7.6. The corresponding 3D-FFT
plot is also shown on the right side of the figure for the quantitative analysis on
pore regularity and/or pore ordering of PAAOs. It is evident that with an increase in
anodizing potential (15–25 V), the pore ordering is significantly improved from the
irregular pore formation to an ordered hexagonal array as evident by the FFT pattern
transition from the ring shape to the hexagon. Here, the ring structure signifies for

Fig. 7.6 FESEM

micrographs and 3D FFT
images of AAO thin
membranes prepared at 3 °C
for voltages of a, b 15 V, c,
d 19 V and e, f 25 V.
Reprinted with permission
from Ref. [38]. Copyright
2016, Microporous and
Mesoporous Materials
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 245

the poor ordering among pores consisting of short-range domains and non-sharp
boundaries (see Fig. 7.6b, d), whereas the enhancement in the ordered domain size
or the uniformity in repeating pore structure depicted by six distinct high-intensity
peaks arranged in the form of a hexagon (see Fig. 7.6f), as reported by Sulka et al.
[121]. This enhancement in pore ordering at higher anodization potential (e.g. 25 V)
could be attributed by the improved interpore spacing, which further reduces the net
pore density. This is evidenced by the reduced ring diameter of the FFT images with
an increase in anodization potential as shown in Fig. 7.6, i.e., the interpore distance
between two neighbouring nanopores is inversely proportional to the ring diameter
[38, 59, 61, 121]. The estimated average pore size (Dp ) and interface pore spacings
(Dint ) from FESEM image analysis are depicted in Fig. 7.6 as 18 nm (44 nm), 23 nm
(52 nm) and 29 nm (64 nm) for three different anodizing potentials (15, 19 and 25 V),
respectively [38]. This study clarifies that the pore ordering highly depends on the
applied anodization potential at constant electrolyte temperature and the best pore
regularity was obtained at 25 V in 0.3 M H2 SO4 medium at 3 °C.

7.3.4 Effect of Anodizing Temperature on Pore Regularity

The pore-ordering as a function of electrolyte temperature (1–15 °C) while keeping

the anodization potential at 25 V constant was studied in detail in 0.3 M H2 SO4
electrolyte [38]. Top-view FESEM images of PAAO membranes prepared at different
electrolyte temperatures along with corresponding 3D-FFT images are shown in
Fig. 7.7. It is well known that the electrolyte temperature directly influences the
diffusion of ionic species such as (Al3+ or O2− /OH− or SO4 2− ). This leads to relatively
increase in current density due to enhanced dissolution of the oxide layer at a constant
applied potential. Ultimately it contributes to the enhanced oxide growth rate as well
as oxide dissolution at the pore wall edges at the top AAO surfaces as indicated
by an arrow in Fig. 7.7i and corroborated with the previous reports by Aerts et al.
[122, 123]. As a result, the pore sizes were enhanced without affecting the interpore
distances. Moreover, the hexagonal symmetry which represents the domain size of
self-ordered hexagonal arranged pores was noticed to effectively increase till 3 °C and
then deteriorated with further increase in temperature due to enhanced etching rate
[38]. In general, the size of the ordered domain in PAAO should follow an empirical
relation with time as described by a formula, R = Bt n , where R is the radius of the
domain, B is a temperature-dependent parameter and n ranges between 0.5 and 0.4.
However, Almasi et al. [124] reported an increase in domain size as a linear function
of bath temperature for temperature below 17 °C whereas it drastically reduced for
temperature above 20 °C. This kind of non-linear behaviour in the domain size may
occur due to different oxide growth rates at different temperatures at a constant
potential.
246 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.7 FESEM micrographs and 3D FFT images of AAO thin membranes prepared at 25 V for
bath temperatures of a, b 1, c, d 3, e, f 7, g, h 10 and i, j 15 °C. Reprinted with permission from
Ref. [38]. Copyright 2016, Microporous and Mesoporous Materials
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 247

7.3.5 Pore Diameter, Inter-Pore Distance and Growth

Kinetics

Figure 7.8a, b show the average interpore distance and pore diameter estimated
from two-step anodization process of Al as a function of electrolyte temperature
at a constant anodization potential in 0.3 M H2 SO4 [38]. At constant potential, the
following observations were made; (i) the interpore distance does not vary much
with temperature, however, (ii) the temperature assisted oxide dissolution signifi-
cantly etches out the inner wall of the pores thereby increases the pore diameter.
It is well known that the pore parameters in AAO membranes are strongly depen-
dent on the applied potential as supported by the literature data [74]. Similarly, the
estimated interpore distance values were found to be increased from 42 ± 3 nm to
64 ± 3 nm with an increase in the anodization voltage from 15 to 25 V at a given
temperature could be attributed to variation in diffusion layer thickness at the Al/E
interface [86]. It is well known that the diffusivity and reactivity of ions in solu-
tion increase with the rise in temperature and this ultimately enhances the chemical
dissolution of Al2 O3 film on Al. This enhanced dissolution, therefore, etches out
preferentially the larger surface area inner wall of the pores in comparison to limited
surface area pore base. In addition to the electrolyte temperature, the pore diameter
also increases with increase in anodizing voltage. Hence, an enlargement in pore
diameter with the rise in temperature followed by a saturation tendency at a higher
temperature was noticed (as shown in Fig. 7.8b) in contrast to the previous literature
[123] which reported a monotonous increase of pore diameter with temperature. It is
now inferred that the pore nucleation pattern on the Al surface is essentially dictated
by the applied potential and the combined effect of potential and temperature facili-
tates unidirectional pore propagation along the Al base via dissolution. Therefore, the
self-ordered nanoporous domain structure is a resultant influence of the composition
of the electrolyte, anodizing potential and temperature. Moreover, the net current

Fig. 7.8 Variation of pore parameters of AAO membrane as a function of electrolyte temperature:
a inter-pore distance and b pore diameter when the voltage is constant at 15, 19 and 25 V, respectively.
Reprinted with permission from Ref. [38]. Copyright 2016, Microporous and Mesoporous Materials
248 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.9 The variation of

growth rate as a function of
temperature for anodizing
potentials of 15, 19 and 25 V.
Reprinted with permission
from Ref. [38]. Copyright
2016, Microporous and
Mesoporous Materials

density/high electric field strength at the pore bottom [30, 125, 126] can also impact
on the pore growth kinetics or the oxide layer thickness, hence the pore regularity
could be controlled.
For detailed analysis, the steady-state current density data during constant poten-
tial anodization was considered to correlate with the oxide growth rate, Rox (nm/s).
A 3D surface profilometer was extensively used to measure the oxide layer thickness
for the given anodization time. Figure 7.9 shows the exponential nature of the AAO
membranes growth rate with electrolyte temperature at different voltages [38]. It
becomes more prominent at 25 V due to greater influence in growth kinetics. On
the other hand, the electrolyte temperature alone has a noteworthy influence on the
pore growth rate apart from the kind of electrolyte and anodizing potential due to
increased oxide dissolution at the pore bottom as well as the pore edges. This not only
increases the pore diameter but also increases the pore lengthening. As a result, at a
higher temperature, the overall thickness of AAO membranes increases. A modified
Arrhenius equation [127, 128] was used to fit the experimental growth rate data and
temperature (Fig. 7.12) as

Rox = A · exp−Ea / RT +c (7.10)

where E a is the activation energy, R is the gas constant (8.314 J/mol K), T (=T
+ 273.15) is the bath temperature in K, c is a constant and A is a field dependent
coefficient. In 0.3 M H2 SO4 medium, for the given applied potentials 15, 19 and
25 V, the E a values calculated are 31.6, 56.9 and 72.8 kJ/mol, respectively [38], which
corroborates nicely with Han and Shen [87] results reported earlier in H3 PO4 medium.
Due to difference in electrolyte type and the voltage applied, a slight difference in
activation energy values could be noticed.
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 249

Fig. 7.10 Variation of

porosity of ordered AAO
membranes in the
temperature range 1–15 °C
for anodizing potentials 15,
19 and 25 V. Reprinted with
permission from Ref. [38].
Copyright 2016,
Microporous and
Mesoporous Materials

7.3.6 Porosity

Porosity (P) of the porous structure is an important characteristic parameter that

defines the pore density and it is estimated from primary pore parameters such as Dp
and Dint (P ∝ (Dp /Dint )2 ). Figure 7.10 shows the variation of porosity as a function of
electrolyte temperature at different anodizing potentials. It is noticed that irrespec-
tive of the anodization potential, the porosity is found to be nearly constant ∼28%
for anodizing temperature up to 3 °C. However, with an increase in temperature, the
porosity increased from 28 to 45% at 15 V, 26–41% at 19 V and 26–33% at 25 V,
respectively [38]. The porosity values were saturated at higher anodizing tempera-
tures due to temperature-assisted oxide dissolution at the pore walls without affecting
the interpore distances at a constant potential, as discussed earlier [30]. On the other
hand, interesting results obtained that the porosity values were found to be decreased
with the increase in applied potential from 15 to 25 V for a given temperature.
This could be explained by the significant effect on pore parameters (i.e., interpore
distance and pore size) which are strongly influenced by the applied voltage than the
electrolyte temperature. This particular effect is more prominent in the calculated
higher porosity value of PAAO membranes fabricated at lower anodizing potentials
15 and 19 V in comparison to 25 V at elevated temperatures. It is worth mentioning
that Nielsch et al. [28] proposed 10% porosity (P) is a pre-requisite for obtaining
self-ordering in pore patterns regardless of the specific anodizing conditions and
pore diameter is mainly governed by the applied voltage. On the contrary, several
subsequent investigations reported self-ordering of pores can occur in a wide range
of the porosity values from 8 to 45% [61] depending upon anodizing conditions [30]
corroborating present data.

7.3.7 Modified Hard Anodization (MHA) Process

During HA process, it is very difficult to maintain a stable anodization condition

above the breakdown or burning of alumina potential (i.e., 27 V for sulfuric acid)
250 S. Boominatha sellarajan and S. K. Ghosh

due to unwarranted corrosive attack associated with other side reactions under a high
electric field. As a result, non-uniform or irregular porous alumina films are formed
without long-range order for nanotechnology applications. Moreover, this kind of
PAAO layers exhibit poor mechanical strength due to incorporation of the high
density of cracks and structural defects which makes them difficult to handle. To over-
come these difficulties, Lee and other group [5, 30, 31, 125, 129–131] have developed
a modified HA (MHA) process in various electrolytes and successfully synthesized
stable PAAO layers for real-life applications. It is noted that unlike conventional
HA process (10-90 V for sulfuric acid), the MHA process differs substantially in
applied voltages (40-70 V for sulfuric, 120-160 V for oxalic and 195-210 V for
phosphoric acids) and oxide film structures [5, 31, 129]. Conventional HA process
provides a compact, thick and locally bulged surface with several cracks consisting
of non-uniformed pores of porous alumina coating [101, 102] contrary to MHA
process which avoids burning effect by adopting several strategies during anodiza-
tion process, as given below [30, 31, 125, 129, 130]. Moreover, the conventional HA
process displays a large current density whereas the MHA process shows a nearly
exponential decay in current density in current-voltage transient behaviour that could
be attributed to a combination of both ionic and electronic current density in the latter
case. There are of course a few advantages and disadvantages of the MHA process
in forming porous AAO structures:
Advantages:
(i) Very high growth rate (~50–100 μm h−1 ) [5, 31, 129] unlike MMA process
(~2–5 μm h−1 ) [5, 38, 75, 132].
(ii) Self-ordered porous AAO structure with thick oxide wall thickness.

Disadvantages:
(i) Due to very high applied potential, a large amount of localized Joule heat
generates and makes the dissolution process extremely faster. The typical Joule
heating is ~2–4 orders of MMA processes that stimulate hasty dissolution
of the oxide layer at the pore bottom (O/E interface) causing uneven stress
development leading to the local breakdown of the alumina layer.
(ii) Very little control over the pore parameters of the synthesized PAAO structure.
(iii) Very poor reproducibility and reliability of PAAO fabricated from a given
electrolyte.
To overcome these difficulties in MHA and to make it commercially viable and
faster process several methodologies were adopted:
• Aged electrolyte solution [30, 125, 131]
• Effective removal of Joule heat by using a combination of voltage ramping and
cooling plate attached to Al substrate during anodization process [5, 31, 129, 130]
and
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 251

• Electrolyte to act as a coolant by the addition of organic solvents such as ethanol,

ethylene glycol that lowers the freezing point of the electrolyte, hence effec-
tively removes the localized Joule heat generated during the anodization process
[5, 36, 69, 118, 119].
Even after adopting all these techniques, the local burning effect or the oxide
dissolution rate at the harsh MHA conditions was not fully solved. Further to that, a
thin (~300 nm) protective alumina layer was formed before the MHA process using
a different MMA process. This effectively prevented the anode from electrochemical
dissolution at the harsh MHA process which exhibited good reproducibility and reli-
ability [5, 31, 129, 130]. On solving a local heating problem during MHA, the PAAO
layer with a non-uniform porous structure containing bulged surface transforms into
a long-range self-ordered porous structure with a uniform pattern and high mechan-
ical strength layer. Note that its overall density and hardness reduce substantially
in comparison to BAAO layer formed during conventional HA process [101, 102].
Lee et al. [5, 31, 129, 130] has succeeded in the formation of highly ordered PAAO
membranes with a very high growth rate (~50–100 μm h−1 ) using MHA process.
Several researchers [5, 30, 31, 122, 125, 129–131] have made considerable efforts
to utilize MHA technique for the synthesis of the new self-ordering regime to obtain
a wide-range of Dint. The resultant alumina layers provided stable and well-ordered
pore structures with relatively larger Dint values under different operating regimes.
Lee et al. [5] have recently summarized these self-ordering voltages for the fabrica-
tion of PAAOs and their corresponding interpore distance under MMA and MHA
conditions in three major electrolytes, such asH2 SO4 , C2 H2 O4 and H3 PO4 , as shown
in Fig. 7.11. This indicates that the applied voltage in MHA processes is higher than
the MMA processes, hence the former results in higher pore growth rate (~50 μm
h−1 ) in comparison to MMA (2–6 μm h−1 ) processes for the same electrolyte. Apart
from this, the MHA process significantly increases the interpore distances without
disturbing the pore diameter. As a result, the overall porosity value is found to be
reduced to ~3.3% [5, 31, 129, 130]. It should be mentioned here that similar to MMA
process, the pore parameters such as pore diameter, interpore distances, barrier layer
thickness are highly dependent upon the anodization voltage, V. In Table 7.3, the
relevant pore parameters obtained under MMA and MHA anodization conditions
are compared

7.3.8 Synthesis of Self-ordered PAAO Nanostructure

by Pulse Anodization (PA)

Self-ordered PAAOs formed by anodization of Al become a popular template system

in the development of functional nanostructures. As discussed earlier, two main
groups of anodization of Al are; modified mild anodization (MMA) and modified
hard anodization (MHA) and then the combined effect of MMA-MHA promotes
a new sub-group, called “pulse anodization” (PA). It is now clear that the MMA
252 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.11 Self-ordering regimes in MMA (filled symbols) and MHA (open symbols) by using
H2 SO4 (black symbols), H2 C2 O4 (red symbols), H2 SeO4 (green symbol), and H3 PO4 (blue
symbols). The black solid lines represent the linear regressions of the data with correlation parame-
ters of ζMMA = 2.5 nm V−1 and ζMHA = 1.8–2.0 nm V−1 . Data for H3 PO4 -MHA () show current
density (j) dependence of the interpore distance (Dint ) at a fixed anodizing potential (195 V).
Reprinted with permission from Ref. [5]. Copyright 2014, American Chemical Society

process is slow, but it produces self-ordered and uniform tubular pore structures in
a narrow window of anodization conditions. Whereas, MHA process enables faster
oxide growth (i.e., ~25–35 times than the MA), with a larger interpore distance and
forms a new set of self-ordering anodization conditions.
Further, in the PA process, the advantages of MMA and MHA processes were
combined and applied in sequential order. It allows one to design the pulse sequences
purposely that results in continuous tailoring of the internal pore structure as well as
the composition of the anodic oxide. Multi-segmented PAAO layers can be obtained
by different combinations of MHA and MMA regimes, hence, resultant PAAOs may
have different pore sizes and interpore distances along the pore channels.
PAAOs with periodically modulated pore diameters along the pore length have
been synthesized by applying several anodization strategies. Lee et al. [130] first
could able to tailor the PAAOs pore structure using a combination of modified HA and
MA processes. This study makes a new revolution in the pore structural engineering
of PAAOs and called as pulse anodization (PA) process. Here, with a controlled
duration of self-ordered MMA and MHA conditions, the corresponding MMA and
MHA pore structures were achieved alternatively along the length of the vertical
pores. For example, the fabrication of PAAOs with periodically modulated pore
diameters is shown in Fig. 7.12 for anodization carried out in H2 SO4 at MMA and
MHA potentials of 25 V and 35 V, respectively. Figure 7.12a shows the schematic of
a typical pulse anodization (PA) process, where the MMA and MHA conditions are
applied to achieve continuously by the periodic pulses consisting of a low-applied
voltage pulse (V MMA = 25 V) followed by a high voltage pulse (V MHA = 35 V),
respectively. During PA in a given electrolyte, the pore structures were periodically
Table 7.3 Comparison of MMA and MHA processes
Conditions/Pore parameters Modified Mild Anodization Modified hard anodization
Applied voltage/current density Less than a breakdown/burning voltage Greater than the breakdown/burning voltage
Anodization setup The special cooling system of the Al substrate is not The special cooling system of Al is required to remove local
required heat during HA in addition to electrolyte cooling
Pre-treatment Surface cleaning and no protective layer required The thin protective oxide layer on aluminium to control the
reaction heat during HA
Oxide growth rate Linear, below 10 μm/h Nonlinear, 5–35 times higher than MA, 50–100 μm/h
Barrier layer thickness Linearly dependent on the applied potential, 1.2 nm/V 0.6–1.0 nm/V
Pore diameter, Dp 0.9 nm/V 0.4 nm/V
Inter-pore distance, Dint 2.5 nm/V 1.8–2.0 nm/V
Porosity (P) 10–45% ~3%
Pore density (n) 109 –1012 pores/inch2 Lesser than MA
Self-ordering Voltage (V) Dp (nm) Dint (nm) Voltage (V) Dp (nm) Dint (nm)
H2 SO4 25 6–30 65 40–70 15–30 90–140
C2 H2 O4 40–45 30–60 100 120–150 49–59 220–300
H3 PO4 195 100–300 300–500 195–235 V/150–400 mA cm−2 80–140 400–550
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates …
253
254 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.12 a Scheme for the preparation of porous AAOs with modulated pore diameters by pulse
anodization (PA). b False-coloured SEM image of AAO formed by H2 SO4 PA. PAAO slabs formed
by MMA and MHA pulses are indicated by MMA-AAO and MHA-AAO, respectively. c SEM image
showing modulated pore diameter. d SEM image of 3D stacks of MMA-AAO slabs, obtained by
selective removal of MHA-AAO slabs by chemical etching. Reproduced with permission from Ref.
[130]. Copyright 2008, Springer Nature

modulated due to the variation in the current density of each MMA and MHA pulse
conditions and the schematic is shown in Fig. 7.12a.
Since the current density at MMA is lower than the MHA process, a layered
structure of smaller pore diameter followed by a larger pore diameter are alternatively
arranged in the formed PAAOs, whereas the thickness of each anodized segment is
determined by the pulse durations (t MHA = 120 s and t MHA = 0.5 s) as shown
in Fig. 7.12b, c [130]. Apart from this, various anodization techniques have also
been used to modulate the pore structures via PA process: (i) combination of two
different MHA voltages [133], (ii) sequentially changing the electrolytes under same
anodizing current density [60], or anodizing potential [88], etc.
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 255

Table 7.4 Summary of recent self-ordered small and ultra-small nanoporous anodic alumina
membrane using H2 SO4
Con. Additives Anodization Electrolyte Pore Interpore Porosity, References
H2 SO4 Ethylene voltage, V temp., T E , diameter, distances, P (%)
Glycol (V) (o C) Dp (nm) Dint (nm)
(wt.%)
10 0 6–18 3 6.8–19.34 20.47–58.25 – Zhang
wt% et al. [32]
0.3 M 0 15–25 1–15 22–39 42–64 24–43 Sellarajan
et al. [38]
0.3 M 0 25 0–3 43–50 62–65 37–44 Syed et al.
[61]
10 0–90 19 0 19–16 50 14.1–9.5 Martín
wt% et al. [36]
10 50 19 5 -15 21–12 50 17.6–5.2 Manzano
wt% et al. [119]
10 50 15–19 -15 21–25 37–47 34–27 Syed et al.
wt% [61]

7.4 Synthesis of Ultra-Small Pore Diameter PAAOs

Studies on low dimensional nanostructures have attracted to enhance the material

properties due to their quantum confinement effects which are useful to explore
the quantum phenomenon and integrate quantum devices [39, 134]. For most of
the materials, this quantum regime could be achieved for structures below 15 nm
[36, 39, 61, 64, 119]. Therefore, it is important to fabricate nanostructures within
the desired range to understand and explore the confinement effect. Porous anodic
alumina membrane with pore sizes less than 15 nm have been achieved in MMA
conditions [36, 39, 61, 64, 119]. Several synthesis strategies have been employed
to fabricate highly ordered arrangement of self-ordered ultra-small pore arrays via
a simple two-step anodization process. In this context, the basic understanding of
the MMA conditions concerning the pore parameters followed by the strategies
employed for the ultra-small pore formation via a two-step anodization process is
given below:
• The interpore spacing, (Dint ) is exclusively controlled by the applied potential
[28, 75, 132], whereas the pore size, Dp is governed by both applied potential and
electric field strength (E) at the O/E growth front due to balance between oxide
formation and dissolution rate [30]. This oxide layer formation-dissolution rate at
the pore bottom also depends on the localized temperature resulted by the Joule
heating as well as by the electrolyte temperature.
• It is reported [30] that self-ordering in PAAO membrane is improved due to change
in porosity (P ∝ (Dp /Dint )2 ) and the ratio (Dp /Dint ) is a function of electric field
strength (E) during anodization and maintains an inverse relationship at constant
applied voltage.
256 S. Boominatha sellarajan and S. K. Ghosh

• The Dp is subjected to widening process due to the solubility nature of alumina

in the acidic electrolyte during anodization thereby relatively changes the film
porosity without altering the interpore distances. The AAO dissolution process is
found to be temperature-dependent and a dynamic process, i.e., the diffusion of
reactants from the electrolyte to pore walls and vice versa.
Therefore, the velocity of the reactants or ions (v) is directly proportional to the
electric field strength (E), zeta potential (ξ) and the dielectric constant (ε) of the
electrolyte and maintains an inverse relationship to the viscosity coefficient (η) of
the electrolyte [33] as described in the following equation in steady-state condition
during the self-ordering process:

εξ E
ν= (7.11)
4π η

According to this equation, the electric field strength (E) is inversely proportional
to dielectric constant ε of the aqueous electrolyte. Hence low ε leads to higher E and
hence smaller magnitude of Dp /Dint under a given potential. It is also clear that low
ε associated with high η would lead to decrease in velocity of ions under a given
anodizing condition which effectively can reduce the pore-wall widening in a self-
ordered regime and results in the smaller magnitude of Dp /Dint . With the following
new strategies, the ordered porous AAO having ultra-small pore diameters have been
fabricated in MMA process utilizing altered anodizing conditions such as [36]:
• By decoupling the Dp /Dint ratio by applying high electric field strength (E) at the
pore-bottom via reduction of dielectric constant (ε) of the electrolyte. This was
obtained by the addition of a highly water-soluble organic solvent such as ethylene
glycol with low dielectric constant (εethyleneglycol = 41.1) than water (ε water = 72
at 20 °C).
• By decreasing the dissolution rate through the addition of an organic solvent in the
acidic medium which ultimately moderates the aggressiveness of the electrolyte,
i.e., the reactivity of the O2− and OH− ions gets reduced for dissolution of pore
wall [33] during anodization.
• By decreasing the anodizing temperature and voltage compared to MHA self-
ordered regime so that overall PAAO growth rate gets suppressed. This is achieved
by mixing of ethylene glycol in the electrolyte which ultimately decreases the
freezing point of water ≤0 °C. Apart from this, the viscosity of the electrolyte
increases with the addition of ethylene glycol that lowers the temperature thereby
reducing the ionic diffusion according to Eq. (7.11).
Several attempts have been made for the fabrication of ultra-small pore diameters
in PAAO membranes are summarized in Table 7.4. The PAAO membranes having
ultra-small pore diameters in the range 6–19 nm and interpore distance of 20–58 nm
obtained at lower anodization potential (6–18 V) in 10% H2 SO4 electrolyte at 3 °C
are shown in Fig. 7.13 [32]. It is well known that in MMA conditions, the Dp and
Dint follow a linear relationship with applied anodization potential, (i.e., Dp ∝ V =
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 257

Fig. 7.13 Plane-view FESEM micrographs of the PAAO membranes. The periodic pore arrange-
ments with pore diameters of a 6.8 nm, b 8.6 nm, c 11.12 nm, d 16.38 nm and e 19.34 nm are
obtained under anodizing potentials of 6 V, 8 V, 12 V, 16 V and 18 V, respectively. The inset
histograms show the Gaussian distributions of the pore diameters for the five samples. Two magni-
fied figures are inset in a for clarity. Reprinted with permission from Ref. [32]. Copyright 1990,
Nanotechnology

kV, and Dint ∝ V = ζV ) with the proportionality constants k ~ 0.9–1.25 nm V−1 and
ζ ~ 2.5 nm V−1 . At lower anodization potentials (2–18 V), Zhang et al. [32] reported
a similar proportionality coefficient for the pore diameter, i.e., k = 0.9666 nm V−1
but with slightly different coefficient for cell diameter or interpore separation, i.e., ζ
= 2.97 nm V−1 . This particular phenomenon was attributed to the difference in pore
formation mechanism in comparison to self-ordered regime obtained at high applied
258 S. Boominatha sellarajan and S. K. Ghosh

potentials in MMA conditions. Here, at lower applied potential (<5 V), the barrier
layer grows at a very slow rate just after pore nucleation within the first 20 s, unlike
moderate high voltage MMA conditions where the barrier layer thickness grows
very fast as mentioned earlier in Sect. 3.7. From Fig. 7.13, it should be mentioned
here that the fabricated AAO membranes using simplest H2 SO4 electrolyte via a
two-step anodization process at low applied voltages have restricted quantitative
characteristics pore parameters with a hexagonal symmetry, pore ordering and larger
domain size for nanotechnology applications.
Fabrication of high-aspect ratio (i.e., length-to-diameter ratio ~3300) PAAO
membranes with self-ordered ultra-small pore diameter <14 nm was successfully
demonstrated by Martin et al. [36] by anodizing Al in electrolyte containing ethy-
lene glycol (0–90wt%) in 10wt.% sulfuric acid at 19 V and 0 °C. A systematic
decrease in pore diameter from 19 to 14 nm without affecting the interpore distance
(~50 nm) was reported with the gradual addition of ethylene glycol into H2 SO4
electrolyte. Thus, it led to a gradual decrease in porosity of the film from 14.1 to
7.1%. It was also demonstrated that the gradual increase of ethylene glycol into
sulfuric acid decreased the pore growth linearly. As shown in Fig. 7.14a–c, an elec-
trolyte containing 50wt% ethylene glycol shows the formation of ordered PAAO
membranes having the smallest pore diameter of ~14 nm with a porosity of 7.1%
after two-step anodization process. A close look into Fig. 7.14a shows the ultra-
small PAAO membrane consists of poly-domain smaller ordered zones resulting a
ring shape FFT image as shown in the inset of Fig. 7.14a. This study opens up a new
scope for preparing ordered arrays with high-aspect ratio of one-dimensional (1D)
quantum nanostructures via PAAOs that could be integrated into quantum devices.

Fig. 7.14 SEM micrographs of the PAAO anodized in the presence of 50 wt % of ethylene glycol.
a Large view where the polydomain structure can be seen (magnification: 100000×); the inset
corresponds to the Fourier transform (FT) of an image taken at 50000×. b High-magnification
SEM micrograph of the hexagonal cell from which the pore diameter has been directly measured.
c Pore diameter distribution diagram obtained from the digitally analyzed image shown in the inset.
d Detailed view of the cross-section where the parallel pore walls can be clearly seen. e The total
thickness of one of the templates (∼50 μm). Reprinted with permission from Ref. [36]. Copyright
2013, Chemical Society
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 259

Fig. 7.15 Anodization temperature as a function of the pore diameter. The whole set anodization
was performed in 50wt.% ethylene glycol containing 10wt.% H2 SO4 electrolyte. Reprinted with
permission from Ref. [119]. Copyright 2014, Microporous and Mesoporous Materials

Recently, the effect of electrolyte temperature (+15 to −15 °C) in 10% H2 SO4
+ 50% ethylene glycol electrolyte on various pore parameters was investigated by
Manzano et al. [119]. The variation of pore diameter with electrolyte temperature
is shown in Fig. 7.15. They obtained a high aspect ratio (>1000) ultra-small PAAO
membrane with pores of 12 nm in diameter even at 19 V and −15 °C. In this study,
the investigators nicely played with the electrolyte viscosity and dielectric constant.
At low temperature (below freezing point of water, −15 °C), the electrolyte viscosity
increases and addition of ethylene glycol (50 wt%) decrease the dielectric constant.
Therefore, in effect, the diffusion rate of the ionic species decreases resulting in
narrow pore formation.
Very recently, Syed et al. [61] have also demonstrated the successful fabrication
of self-ordered AAO membranes at 15 and 19 V in 10% H2 SO4 + 50% ethylene
glycol at −15 °C. The FESEM images of AAOs prepared are shown in Fig. 7.16. The
obtained average Dp and pore regularity parameters are in the range of 23–27 nm
and ~108 after post anodization process using 5% H3 PO4 . It should be mentioned
here that the post-anodization process includes removal of unreacted Al followed by
barrier layer etching along with the widening of the pore wall using H3 PO4 . This
leads to an increase in the average pore diameter without affecting the interpore
distances, hence the porosity value is also increased, i.e., the obtained porosity was
in the range 31–35%.
260 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.16 FESEM image of PAAOs prepared in 10% H2 SO4 + 50% glycol at − 15 °C. a 19 V;
inset shows typical hexagonal cell pattern and b 15 V, respectively. c, d Pore size distribution of (a),
and (b). Reprinted with permission from Ref. [61]. Copyright 2018, Microporous and Mesoporous
Materials

7.5 Self Standing PAAO Membrane Formation

Previous sections have covered about the synthesis of nanoporous and ultra-
nanoporous AAO structure on Al substrate by different techniques. However,
for applications, the preparation of the self-supporting/free-standing AAO
membranes/templates that are separated from the untreated bare Al substrate is
required and the removal of the base Al layer is another challenging task. Several
techniques have been attempted to detach the PAAO membrane from the bare Al
such as:
• Electrochemical Etching: The electrochemical reduction either by exponential
decay linear/gradual or step-wise decrease in applied potential/current density at
the last stage of anodization process [35], which leads to thinning down the barrier
layer thickness effectively without affecting the other pore parameters.
• Dry Etching: Selective dissolution of Al substrate chemically followed by the
controlled removal of bottom side barrier oxide layer by using dry etching with
the help of Ar+ ion beam [29], BCl3 reactive ions [135] and focused ions beams
of Ga+ [136]. This process also may not influence the pore diameter. However,
the dry-etching processes are rather expansive and time-consuming.
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 261

• Wet Chemical Etching: Wet-chemical route using H3 PO4 solution [137] for
suitable etching of Al and the attached oxide layer is another alternative. However,
the wet-chemical process might enlarge the pore size due to the pore-wall etching
mechanism.
Among these techniques, wet-chemical etching is preferred and very common due
to its simplicity, faster and inexpensive processes for removal of Al as well as barrier
oxide layer with controllable pore size using an H3 PO4 solution and is considered
here for discussion.
Before removal of the barrier layer, the unreacted bare-Al film first dissolves
using CuCl2 solution as mentioned in Fig. 7.5. However, the most critical step in the
fabrication of a self-sustained AAO template is the pore opening just after the removal
of barrier oxide layers by a wet chemical process. As mentioned earlier, H3 PO4 acid
is used to etch the bottom cap alumina layer. This process is time-consuming and
depends mainly on the etchant concentration, temperature and the uniformity of the
barrier layer (locally). At first, it dissolves the oxide layer to thin down the barrier
alumina from the centre of the hemisphere structure [137]. Once the pore opens up
with the thin barrier layer, the migration of solution inside the pores would induce
isotropic chemical etching throughout the alumina film, i.e., simultaneous etching
on the inner pore walls and the exposed AAO surface kept inside the etchant bath.
Therefore, the pore size could be tuned by controlling the etching rate and time in
this wet-chemical process, without affecting the pore density and Dint . The samples
used here are prepared by the self-ordered PAAO membrane at 25 V and 3 °C in
H2 SO4 .
FESEM images of PAAO membranes after the removal of bare Al followed by the
barrier oxide layer at different etching time, i.e., 20–30 min at room temperature are
shown in Fig. 7.17. With the progressive increase in etching time, the barrier layers are
seen to thin down with opening up of pores from the center of each pore on the PAAO
membrane and thereby increases the pore size. At 20 min of H3 PO4 etching time,
an average pore size of 25 nm was obtained, whereas, these pore sizes were further
widened with longer duration etching i.e., 35 ± 4 to 45 ± 4 nm for 25 and 30 min,
respectively. At 30 min of etching time, the disintegration of the honeycomb network
structure on the PAAO surface has been seen to be initiated as shown in Fig. 7.17c.
This reveals that the pore walls can be fully etched by prolonging etching time, and
the upper boundary limits of the etching time may vary with the pore characteristics
parameter, for this case the upper boundary time is as <30 min. Therefore, the porous
AAO membranes were etched for the time interval of 20–28 min to produce 25–45
± 4 nm pore size.
262 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.17 FESEM image of AAO membranes after widening the pores in H3 PO4 solution at RT
for a 20, b 25 and c 30 min; images are having the scale bar of 200 nm. The corresponding pore
size distribution is shown in the right column

7.6 PAAO Template Based Nanomaterials Fabrication

In this section, suitable surface modification of these synthesized PAAO templates

followed by fabrication of various nanostructures (NSs) and their potential applica-
tions are discussed. In general, the functionalities and the properties of the materials
differ if one or more of their dimensions are reduced between 100 and 1 nm from
its bulk form (three-dimensional or 3-D). This is called the ‘nanosize regime’ and
are classified as (i) thin films/antidot arrays (two-dimensional, or 2-D; one of the
dimension is confined to nm), (ii) nanowires/nanotubes (one-dimensional, or 1-D;
two of the dimensions are confined to nm) and (iii) nanoparticles/quantum dots (zero-
dimensional, or 0-D; three of the dimensions are confined to nm). The existence of
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 263

nanoporous channels inside the PAAO membrane helps to act like mould to fabricate
the desired dimension of nanomaterials by controlling the pore filling process. The
main advantages of the PAAO template approach are:
(a) A non-lithography approach for patterning of nanoarrays via a simple and low-
cost process. Pore structures are arranged parallel to each other and their size
and separation can be properly adjusted by anodization conditions.
(b) Highly stable in chemical over a wide pH range (3–9) and temperature upto
1000 °C without degradation of pore parameters.
(c) High surface area (180–250 m2 g−1 ), high pore density (1010 –1012 pores cm−1 );
and are robust and biocompatible.
(d) Post deposition, AAO membranes can easily be dissolved selectively in an
acidic or basic solution due to its amphoteric nature and helps to fabricate the
free-standing highly ordered NSs for over a large area with high throughput.
Through-hole AAO membranes used for nanostructure synthesis:
(a) Synthesis of large/small-aspect ratio nanowires (rods)/nanotube (rings) arrays
via chemical (liquid/gas) phase mechanism.
(b) Evaporation or sacrificial masks: synthesis of ordered nanodot and nanohole
(antidot) arrays via gas-phase deposition and etching respectively.
Various materials like metals, semiconductors, polymers, carbon nanotubes, bio-
materials, proteins can be grown inside the pores of porous AAO membrane either
by gas phase and wet-chemical process.
Bottom-up Techniques: The pore filling of PAAO membrane is normally done by a
bottom-up approach. Two important methods are normally practised to grow nano-
materials, that are classified as dry and wet processes. The dry process includes the
physical vapour deposition, chemical vapour deposition, molecular beam epitaxy,
pulsed laser deposition techniques, etc. It should be mentioned here that similar to
lithography process, these dry processes also require sophisticated equipment to grow
nanostructured materials in the gas-phase environment. Wet-chemical processes
include sol–gel, hydrothermal, electroless and electrodeposition methods which are
very simple, hence, used to grow nanostructures at low cost within a short period
and allows one to fabricate ordered arrays of nanowires (NWs), nanotubes (NTs) and
nanodots (NDs) structures [133–136, 138–140].
Figure 7.18 represents the schematic view for the scopes of PAAOs in mimicking
various nanostructures: 3D (nanopore arrays), 2D (films of antidot arrays), 1D
(nanowire/tubes) and 0D (nanodot arrays), and different kinds of materials and
fabrication techniques used to fulfil the applications.
264 S. Boominatha sellarajan and S. K. Ghosh

Fig. 7.18 The schematic view represents the PAAO-based template-assisted nanostructures
developed for emerging nanotechnology applications

7.6.1 Fabrication of Nanomaterials

7.6.1.1 Nanorod and Nanotubes

Large aspect ratio nanowire/tube arrays were fabricated by electroless and electrode-
position processes [10–12, 133, 136, 138–140] through the channels of the porous
metallized alumina membranes having variable pore diameters and the inter-pore
distances. The electroless process being an autocatalytic reduction reaction helps
the metal nucleation to start anywhere on the exposed surface of pore walls or pore
bottom. Since the deposition starts from the pore walls and proceeds inwardly, elec-
troless deposition often grows nanowires or nanotubes concerning deposition time.
The major advantage of this method is, it does not require an electrically conductive
surface or the deposited material. Hence, a large variety of materials has been grown
as nanowires or nanotube arrays within the pores of the PAAO membrane [13, 14,
66, 133, 136, 138–140]. On the other hand, the electrochemical reduction of the ions
of one or more metals requires a bottom electrode, which is normally obtained by
metalizing one surface of PAAO membrane by PVD technique. This pore bottom
metallized surface forces unidirectional growth of metals through the nanochannels
of an insulating alumina membrane. Figure 7.19 shows the schematic representa-
tion of template-assisted electrodeposition for the preparation of nanowire arrays. It
should be mentioned here that the unwanted electrically conducting surfaces and the
chemically reactive surfaces must be masked from the electrolytes by using a suitable
insulating material. Due to higher and uniform filling rate inside the nanopores of
an AAO membrane, solid nanowires have been grown [10–12], however, one can
tune the growth morphology either rod or tube and properties of these materials by
suitably adjusting the pH, applied current density and chemical composition of the
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 265

Fig. 7.19 Schematic view of the template-assisted electro-deposition process for the growth of
uniform and high-aspect nanowire arrays

electrolyte [10–12]. The length of the nanorods or nanotubes can be adjusted by

simply controlling deposition time.

7.6.1.2 Nanodot and Antidot Arrays

Fabrication of nanodot array requires ultrathin PAAO membranes to get rid of shadow
effect while deposition. The ultra-thin alumina membrane, so-called UTAM (i.e.,
thickness ≤100 nm) have been fabricated via two-step anodization process which
is then transferred to a variety of optically flat substrates such as mirror-polished Si
suitably to obtain base support. This Si supported UTAM membrane then serves as a
shadow mask for the fabrication of a highly ordered array of nanodots [16, 18, 21–23,
67] by sputtering or other physical vapour deposition technique. Using this technique,
high-quality nanodot array of different materials (i.e., metallic, magnetic and semi-
conductor) has been fabricated [13, 15, 17–20, 65, 135]. The schematic presentation
of process steps to fabricate ordered nanodot arrays via vapour phase deposition
is shown in Fig. 7.20. During the deposition process, the sputtered materials are

Fig. 7.20 Schematic view of synthesis of nanodots and antidot arrays on Si substrate using gas
phase deposition process: a Highly ordered ultra-thin alumina membrane, b UTAM transferred on
Si substrate and ready for sputter deposition process, c sputtered particles on UTAM/Si substrate,
d antidot arrays formed on the top surface of the alumina membrane and e ordered nanodot arrays
after removal of the alumina membrane on Si substrate
266 S. Boominatha sellarajan and S. K. Ghosh

entered through nanopores of the mask and formed nanodot arrays on the flat base
surface. At the same time, the coated materials on the top of the membrane formed
an antidot array. Therefore, the ordered nanodot arrays were prepared on Si substrate
after suitably dissolving the alumina membrane in NaOH solution. At the same time,
the films deposited over the porous surface result in antidot nanoarray structures,
as shown in Fig. 7.20d. These structures have been used to investigate the reversal
magnetization process as a function of size and separation in perpendicular magnetic
recording media applications (FePt, CoPt, etc.) [16, 18, 21–23, 67]. Similarly, the Si
nanohole arrays have been fabricated by reactive-ion-etching while serving UTAM
as etching mask/sacrificial layer, in which the bottom surface is etched through the
nano-channel arrays [70, 71]. This technique replaces conventional photolithography
and electrochemical etch methods.
As shown in Fig. 7.21, AAO membrane serves as the evaporation mask to prepare
customized plasmonic nanoarrays such as nanodot, nanocluster, nano-island by elec-
tron beam evaporation using varying membrane surface morphology and deposition
conditions [17, 19, 20, 65]. Figure 7.21a1–a8 displays the Ag and Al nano-island
arrays with different sizes produced with ultrathin hexagonal PAAO membranes and
their extinction spectra as a function of the quantum size effect. This reveals that the

Fig. 7.21 Fabrication of plasmonic nanoarrays by adopting the AAO membranes as masks: a SEM
images of the patterned plasmonic nanoarrays fabricated by electron evaporation utilizing ultra-
thin AAO as masks. The large-area SEM image exhibits the patterned silver cluster nanoarray
fabricated with a ∼100 nm thick AAO mask. (a1)–(a5) Evolution of the plasmonic nanoarrays
during evaporation with alayer thickness of 5 nm, 10 nm, 20 nm, 40 nm, and 60 nm, respectively.
(a5)–(a7) 60 nm thick metallic nano-islands fabricated by adopting the AAO masks with d = 65 nm,
50 nm and 35 nm, respectively. (a8) Ultra-small nanodots fabricated by partial removal of the AAO
barrier layer and the etching time for the AAO mask is t 1 = 1200 s and t2 = 1400 s. b UV–V is
spectra of the Ag and Al plasmonic arrays from (a5)–(a7) on the quartz substrate. The scale bars
in the SEM images are 100 nm. Reproduced with permission from Ref. [19]. Copyright 2017 IOP
Publishing
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 267

Fig. 7.22 Template assisted

magnetic Co nanostructure
arrays: a electrode posited
nanowires; b nanotubes;
c sputter deposited nanodots
and d nanostructured
anti-dots. Inset in a shows a
small-aspect ratio
electrodeposited nanowires
embedded inside PAAOs

localized surface plasmon resonance (LSPR) can be tuned precisely by varying the
nanoarrays size and distances. These nanostructures and their reduced size offer an
opportunity to investigate the quantum confinement effect, i.e., surface plasmon reso-
nance is highly sensitive. Moreover, the advantage of using these structured arrays in
various applications such as imaging, sensing and catalysis as well as novel quantum
devices due to the increased surface-to-volume ratio [19, 65].
Figure 7.22 shows the template-assisted growth of various Co nanostructures: (a–
b) electrodeposited nanowires/nanotube arrays and (c–d) sputter deposited nanodots
and antidot arrays through the pores of porous alumina membrane prepared by two-
step anodization process [10–12, 17, 18, 20, 23].

7.6.2 Applications

(1) Filtration and separation: Freestanding PAAOs of through-hole membranes

with various pore sizes have been used to separate chemical species for bio-
applications [67, 68, 141].
(2) Metal oxide nanostructures: Atomic layer deposition techniques have been
successfully employed to grow metal oxides within the pores of porous
AAO, such as zinc oxide [65, 142], titanium oxide and silicon oxides
[143–146]. These hybrid nanostructure oxides find potential applications in
energy storage (coaxial nanowire ultra-capacitors) [9], energy conversion
(photovoltaics), chemical sensing [62–64, 78, 80, 81], photocatalysis [142],
photoelectrochemistry [142] and cell culture [65, 78–82, 147, 148].
(3) Template assisted carbon-based nanostructures: Chemical vapour deposi-
tion (CVD) process have been utilized to fabricate different carbon-based struc-
tures within the pores of the porous AAO membranes: (i) vertically aligned
carbon nanotubes based alumina membrane prepared from the metal cata-
lyst at the pore bottom of the AAO membrane via electrodeposition process
268 S. Boominatha sellarajan and S. K. Ghosh

followed by CVD process [62, 149], (ii) diamond-like-carbon (a mixture of

graphite and diamond phase) have been homogeneously grown over the inside
pores and also outside porous AAO surface via CVD process [149] and (iii)
Ultra-nanocrystalline diamond films have been demonstrated grown on the top
surface of the AAO membrane by CVD process [150, 151]. These carbon-based
composites have been attracted for their improved mechanical, electrical prop-
erties with the biocompatibility and chemical resistivity behaviour that can be
functionalized with various chemical groups and suitably applied for numerous
biomedical applications [149–151].
(4) Functionalized PAAO Membranes: To make the PAAO nano-channels
biocompatible, suitable functionalization has been done. Such as n-
heptylamine plasma polymer (HAPP) coatings have been synthesized using
plasma-enhanced chemical vapour deposition process to functionalize the
nanoporous channels of AAO membrane. The HAPP coatings on the AAO
surface lead to subsequent functionalization of amino or other chemical groups.
These functionalized AAO surfaceshave been utilized for various separation
and drug delivery applications [62, 65, 149].
(5) Biomedical applications: Nanoporous PAAOs have found applications in
implant modifications [151], cell culture substrates (neuronal, connective tissue
cells, epithelial cells, muscle cells, blood cells, etc.), immune isolation and
drug delivery applications in biotechnology and medicine [4, 6, 62–64, 67, 78,
80, 81, 149, 152, 153]. Recent past, Aw et al. [8] have reviewed the progress
in PAAOs application based on their structural factors and biocompatibility
studies.
(6) Biosensors: Due to the unique properties of PAAOs such as (i) the possibili-
ties like immobilization of target molecules on nanopores and (ii) the enhanced
optical properties, it plays an important role in chemical sensors and biosen-
sors. Recently, Sriram et al. [63] and Santos et al. [154] have summarized the
utilization of PAAOs as chemical and biosensors via optical (luminescence,
plasmon resonance, reflectance, interferometer and scattering effect) and elec-
trochemical (voltammetric, amperometric, impedance, capacitive, resistive and
conductive effect, etc.) sensors.
(7) Quantum Efficiency: Hsu et al. [155] have shown recently the morphologi-
cally manipulated wavelength tunability (i.e., blue shift) and external quantum
efficiency (i.e., ~2.7 × 10–2 %) in the silicon quantum dots (Si-QD) doped Si-
rich SiOx metal–oxide–semiconductor light-emitting diode (MOSLED) which
was fabricated within the nanoporous PAAO membrane to spatially confine the
size of silicon quantum dots (Si-QDs) embedded in silicon oxide (SiOx) during
synthesis.
7 Synthesis of Highly Ordered Nanoporous Anodic Aluminium Oxide Templates … 269

7.7 Summary

Synthesis strategies of fabrication of self–ordered PAAOs with nanoporous and ultra-

nanoporous pore sizes with dimensions in the range of 10–50 nm have been discussed
based on MMA, MHA and pulse anodization technique mainly in H2 SO4 electrolyte.
Various advantages and disadvantages of MA and HA processes have also been
covered. Modified mild anodization is found to be most cost-effective for large scale
production of PAAOs. The detailed mechanism of BAAO layer formation followed
by field-assisted selective dissolution of the oxide layer, the formation of pore nucle-
ation and subsequent pore growth along the oxide layer was discussed. In H2 SO4
medium, the pore diameter is strongly dependent on anodizing voltage, temperature
and but the interpore distance is strictly dependent on the applied potential. The
self-ordered regime in H2 SO4 medium is 25 V at 3 °C. Addition of low dielectric
constant solvent like ethylene glycol into H2 SO4 electrolyte led to the formation of
ultra-nanoporous PAAOs with a pore diameter of ~12–15 nm at a lower anodizing
temperature below the freezing point of water. Post anodization, fabrication of self-
sustained PAAOs with precise pore diameters via controlled dissolution of Al and
underneath BAAO layer has also been demonstrated. During this stage, one can even
control over the pore size. Utilization of PAAOs and template-based fabrication of
various nanomaterials by controlling synthetic processing techniques and application
of these nanostructured materials were discussed.

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Chapter 8
Synthesis Aspects of Nanoporous
and Quasi-One-Dimensional Thin Film
Architecture Photoelectrodes
for Artificial Photosynthesis

Rajini P. Antony

Abstract Artificial photosynthesis is a promising concept (soon to be realized)

where one can use natural resources such as sunlight and water for converting
energy to hydrogen and then to electricity. This is achieved by employing functional
materials which can generate photogenerated electrons and holes which facilitates
hydrogen generation and water oxidation, respectively. In this respect appropriate
materials should be chosen, which possess good visible light absorption, suitable
band position straddling with water oxidation and reductions potentials, chemi-
cally/photochemically stable and earth abundant. Hence, transitions metal oxides like
TiO2 , Fe2 O3 , BiVO4 , WO3 , etc. are generally explored to this end. However, all these
materials have limitations with respect to recombination of charge carriers, diffusion
lengths and conductivity. To overcome these limitations, different strategies have
been adopted such as doping, nanostructuring and making hetero-junctions. Because
of the short penetration depth of photons into the bulk and the short mean free paths of
charge carriers, for a conventional semiconductor, a single atomic layer of semicon-
ductor is insufficient to absorb the solar flux, typically of the order of a few microme-
tres are required to absorb a significant fraction of light. Thus, a high percentage of
charge carriers recombine in the oxide bulk before diffusing to the semiconductor
surface, resulting in poor surface reaction kinetics. The issue can be addressed to a
certain extent by manipulating the semiconductor morphology—for example, quasi-
one-dimensional morphologies such as nanotubes, nanorods and nanoporous struc-
tures can improve photoelectrochemical performance. This is because the electron
transport down the length of the tube/rod is increased in comparison with a collec-
tion of nanoparticles, while the distance holes must travel to reach the semicon-
ductor/liquid interface is relatively small (the upper limit is half of the tube wall
thickness). Thus, the radius of the semiconducting material should be tuned to the
minority carrier collection length and the length should be adjusted for optimal
light absorption. Moreover, the idea of an inexpensive approach of constructing of

R. P. Antony (B)
Water and Steam Chemistry Division, BARC Facilities, Indira Gandhi Centre for Atomic
Research, Kalpakkam 603 102, India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 277
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_8
278 R. P. Antony

photoelectrode assembly includes the development of one-dimensional nanostruc-

tured photoelectrodes, electrocatalyst and finally constructing the tandem cell can
reduce the overall cost of the device. The advancement of nanotechnology has enabled
scientific community to engineer nanostructured materials with enhanced electronic,
catalytic and surface properties. In view of this, the present chapter provides an idea
of the fabrication of nanostructured thin films by different inexpensive synthetic
routes which can be scaled up for commercial devices.

Keywords Thin films · Photoanodes · Photocathodes · Photoelectrochemical

water splitting · Nano-architectured photoelectrodes

8.1 Introduction

Solar to energy conversion by utilizing earth abundant resources is the urgent require-
ment for energy researchers in the context of depletion of fossil fuels, global warming
and environmental pollution [1]. Natural photosynthesis is considered to be the main
energy supply in the earth, where plants produce carbohydrates using carbon dioxide
and water. Under optimum conditions maximum conversion efficiency that can be
achieved is 7%, but only ~1% is the average conversion efficiency from the plants
during its entire life span. Artificial photosynthesis (AP) is a promising concept,
where the idea is to mimic natural photosynthesis process, and one can use natural
resources such as sunlight and water for converting solar energy to hydrogen and
related hydrocarbons and then to electricity [2]. This is achieved by employing func-
tional materials which can produce photogenerated electrons and holes, and facil-
itates hydrogen generation and water oxidation, respectively. However, the major
issues associated with the AP systems are the difficulty in fabricating an efficient
device which can compete with the existing fossil fuel system with respect to cost
and scale up. Thus, much improvement is required for an AP device and a faster
research is vital pertaining to material development, cell construction and long-term
running of the device. Similar to natural photosynthesis process, the AP involves
absorption of light, charge carrier generation and separation followed by catalytic
reactions. Thus, in the context of immediate energy requirement, one should look
for realizing efficient AP devices, the fundamental and mechanistic understanding of
the processes, energetics involved, and cost-effectiveness and up-scaling possibility
of the device in terms of practical application.
Photoelectrochemical (PEC) water splitting is a category of AP, where visible light
active semiconductors and sunlight are utilized for splitting water under applied
bias/no bias generating oxygen and hydrogen in separate compartments [2–5]. A
PEC cell consists of a photoanode and a photocathode where water oxidation and
reduction reactions occur, generating oxygen and hydrogen gas, respectively. The
overall reaction involved is given by following equations

4H+ + 4e− ↔ 2H2 , E red

0
= 0 V versus NHE (8.1)
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 279

2H2 O + 4H+ ↔ O2 , E ox
0
= −1.229 V versus NHE (8.2)

Overall water splitting process can be expressed as

2H2 O + 2H2 + O2 · · · E cell

0
= 1.229 V versus NHE (8.3)

The Gibbs free energy change involved in the overall water splitting reaction is
given by the equation

G = −n F E (8.4)

When the cell voltage is 1.23 V at standard temperature (298 K) and concentration
(1 mol/L, 1 bar) the value of G is + 237 kJ/mol showing that the water splitting
reaction uphill. A schematic representation of the water oxidation and reduction
process using a photoanode and photocathode is shown as Fig. 8.1a, b. The overall
water splitting experimental set up is pictorially given in Fig. 8.1c where optimized
photocathode and photoanode are used for water splitting reaction. In real situation,
one has to apply a potential higher than 1.23 V due the over potentials involved.
The main challenge faced by the PEC system is with respect to photoelectrode
materials used, where a combination of efficient light absorption, charge separation,
and transport are the key factors to be achieved. Other aspects include abundant avail-
ability, low toxicity and long-term stability. Different systems have been explored
to this end which includes molecular4 and semiconductor [3]-based materials. In
these, semiconductor-based materials are of utmost interest which have great poten-
tial scope for commercialization due to its earth abundance, photo-stability, suitable
band edge straddling with water redox levels and good visible light absorption capa-
bility. Several significant achievements have already been realized in the material
development aspect; however, working optimization of the devices is still lagging.
Several questions to be addressed in the material context are as follows:

Fig. 8.1 photoelectrochemical water splitting systems using a n type semiconductor photoanode,
b p-type semiconductor photoanode and c tandem device. Image taken with copy right permission
from Elsevier [6]
280 R. P. Antony

1. How to improve the visible light absorption or light trapping ability of the
material?
2. Can it be improved by engineering the surface structure of the material?
3. What are the modifications to be made to minimize the charge carrier
recombination and maximize the charge separation?
4. Whether single materials serve the purpose of improving all these criteria or it
is required to use heterojunctions?
A practical solution to the above questions can help one to come up with a
promising system which can be utilized to make a commercial PEC device for
efficient energy conversion. The following section discusses main features of semi-
conducting materials which can be used as photoelectrodes in PEC systems. The
chapter then focuses on the key requirement for the morphological modification
using different synthesis strategies followed by a discussion on most common
synthesis strategies adopted for fabrication of quasi-one-dimensional nanostructure
based photoanodes.

8.2 Desired Features of Photoelectrodes Used

for Photoelectrocatalysis

As discussed in the previous section, the appropriate materials to be chosen should

possess good visible light absorption, suitable band position straddling with water
oxidation and reduction potentials, chemically/photochemically stable and earth
abundant [6, 7]. A pictorial representation of an overall water splitting device using
quasi-one-dimensional nanostructured photoelectrodes is shown in Fig. 8.2a, where
the device is composed of a photoanode and photocathode separated by a proton
ion conducting membrane. Both photoelectrodes are coated with electrocatalysts
to improve the charge transfer kinetics involved in hydrogen and oxygen evolution
reactions. Thus, transitions metal oxides like TiO2 [8–11], Fe2 O3 [12–15], BiVO4
[16–19] and WO3 [20–23] are generally explored as photoanodes and the band edge
straddling with water redox levels are schematically shown in Fig. 8.2b. Also, the
theoretical photocurrents that can be achieved by each semiconducting material is
limited by its band gap and the values are graphically shown in Fig. 8.3 [3]. Though
the band edge straddling is suitable for water splitting, these materials have limitations
with respect to recombination [3, 24], diffusion lengths [18, 25–27] and conductivity
[15, 28]. To overcome these limitations, different strategies have been adopted such
as doping [29], nanostructuring [12, 30–34] and making heterojunctions [19, 35–
37]. For a conventional photoelectrode, due to the large penetration depth of photons
into the bulk and the short mean free paths of charge carriers, a single atomic layer
of semiconductor is insufficient to absorb the solar flux efficiently and a too thick
layer will prevent the photogenerated charge carriers from reaching the surface for
reactions. Thus, when a bulk electrode is used a high percentage of charge carriers
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 281

Fig. 8.2 a Conduction and valence band straddling of semiconductors with water reduction and
oxidation potentials and b typical pictorial illustration of an AP-based PEC device where the
photoelectrodes are composed of Q-one-dimensional architecture. The zoomed portion shows the
orthogonal separation and transport of photogenerated electrons and holes

recombine in the oxide bulk before diffusing to the semiconductor surface, resulting
in poor surface reaction kinetics.
The above issues can be addressed to a certain extent by manipulating the semi-
conductor morphologies like quasi-one-dimensional (Q-one-dimensional) structures
such as nanotubes, nanorods and nanoporous structures. These structures can improve
transport properties of the device because the electron transport down the length of
the tube/rod is increased in comparison with a collection of nanoparticles [3, 26]. In
addition, the physical dimensions are similar to that of the charge carrier diffusion
length to enable photogenerated charge carriers to reach the surface easily from the
exciton generation point [38–40]. In other words, the distance with which holes must
travel to reach the semiconductor/liquid interface is relatively small; the upper limit
is half of the diameter of the one-dimensional structure. Thus, improvement in both
the transport properties and orthogonal charge separation by one-dimensional struc-
tures can enhance the overall efficiency of the device. The fundamental issues posed
282 R. P. Antony

Fig. 8.3 Graph showing the theoretical photocurrent density achieved different semiconductor
materials under 1 sun illumination conditions. Reproduced with copyright permissions from ACS
chemistry of materials [3]

by the notoriously shorter hole diffusion length of the metal oxide-based electrode
can, therefore, be overcome by fabricating nanostructures having dimensions lesser
than twice the diffusion length of the material used.
Based on the above discussions, it is now clear that the dimensions of the semicon-
ducting material should be tuned to optimize the minority carrier collection length
and light absorption for achieving higher efficiencies in the commercial devices.
Moreover, the idea of inexpensive photoelectrode assembly mainly includes the
development of one-dimensional nanostructured photoelectrodes, electrocatalyst and
finally constructing the tandem cell. The advancement of nanotechnology has enabled
scientific community to engineer nanostructured materials with enhanced electronic,
catalytic and surface properties [26, 28, 41–44]. Different forms of one-dimensional
nanostructures have attracted the attention recently in the field of energy storage
and conversion devices. The family of one-dimensional nanostructures consist of
systems such as nanotubes [45], nanowires [46], nanorods [47] and nanofibers [48].
For developing these one-dimensional nanostructures, different strategies are gener-
ally adopted which include nucleation and growth, self-assembly or self-organization
and size reduction from two dimensions [26, 43, 44, 49]. In view of these aspects, a
basic idea of the Q-one-dimensional nanostructures is discussed in next section.
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 283

8.3 Quasi-One-Dimensional Nanostructures

The word “nano” is a term indicating a fraction of 1 billionth of a quantity. Mate-

rials which have dimensions in these regimes have shown extraordinary physical,
chemical, electronic and mechanical properties [26, 28, 41–44]. Excellent reviews
and books are available in the literature where detailed reports in which nanostruc-
turing of a material and related improvement in physical and chemical properties [26,
42–44, 49–52]. The classical examples are carbon nanotubes and fullerenes which
are the breakthroughs [53] in the field of nanoscience and technology. Following
these inventions, extensive research has been carried out on these carbon mate-
rials with respect to its morphological, physico-chemical and mechanical proper-
ties. Later many inorganic-based one-dimensional nanomaterials were developed by
various researchers [49, 53, 54] and rigorous researches were conducted and still
on-going for controlling the size and shape of the materials and understanding its
changes in physico-chemical behaviour with respect to the bulk materials. For this
advanced microscopic and spectroscopic tools have been developed, which enabled
the researcher to unveil the physics and chemistry of these nanomaterials.
One important parameter which distinguishes different types of nanomaterials is
its dimensionality aspect. A material is considered to be of nanometer size when at
least one of its dimensions is confined to less than 100 nm. Thus, the nanomaterials
are classified into 0-D, one-dimensional, two-dimensional and three-dimensional
nanomaterials. In the case of 0-D materials the confinement is in the three directions,
for one-dimensional materials the confinement is in the two directions and for the
two-dimensional structure the confinement is on 1 direction. Another subtype of the
class of nanomaterials are quasi-one-dimensional structure where the confinement is
in two directions and weak confinement in the third direction due to the axial direction
and are having interesting applications and expected to play and major role in the form
of interconnects and individual structures in electronic and optical-based devices [44,
49]. Thin films-based nanotubes, nanorods, nanowires and nanofibers belong to these
classes of materials and are pictorially represented in Fig. 8.4 [44]. These quasi-one-
dimensional nanostructures have shown good performance as photoelectrodes in AP
device compared to other nanostructures.
The present chapter does not intend to give a comprehensive idea of fabrication of
quasi-1D nanostructure, rather focussing on the methodologies adopted commonly
for the fabrication of quasi-1D thin film to be used as photoelectrodes in artificial
photosynthesis devices. Thus, the chapter mainly discusses selective and the most
widely adopted synthesis techniques used for the fabrication quasi-1D nanostruc-
tured thin films which are expected to improve the efficiency compared to particu-
late nanostructured thin films. Each section discusses the basic technique and instru-
mentation involved in fabricating the quasi-1D nanostructures and nanoporous struc-
tures followed by advantages and disadvantages of the respective technique. Selected
results on the performances of the photoelectrodes fabricated by the technique, for
the water splitting application, are also summarized in each section.
284 R. P. Antony

Fig. 8.4 Schematic representation of different types of one-dimensional nanostructures which

include a nanowires or nanofibers, b nanorods, c nanobelts or nanoribbons and d nanotubes. These
structures typically have one dimension in the nanometer regime and the second dimensions in few
hundreds of nanometres. Reproduced with the copyright permission form Elsevier [44]

8.4 Role of Quasi-One-Dimensional Photoelectrodes

in Improving the Efficiency of the Photoelectrodes

8.4.1 Improvement in the Light Absorption

Light absorption efficiency of the photoelectrode directly affects the performance

of the photovoltaic/PEC devices. Implementing the surface texture on the surface
of the photoelectrode thin film can enhance the light trapping and absorption. It
is well understood that the nanomaterials having dimensions less than 100 nm are
transparent to light as the dimensions are lesser than the wavelength of the light. The
light absorption can be improved by incorporating three-dimensional texturization on
the surface of the photoelectrode. This can be realized by using arrays of nanowires,
nanorods, nano pillars and nanotubes. By a series of experimental and theoretical
studies by Katzenberg and Korsten et al. showed that Si nanowire array improved
the efficiency of the solar to light conversion [42]. Thus, light absorption of the
materials should be improved by modifying the dimensions of the materials under
investigation. Here, the one-dimensional structures have an advantage of having
longer axial lengths and enable improved scattering of light thereby the neighbour
one-dimensional structure can absorb the light efficiently. In the case of nanotubular
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 285

structures, the light absorption can be further enhanced by the multiple scattering
and absorption of light when the light traps inside the tube. The light harvesting
efficiency (LHE) is calculated from the reciprocal of the absorption length as given
by Eq. 8.5 [18]

LHE(λ) = 1 − 10−A(λ) (8.5)

where A is the absorption at particular wavelength, λ.

Other advantages of one-dimensional structures are higher charge carrier mobility,
superior mechanical strength and mechanical flexibility compared to other dimen-
sional materials, which can prevent the cracking of the devices as well as its use in
flexible devices.

8.4.2 Improvement in the Carrier Collection Efficiency

An important aspect in the AP devices is the carrier collection efficiency. A properly

designed quasi-one-dimensional nanostructure can also enhance the photo generated
carrier collection efficiency. Normally for efficient light absorption, the material
should possess sufficient thickness to have maximum absorption, whereas for better
carrier collection efficiency, the material should be thin to minimize the minority
carrier travel distance. Thus, there is a competition in light absorption and charge
carrier efficiency. This effect becomes pronounced in the case of semiconducting
polycrystalline materials which are facing the notorious issue of “shorter diffusion
length”. For example, the hole diffusion length of the Fe2 O3 photoanodes is reported
to be in the range of 5–20 nm while a film thickness of a few hundreds of nm are
required for good light absorption [55, 56]. Hence, it is an important requirement that
the dimensions of the material to be tuned in such a way that maximum hole transfer
should be achieved either by increasing the hole diffusion length of the material
or by nanostructuring process. To minimize these issues, self-organized structures
of one-dimensional nanostructures are proposed, where charge carrier collection
occurs perpendicular to the light absorption. Experimental studies on nanopillar
structures of materials having shorter diffusion length showed an improved light
absorption and charge collection efficiency, which lead to the production of highly
efficient photoelectrodes with earth abundant materials using a low-cost production
technology [18, 36].
Many researchers have adopted different synthesis strategies for fabricating Q-
one-dimensional nano-architectured thin films of pristine, doped, composite and
heterojunctions-based semiconductors to improve the conductivity, hole diffusion
length, light absorption and charge separation. The following section provides a brief
idea about classic techniques adopted for the fabrication of thin film photoelectrodes.
286 R. P. Antony

8.5 Conventional Synthesis Methods Adopted

for Fabrication of Nanostructured Thin Film
Photoelectrodes

The present section essentially gives a brief idea of the conventional and cost-effective
techniques used for the fabrication of thin film photoelectrodes. A number of tech-
niques are discussed in detail covering the basic principle, instrumentation, and
selected photoelectrochemical results for photoelectrodes fabricated by respective
technique for having a better insight on each route and its influence in increasing the
PEC activity.

8.5.1 Drop Casting

Drop casting technology is nothing but dropping the solution on the substrate
followed by evaporation of the solvent leading to the formation of thin films. The
method is a very simple route for fabrication thin films photoelectrodes where easily
evaporating solvents are employed for making the precursor solution.
When considering the fabrication of thin film photoelectrodes using this tech-
nique, normally precursor of photoelectrode materials are dissolved in a suitable
solvent (should be evaporated at moderately faster rate; systems such as ethanol–
water mixture, ethanol and any other easily evaporating solvents/ mixture) and is
dropped onto the conducting substrates, thereafter subjected to calcination at desired
temperature for crystallization and adhesion. An alternate way of fabricating thin
film photoelectrode using the same methodology is to disperse the semiconductor
nanoparticles in an appropriate solvent, drop casting followed by calcination at high
temperature for improving the adhesion of the nano particulate thin film onto the
substrate. The drop casting method is generally used for the preliminary evaluation
of the performance of the novel materials, where the homogeneity of the thin film
is not critical. Cluster-modified photocathodes were fabricated by drop casting tech-
nique by Hou et. Al. using Mo3 S4 clusters and H terminated p-Si electrode which
demonstrated the water splitting capability with an over potential of 400 mV [57].
Zhao and co-workers studied the water oxidation activity of drop casted monoclinic
WO3 photoanode and reported a photocurrent density of 3.8 mAcm−2 at 1.36 V
versus RHE in 0.1 Na2 SO4 with a Xenon lamp illumination [58]. Lionet and co-
workers reported the PEC activity of MIL-101(Fe) photoanode fabricated by drop
casting route [59]. All these studies show that the present fabrication route can be
used as a preliminary technique to evaluate the solar water splitting activity of novel
materials. The main advantages and disadvantages of the technique are listed below.
Advantages
1. Quick and accessible method to fabricate thin films in relatively small area
2. No waste of precursor solution during synthesis
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 287

3. Can be used for the preliminary performance evaluation of the novel materials
fabricated.

Disadvantages
1. Non-uniform film thickness or internal structure (surface roughness) due to the
different evaporation rates across the substrate or change in concentration even
under best conditions
2. Difficult to control the thickness of the film
3. Cannot be used in large area film synthesis.

8.5.2 Spin Coating

Spin coating is one of the most commonly adopted techniques for the fabrication
of thin films due to the ease of handling and quality of the film. The technique is
widely applied in organic electronics, nanotechnology and semiconductor industries.
This is because; the technique can generate films of varying thicknesses (from few
nm to several micrometres) with good uniformity, and is essential for electronic
devices. The spin coating process involves dropping of the precursor solution or ink
onto the desired substrate, similar to the drop casting technique. The drop casted
substrate is then rotated at a high speed (decided by rotations per minute, rpm),
thereby spreading the ink uniformly all over the substrate. The substrate to be coated
is normally fixed on the rotor with the help of vacuum. During the rotation period,
the solvent evaporates and the desired material coating is achieved on the substrate
uniformly. The thin films thus formed are subjected to calcination for crystallization.
The pictorial representation of the fabrication steps of the thin film photoelectrode
using this technique is as shown in Fig. 8.5. Along with the drop casting technique,
spin coating technique is considered as the benchmark for the research and industrial
level fabrications. The thickness of the spin-coated film is dependent on the rotation
speed, viscosity of the solution used, and the time of rotation. The parameter which
decides the thickness of the film is governed by the following Eq. (8.6).

Fig. 8.5 Schematics representation of fabrication of thin films by spin coating route
288 R. P. Antony

    13
1 − ρA 3ηm
t= · (8.6)
ρ A0 2ρ A0 ω2

where t is the thickness of the film, ρ A = density of volatile liquid, η= viscosity of

solution, m = rate of evaporation and ω is the angular velocity. Thus, the thickness of
the film is inversely proportional to the square root of the angular velocity as shown
in Eq. (8.7) and can be used as a simpler route Eq. (8.6) to calculate the thickness of
the film.
1
t∝ √ (8.7)
ω

Thus, spin-coated films having thickness in the nanometer regime is generally

fabricated under high rpm. This dependence allows the precise control of the film
thickness.
In the same way, the concentration of the ink also governs the film thickness,
where at low concentration range; the film thickness will have a linear dependency,
whereas at higher concentration a nonlinear relationship will develop due to the
increased viscosity of the ink. The spin coating duration also affect the thickness of
the film and generally the duration of the rotation is kept in the range of 30–60 s
for common solvents such as water, isopropyl alcohol, ethanol and methanol when
solvents such as ethylene glycol and glycerol (high viscous solvents) are used a
longer spin duration is required to achieve similar thicknesses.
The spin coating technique is also an effective way of constructing three-
dimensional nanoporous films having a controllable thickness, which has shown very
good performance in PEC devices. This is generally achieved by incorporating high
molecular weight sacrificial polymers such as polyvinyl pyrollidone [60–62] or poly
vinyl alcohol [63, 64] into the precursor solution for spin coating and the nanoporous
structure is thus achieved by repeated spin coating–annealing steps. The porosity of
the film in this case can also be varied by changing the amount of polymer incorpo-
rated. Thus, the light absorption and catalytic efficiency can be varied by changing
the porosity of the thin films fabricated using this technique.
Parmar and co-workers reported the fabrication of BiVO4 -based photoanodes
using spin coating technique where the Mo, W co-doped BiVO4 photoanode showed a
water oxidation photocurrent of 2.38 mAcm−2 at 1.23 V versus RHE [65]. Biswas and
Baeg fabricated W doped FeVO4 photoanodes by layer by layer deposition by spin
coating having a photocurrent density of 0.4 mAcm−2 [66] Fabrication of CuWO4
photoanode through spin coating was reported by Zhang et al. which demonstrated
a photocurrent of 1.5 mA cm−2 in phosphate buffer [67]. A layer by layer porous
gradient Mo:BiVO4 was fabricated by Antony et al. by repeated spin coating route
and PVP was used a sacrificial polymer to introduce porosity in thin film [68]. The
resultant photoanode could generate a photocurrent of ~1.74 mAcm−2 at 1.23 V
versus RHE in 0.5 M Na2 SO4 . Quinonero et al. have used the spin coating technique
to fabricate La and Ce doped BiVO4 photoelectrode and reported an increase in the
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 289

photocurrent with doping process [69]. All these studies point towards the impression
that the spin coating route for the fabrication of photoelectrode is an efficient method
to have preliminary evaluation of the PEC performance of novel photoelectrodes
fabricated. In addition, in case of porous thin films fabricated by this route, where
sacrificial polymers are employed, and the water oxidation performance is promising
and the technique can be up scaled for commercialization. Few advantages and
disadvantages of the current technique are given below.
Advantages
1. Simple and cost-effective technique
2. Good reproducibility of the technique due to high rotation speed, air flow and
drying
3. Good uniformity of the spin-coated film
4. Good control over the thickness of the film
5. Multilayer deposition can be achieved.

Disadvantages
1. Technique cannot be applied for large surface area coating
2. Wastage of the precursor during deposition
3. Faster drying of the film leads to lesser molecular disordering, thus resulting a
lower performance of the device
4. Relatively lower throughput.

8.5.3 Dip Coating

Dip coating is an easy, simple and controlled process where the substrate of interest
is dipped in a precursor solution with precise withdrawal rate under controlled condi-
tions of temperature and pressure. The thickness of the film formed is mainly decided
by the withdrawal speed, amount of precursor in the solution and the viscosity of
the solution. During the withdrawal of the substrate, the solution homogeneously
spreads on the substrate surface due to the combined effect of viscous drag and
capillary rise. After withdrawal of the substrate, the drying process of the film can
be done by conventional thermal/UV/or IR techniques. The coating thickness can be
calculated by the Landau–Levich equation [70] (Eq. 8.8) as given below.

(η.v)2/3
h = 0.94. 1/6
(8.8)
γ L V (ρ.g)1/2

where h = coating thickness, η = viscosity, γ L V = liquid–vapour surface tension, ρ

= density and g = gravity. A schematic representation of the dip coating technique
is shown in Fig. 8.6 where different steps involved in the dip coating process leading
to the formation of thin films are picturized. For an efficient coating, the whole
290 R. P. Antony

Fig. 8.6 Schematic representation of conventional dip coating unit. The zoomed portion shows
different process happening during the dipping and withdrawal of the substrate leading to the
formation of thin film electrodes

experimental facility should be kept on a vibration free table to ensure the film
thickness homogeneity formed at each deposition step.
Dip coating technique was applied for the fabrication of WO3 photoanodes by
Hilliard et al. and the PEC studies showed a photocurrent of 0.6 mAcm−2 in potas-
sium phosphate buffer [23]. Similarly, Mo doped BiVO4 photoanodes fabricated
using this technique showed an efficient water oxidation photocurrent of 1.9 mAcm−2
which is a promising value for researchers to use this technique and material for
commercial application [71]. In a parallel publication, it was reported that sol gel
dip coating route can be adopted to fabricate BiVO4 films for photoanode appli-
cation showing a photocurrent value of 2.1 mAcm−2 under 300 W Xenon lamp
illumination (phosphate buffer—pH = 7) [72]. Landsmann et al. adopted a dip
coating strategy to fabricate reproducible, and scalable particle based photoanode
system employing LaTiO2 N with a maximum photocurrent density of 2.52 mA/cm2
at 1.23 V versus RHE under 1 sun illumination [73]. Efficient solar water splitting
performance was observed for highly aligned Cu2 O/CuO/TiO2 core/shell nanowire
array photocathode, where TiO2 is coated on Cu2 O/CuO by a dip coating route [46].
Thus, photoanodes fabricated by this method is proved to show good water oxidation
behaviour and can be adopted for a large-scale electrode fabrication. Some of the
merits and demerits of the dip coating technique is listed below.
Advantages
1. Easy and simple technique
2. Minimal wastage
3. Uniform film coating can be achieved
4. Large area coating can be achieved
5. Very thin layers can be generated.
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 291

Disadvantages
1. Technique results in coating on both side
2. No control over the surface roughness
3. Time consuming process
4. Requirement of clean room
5. Proper training and optimization is required for getting a high-quality film
6. A good dip coating machine is normally expensive.

8.5.4 Doctor Blading

Doctor blading is a widely accepted thin film fabrication technique which is applied
for large-scale fabrication. In this process, well-dispersed slurry containing the nano-
materials of interest is applied on the substrate to be coated which is kept under
vacuum for adhesion. The blade helps to spread the slurry homogenously on to
the substrate. A constant relative movement between substrate and the blade with a
specific distance (typically 10–500 μm) enable the formation of thin wet film. The
thickness of the film can be controlled by adjusting the gap between the blade and
the substrate. A schematic representation of the doctor blading technique is shown
in Fig. 8.7a. The wet thickness of the film is generally half of the gap between the
blade and the substrate and is influenced by the substrate surface energy, surface
tension and viscosity of the coating solution. The dried film thickness as a result of
doctor blading can be calculated by the empirical relation given below in equation
[74] (8.9)

1 c
d= g( ) (8.9)
2 ρ

Fig. 8.7 Pictorial illustration of a doctor blading technique and b spray coating technique
292 R. P. Antony

where d is the dried film thickness, g the gap width between the blade and the
substrate, c the concentration of the precursor solution in gcm−3 and ρ the density of
the material in the precursor solution in gcm−3 . Doctor Blading technique is widely
used for the fabrication of TiO2 -based photoanodes for dye sensitized solar cells
(DSSC) [75–77]. Doctor Blading technique was employed to fabricate BiVO4 thin
film on FTO glass by Mohamed and co-workers employing an ionic liquid medium
[78]. Franking et al. have fabricated doped hematite photoanodes by doctor blading
route and demonstrated a post-doping strategy for improving the efficiency [12].
Advantages
1. Simplest and low-cost printing methods for the fabrication of semiconducting
coating
2. Can be used for large-scale film development
3. Less than ~5% loss of materials
4. Good uniformity.

Disadvantages
The process is relatively slow, leading to a chance of aggregation of materials at high
precursor concentration.

8.5.5 Spray Coating

Spray coating is an easy and promising technique which can be used as a large-
scale thin film fabrication technique. The method is generally employed either in
the solution coating mode where the precursor is dissolved in a suitable solvent
and sprayed or in the solid form where the coating is done at a temperature above
which the precursor of interest is decomposed. The technique can be applied for the
fabrication of a variety of nanomaterials such as dense and porous thin films, multi-
layers and powders. The instrumental set up for a spray pyrolysis unit is relatively
simple and cost-effective. Typically, a spray pyrolysis unit consists of a precursor
solution, atomizer, substrate onto which the film has to be deposited, heater for a
desired substrate temperature, and a temperature controller to adjust the temper-
ature. A schematic representation of the simple spray pyrolysis unit is shown in
Fig. 8.7b. The role of an atomizer is to create a spray of the precursor solution having
droplet size varying in the range of a few nanometers to micrometres. This enables
one to tune the morphology and dimensions of the films fabricated. For this, different
types of atomizers are employed, which are generally pneumatic or ultrasonic-based
atomizers. Usually, three processes are involved in the spray deposition process.
1. Atomization of precursor taken in a suitable solvent which is realized by
compressed air, electrostatic mode or ultrasonically. The formation and the size
of the aerosols thus formed influence the morphology and porosity of the thin
films.
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 293

2. Transportation of aerosols is the next process which is normally carried out

with the help of gravitation, electrical or by thermoelectric methods. During this
transportation, the solvent in the aerosols is evaporated leading to a decrease in
the size of the droplet. The droplets then precipitate on the substrate when the
concentration of the precursor in the droplet exceeds the solubility limit.
3. Decomposition of the precursor is the final step, where the precipitate is
decomposed leading to the desired product depending on the temperature of
the substrate.
When the spray generated from atomizers hit on the substrate, the atom loses its
energy, spreads on the substrate and interacts with the adsorbed atoms. This will
lead to the formation of islands and merge to form continuous film. The technique
can be used for the fabrication of nanomaterials in the powder form, thin films and
multilayer films for various applications. Different types of spray pyrolysis systems
have been developed which includes, ultrasonic spray pyrolysis [79], plasma assisted
spray pyrolysis [80] and flame pyrolysis [81]. The qualities of the thin films are varied
with the experimental conditions such as type of precursor, precursor concentration,
and temperature of the substrate, drop size and the time of deposition.
Many researchers have attempted fabricating photoelectrodes for AP device using
this technique as it is easily scalable for fabricating large area electrodes. Mesoscopic
leaflet type α-Fe2 O3 thin films was fabricated by ultrasonic spray pyrolysis (USP)
technique and the PEC water oxidation activity was reported to be 1 mAcm−2 at
1.23 V versus RHE [82]. Later in 2006 Cesar et al. fabricated translucent hematite
thin films by USP technique and an improved response was reported with Si doping
[15]. Fabrication of a different system like ZnO-based structures are explored using
spray pyrolysis technique for application as photoanode in DSSC [83]. In a similar
way, spray pyrolysis route was adopted to fabricate doped [84], heterojunctions [79]
and derivative of hematite structures [85] for the obtaining efficient photoanodes for
AP device. A cold spray technique was adopted by Haisch et.al. to fabricate WO3
and TiO2 thin films for water and methanol oxidation reactions [86].
Advantages
1. Layer thickness can be tuned
2. Large area fabrication can be achieved
3. The coating by this method is independent of the substrate morphology
4. Effective tool to fabricate metal oxide thin films
5. Cost-effective.

Disadvantages
1. Non-uniformity in the film
2. Nonstoichiometry and defects in the film
3. Use of inorganic precursors is limited; generally, organic precursors are more
favourable for spray coating as they have low volatility and require low
deposition temperatures.
294 R. P. Antony

All the above-mentioned techniques are conventional synthesis technologies for

the fabrication of thin film photoelectrodes which leads to the formation of nanos-
tructured and nanoporous thin films based on the modified conditions with respect to
instrumentation and precursor compositions. Most of these techniques though while
possessing advantages related to simplicity, cost-effectiveness and good accessi-
bility yield photoelectrodes which are inefficient with respect to light absorption
and charge separation. In the upcoming section of the present chapter, some basic
knowledge, experimental methodology and selected efficiency results of the quasi-1D
photoelectrode fabricated by different routes is discussed.

8.6 Synthesis Strategies for the Fabrication

Quasi-One-Dimensional Thin Films

8.6.1 Hydrothermal/Solvothermal

Hydrothermal synthesis is the most widely and popularly used synthesis technique
for the fabrication of nanomaterials nowadays. The term hydrothermal is of geolog-
ical origin, first used by Sir Rodrick Murchison, a British geologist, who explained
the behaviour of water at high temperature and pressure, which can bring changes
in the earth crust leading to the formation of rocks and minerals [87]. The synthesis
procedure has been defined by Byrappa and Voshimura as any heterogeneous chem-
ical reaction in the presence of an aqueous or non-aqueous solvent above room
temperature and pressure greater than 1 atm in a closed system [88]. Based on the
solvents used in the system, the technique can be defined as ammono-thermal [89–
91], glycothermal [92–94], alcohothermal [95–97], supercritical hydrothermal [98–
100], etc. and hence the technique can also be named as solvothermal synthesis. Each
parameter employed in this synthesis technique has a specific role in the formation
of nanomaterials. The role of temperature is to increase the kinetics of the product
formation and thermodynamic stability. Another parameter is pressure which influ-
ences the solubility and recrystallization process and stability of the product. Gener-
ally, hydrothermal syntheses are conducted without agitation and under isothermal
and isobaric conditions.
The general synthesis strategy of the nanomaterials in the powder form by
hydrothermal route is already given in detail in other chapters. In the present chapter,
we are trying to discuss the extension of this synthesis route for the fabrication of
nanostructured thin films on conducting glasses, which can be used as photoelec-
trodes after calcination at the desired temperature. For fabricating thin films, normally
the substrate to be coated is immersed in the solution and kept for hydrothermal reac-
tion. A schematic representation of fabrication of photoelectrodes by hydrothermal
route is shown in Fig. 8.8. It is a two-step process, where the first step is the fabri-
cation of amorphous one-dimensional nanorod array at controlled temperature and
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 295

Fig. 8.8 Synthesis steps involved in the fabrication of 1 dimensional semiconductor thin films for
photoelectrode preparation by hydrothermal route

pressure, followed by the second step of calcination of the amorphous thin films
leading to the formation of photoelectrodes.
A classic example of fabrication of photoelectrodes by hydrothermal route is
the synthesis of one-dimensional nanorod arrays of hematite on fluorine doped tin
oxide (FTO) glass which was first reported by Vyssires et al. in 2000 [101] and
later the technique was explored by many researchers for fabrication hematite-based
photoelectrodes for solar water oxidation [29, 102, 103]. Cleaned FTO glasses are
inserted into Fe precursor a solution with structure directing agent (urea) and kept for
hydrothermal reaction [47]. Typically, in the first step of reaction, FeOOH nanorods
on FTO/ITO glass are formed at a temperature of ~90 °C, followed by high tempera-
ture annealing (550–700 °C) for fabricating crystalline red hematite-based electrode
which can be used directly as photoanodes in solar energy conversion devices. The
methodology is now widely adopted by various researchers in the field of artificial
photosynthesis [102]. Necessary modifications in experimental parameters such as
alternative structure directing agents (sodium nitrate) [104], temperature, time of
reaction, incorporation of dopants (Ti [102], Sn [105], etc.) are the latest approaches
employed to improve the efficiency of the hematite-based photoanodes. Other semi-
conducting one-dimensional nanostructures such as ZnO [106, 107], TiO2 [108],
and their heterojunctions with Fe2 O3 are explored using this synthesis technique.
Typical surface and cross-sectional morphology of the hematite thin films developed
by this route is shown in Fig. 8.9b, c with nanorod diameter of 50 nm and typical
length of 500 nm. The photocurrent response of the Fe2 O3 –Fe2 TiO5 heterojunctions
fabricated by hydrothermal route by Prince et al. is shown in Fig. 8.9c, d [36]
Numerous studies are available in the literature which discusses the fabrication
of photoelectrodes using hydrothermal route. Table 8.1 gives an idea of the variety
of Q-1D semiconductors-based photoelectrodes fabricated by hydrothermal method
and their typical performance towards water splitting.
296 R. P. Antony

Fig. 8.9 Typical FESEM images showing surface view of the a amorphous FeOOH nanowires,
b Fe2 O3 nanowires formed after annealing FeOOH nanowires, cross-sectional view of c FeOOH
nanowires (length ~500 nm) and d Fe2 O3 nanowires fabricated by hydrothermal route and e The
photocurrent response of Fe2 O3 –Fe2 TiO5 heterojunctions fabricated by hydrothermal route. Image
reproduced with permission from Elsevier [36]

Advantages
1. Easy control of the size and shape of the nanomaterials by changing the
temperature, solvent concentration and type, precursor type and time of reaction
2. The synthesis technique can be up scaled to large-scale synthesis.

Disadvantages
1. Expensive autoclaves
2. Careless handling such as uncontrolled temperature, crack in the autoclaves and
use of unsuitable solvents can lead to explosion.
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 297

Table 8.1 Table showing the PEC performance of photoanodes grown by hydrothermal method
Material Photocurrent Electrolyte used References
(1.23 V vs RHE)
Ti-doped-Fe2 O3 nanorod arrays 0.72 1 M NaOH Vayssieres
et al. [102]
CoPi-modified-Fe2 O3 nanorod arrays 0.27 1 M KOH Fu et al. [13]
S-doped hematite nanorod arrays 0.1 1 M KOH Varghese et al.
[109]
Sn-doped-Fe2 O3 nanorod arrays ~1 1 M NaOH Annamalai
et al. [105]
Single crystalline α-(Fe0.99 Sn0.01 )2 O3 0.74 1 M NaOH Antony et al.
[110]
post-growth Ti doping of a-Fe2 O3 ~0.4 1 M KOH Franking et al.
[12]
Dendritic Au/TiO2 nanorod arrays ~2.32 1 M KOH Kong [111]
Ti-doping + oxygen vacancies in 2.25 1 M NaOH Mor et al.
hematite [112]
Flame processed Ti-doped-Fe2 O3 ~1.5 1 M NaOH Macak [113]
nanorod arrays
Mn-doped hematite nanorod arrays 1.6 1 M NaOH Gurudayal
et al. [47]
Silica encapsulation in Sn doped 1.36 1 M NaOH Huan [114]
hematite nanorod arrays
Low temperature activated Sn-Fe2 O3 0.1 1 M NaOH Yang [115]
nanorod arrays
titanium dioxide interlayer that serves 2.5 1 M KOH Luo et al. [34]
as passivation layer and dopant source
for hematite (a-Fe2 O3 ) nanoarray
Hematite nanorod array in a plasmonic ~1 1 M NaOH Hoyer [116]
gold nanohole array pattern
Ti doped hematite nanorod 2.28 1 M NaOH Takahashi
et al. [117]
α-Fe2 O3 /GIO 0.8 1 M NaOH Shinde et al.
[118]
rutile TiO2 nanorods 0.5 1 M NaOH Formhals
[119]
Branched TiO2 nanorods 1 1 M KOH Mor et al.
[108]
TiO2 Nanorod Arrays Decorated with −0.015 0.1 M NaOH Bang and
CdSe Kamat [10]
Branched TiO2 nanoarrays sensitized 4 at 0 V versus 1 M KOH Taylor [120]
with CdS quantum dots RHE (hydrogen
generation
current)
Branched TiO2 Nanorods ~1 1 M KOH Cho et al. [30]
(continued)
298 R. P. Antony

Table 8.1 (continued)

Material Photocurrent Electrolyte used References
(1.23 V vs RHE)
Fluorine-doped hierarchical porous 0.9 1 M KOH Han et al.
single-crystal rutile TiO2 nanorods [121]
N-modified TiO2 nanowire arrays 0.5 1 M KOH Reneker and
Yarin [122]
Rutile TiO2 nanowires ~0.75 1 M KOH Hwang et al.
[9]
two-dimensional ZnIn2 S4 0.6 0.35 M Na2 SO3 Huang et al.
Nanosheet/one-dimensional TiO2 and 0.24 M Na2 S [123]
Nanorod Heterostructure Arrays (pH 11.5)
Fe2 O3 /Fe2 TiO5 heterojunction 1.4 1 M NaOH Bassi et al.
nanorods [36]
Fe2 TiO5 nanorods ~0.5 1 M NaOH Bassi et al.
[36]

3. Toxic and corrosive solvents create damage to autoclave

4. Inability to observe the growth of the nanocrystals.

8.6.2 Electrochemical Anodization

Electrochemical anodization is a well-known technique for the fabrication of metal

oxide nanotube arrays, mainly of valve metals such as Ti, Al, Si and Zr. Valve metals
are the class of metals which allows the current to flow only in one direction (analogy
to the rectifying behaviour of a diode). The technique is simple and easy to do in a
normal laboratory with the help of a DC power supply which can go up to an applied
DC voltage of 60 V. This synthesis method enables one to fabricate self-organized,
highly ordered nanotubes arrays having dimensions in the nano-regime with narrow
size distribution. For energy conversion applications, TiO2 nanotube arrays (TNTA)
are promising among other quasi-one-dimensional materials because of its strad-
dling band edge positioning with respect to water oxidation and reduction potentials.
Though the first report on fabrication of porous TiO2 is by Zwilling et al. [36],
synthesis of TNTA by anodization of Ti foil was reported by Grims and co-workers
[108, 109]. Later optimization of the nanotube lengths, diameter and wall thickness
was done by varying the time of anodization, electrolyte concentration and applied
potential by various research groups working in this field. The electrolyte composi-
tion is an important parameter in the formation of TNTAs. Thus, the discussion on
this synthesis method will be mainly based on the TNTA. The experimental setup for
the synthesis of TNTA is shown in Fig. 8.10a. A two-electrode system is employed, in
which Ti foil or Ti metal coated substrates are used as anode with a counter electrode
(cathode, normally Pt foil) kept at specific separation of about 1–2 cm. The elec-
trolyte used for anodization is generally fluoride-based organic/aqueous electrolyte.
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 299

Fig. 8.10 a Experimental setup used for electrochemical anodization of valve metals, b Oxide
formation mechanism of Ti metal under potentiostatic condition, c mechanism showing the forma-
tion of nanotube in presence of fluoride ion, d FESEM image of surface view of TNTA (inset shows
the back side view of the TNTA revealing the hemispherical active area and e the cross-sectional
FESEM view of TNTA showing the self-organized formation of TNTA (the dimples on the Ti metal
is clearly visible where imprint of hemispherical area was present)
300 R. P. Antony

For this, the basic mechanism behind the formation of TNTAs should be understood
first. The formation mechanism of nanotube by anodization in the case of Ti foils is
similar to the case of anodic porous alumina. The main processes that occur during
electrochemical anodization are the following.
First step is the formation of oxide layer with the help of an external field in the
presence of O2 and OH− followed by the movement of metal oxide-metal interface
layer towards inside of the metal by the reaction of anions formed with the Ti metal.
At the same time transfer of Ti4+ ions takes place and these move outwards to metal–
metal oxide interface and reach the metal oxide-electrolyte interface with the help
of an electric field. Thus, oxide formation and chemical dissolution are the two
competing processes that are involved in the formation oxide layer on the Ti substrate.
The experimental setup and processes involved are schematically represented as in
Fig. 8.10a, b. The overall chemical reactions involved are given as follows:

2H2 O → O2 + 4H+ 4e− (8.10)

Ti + O2 → TiO2 (8.11)

The process thus creates a passivation layer on Ti substrate and becomes a corro-
sion resistant coating. The trend shows a change when anodization is conducted in
fluoride containing electrolytes. It is well studied on the behaviour of passivated tita-
nium metal when subjected to fluoride containing electrolyte [110–114]. The stable
oxide layer is attacked by the fluoride ions in the electrolyte leading to the forma-
tion of [TiF6 ]2− complexes in the solution. The chemical reaction is shown as given
below.

TiO2 + 6F− + 4H+ → [TiF6 ]2− + 2H2 O (8.12)

Ti + 6F− → [TiF6 ]2− (8.13)

Initially, the field assisted attack of fluoride ions on anode occurs locally leading to
formation pits in the nanometer scale on the surface. The presence of H+ and F− ions
increases the chemical dissolution current density. Consequently, the applied field is
equally shared by the pores formed and continuous growth of the pore is assisted by
an equifield mechanism. Thus, the hemispherical area becomes the active site for the
oxide formation and chemical dissolution. At equilibrium, the rate of oxide formation
and chemical dissolution will be same and continuous growth of nanotube will occur
towards the metal oxide-metal interface. The pictorial representation of the formation
of nanotube arrays, where an equifield hemispherical active area plays a major role
is shown in Fig. 8.10c. This behaviour is generally inferred from the current density
transient recorded during the anodization. During the commencement of the reaction,
the current density recorded as a function of time (constant potential) is high as the
metal substrate is exposed to the electrolyte with a constant potential applied between
the electrodes Ti metal reacts with oxygen and hydroxyl ions leading to the formation
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 301

oxide layer on the metal and thus a drastic decrease in the current density. Thereafter,
there is a competition between the field assisted oxidation and dissolution and due to
this a hump is visible in the current density transient. When equilibrium is attained
the current density becomes constant and thus indicating continuous formation of
nanotubes. The surface, bottom and cross-sectional views of the nanotube arrays
thus prepared are shown in the FESEM images given in Fig. 8.10d, e. The potential
window applied for the formation of nanotubes by anodization also depends on the
electrolyte employed.
Numerous reports are available in the literature where photoelectrode made of
electrochemical anodization route is investigated for its water oxidation activity.
Nanotube arrays of oxides of valve metals have used as photoanodes in solar water
oxidation among which the most commonly used are TiO2 , WO3 , Ta2 O5 and Fe2 O3
nanotube arrays. Selected results are tabulated in Table 8.2 where the achieved
photocurrent values are listed for each type of photoanodes employed.
Advantages
1. Simple and highly reproducible with the same quality of metal foils
2. Dimensions of the self-organized arrays can be tuned by changing the
anodization parameters
3. Utilization of cost-effective electrolyte.

Disadvantages
1. The technique cannot be applied for the synthesis of all metal oxide nanotubes
2. Peeling off of the nanotube is observed when anodized for longer time and
during sonication for longer time.
3. Though the synthesis of nanotube arrays is pretty easy by anodization process,
the film transfer to a transparent substrate is a tedious procedure when it comes
to device application.
4. Fabrication nanotube arrays by anodization of Ti thin films on conducting glass
are a challenge as the process involves deposition of Ti layer on conducting
substrates, anodization od deposited films till all the Ti reacts to form TNTA.
A problem observed in this case is the peeling of the Ti metal coating during
anodization and incomplete oxidation of Ti metal at the conducting glass-metal
interface leading. The peeling off issue should be addressed by selecting a
deposition technique which can produce an adhesive metal thin film on FTO/ITO
glasses.

8.6.3 Electrodeposition

The electrodeposition technique is a process by which single/composite thin films

can be fabricated on to preferred substrates by means of electrical energy. The
process is carried out either in a two-electrode or a three-electrode configuration.
302 R. P. Antony

Table 8.2 Table showing the water oxidation activity of the photoelectrodes fabricated by
electrochemical anodization technique
Material Photocurrent Electrolyte used References
(1.23 V vs RHE)
TiO2 nanotube arrays 5 1 M KOH Shankar et al. [8]
N doped TiO2 nanotube ~0.3 1 M KOH Choi et al. [131]
arrays
Micron-Length 30 1 M KOH Shankar et al. [8]
Highly-Ordered Titania
Nanotube Arrays
Black TiO2 nanotube ~3.5 1 M NaOH Zhang et al. [132]
arrays
Reduced TiO2 nanotube 0.73 1 M NaOH Kang et al. [11]
arrays
hierarchical TiO2 1.59 1 M KOH Bedford and Steckl
nanotube arrays [133]
Plasmonic Gold ~2 1 M KOH Lepcha et al. [134]
Nanocrystals Coupled
with Photonic Crystal on
TiO2 Nanotube
Vertically Aligned WO3 1.43 0.1 M Na2 SO4 Mao et al. [135]
Nanowire Arrays
2 electrode system 2–2.8 at −0.4 V 1 KOH Croce et al. [136]
(TiO2-x Cx Nanotubes as versus AgAgCl
anode and Pt/TiO2
Nanotubes as a Cathode
Sulphur treated TiO2 2 0.1 M KOH Einert et al. [137]
nanotube arrays
multi-anodized TiO2 ~5 0.5 M KOH Jung et al. [138]
nanotube arrays
p-type Zn-doped 0.04 1 M NaOH Qi et al. [25]
a-Fe2 O3 nanotube arrays
Self-Assembled <0.1 1 M NaOH Saveh-Shemshaki
Hematite (r-Fe2 O3 ) et al. [139]
Nanotube Arrays
Ultrathin r-Fe2 O3 ~1 1 M NaOH Sander and Tan [140]
Nanotube Arrays
L-cysteine @ Fe2 O3 ~8 1 M NaOH Lee et al. [141]
nanostructure
Ta3 N5 Nanorod Arrays ~4 0.5 M Na2SO4 Han et al. [142]
W-doped Ta2 O5 ~1 1 M KOH Li et al. [143]
nanotube arrays
Porous Ta3 N5 nanotubes 7 0.1 M K4 [Fe(CN)6 and Kim et al. [144]
0.1 mM
K3 [Fe(CN)6 ](pH =
7.5)
(continued)
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 303

Table 8.2 (continued)

Material Photocurrent Electrolyte used References
(1.23 V vs RHE)
TaON nanotube arrays ~2 1 M KOH Kim et al. [145]
Ta3 N5 Nanotube ~6 1 M KOH Yoon et al. [146]
Photoanodes with
subnitrides
Hybrid tungsten 2 1 M KOH Lai and Sreekantan
trioxide-titanium dioxide [22]
(WO3 -TiO2 ) nanotube
Hierarchical WO3 –TiO2 0.6 1 M NaOH Shi et al. [147]
nanotube arrays
Anodically Grown WO3 8 1 M H2 SO4 Cristino et al. [20]
Electrodes

Figure 8.11 shows a schematic of an electrodeposition system which utilizes 3-

electrode systems for fabricating nanostructured thin films. The substrate normally
used as the working electrode will be conducting glasses (FTO/ITO), conducting

Fig. 8.11 Schematic presentation of electrodeposition setup used for the fabrication of nanostruc-
tured thin films
304 R. P. Antony

plastics, metal coated glass substrates and metallic substrates. Different electrochem-
ical techniques such as pulse electrodeposition, chronoamperometry, chronopoten-
tiometry and cyclic voltammetry are employed for the synthesis through this route.
The salt solution of the metal to be deposited is generally used as the electrolyte.
The substrates used for fabricating Q-one-dimensional structures can be template-
assisted electrodeposition where a template like anodic alumina is used or a template-
less deposition where intrinsic anisotropic crystallographic structure of the target
material can be utilized. Fabrication of the one-dimensional metal oxide nanostruc-
tures using template assisted electrodeposition can be achieved by removal of the
template followed by annealing under oxygen rich atmosphere to convert the metal to
metal oxide. Direct oxide deposition is also achieved by the electrodeposition route
[115–117].
When electrodeposited photoelectrode are used for solar water oxidation
nanoporous BiVO4 photoanodes are the classic example of electrodes fabricated by
electrodeposition route, which was reported for the very first time Choi’s research
group in 2014 [17]. The anodes showed a typical photocurrent density of ~2.5
mAcm−2 at an applied bias of 1.23 V in 0.5 M Na2 SO4 . Shinde and co-workers fabri-
cated hierarchical hematite (α-Fe2 O3 ) nanopetals-based photoelectrodes by pulse
reverse electrodeposition and demonstrated the solar water oxidation activity [118].
The advantages of these techniques are as follows:
1. Low cost
2. Environmentally friendly
3. Low energy consumption
4. Easy to handle
5. High growth rate at low temperatures
6. Good control over the film thickness, size and shape of the nanostructures.

Disadvantages
1. Substrate adhesion is an issue
2. Not all metal oxides can be fabricated by this route.

8.6.4 Electrospinning

Electrospinning is an alternative and efficient technique to fabricate one-dimensional

nanostructures, mainly nanofibers and nanotubes. The first electrospinning apparatus
is demonstrated by A. Formhals and later it was patented in 1929 [119]. Thereafter
in 1960s G Taylor presented research findings, explaining the physics involved in
the electrospinning process [120]. In 2000s, Reneken and Yarin made investiga-
tions on electrospinning polymer solution and clarified the theory behind the forma-
tion of such fibres [121, 122]. Later this idea was transferred to other materials
and their derivatives such as carbon fibres and inorganic nanowires, nanofibres and
nanotubes [123, 124]. A schematic representation of the electrospinning unit is given
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 305

Fig. 8.12 a Schematics of the instrumentation setup used for electrospinning of polymers, metal
oxides and carbon fibres, b typical SEM image of the metal oxide nanowires fabricated by
electrospinning and c Carbon nanofibers fabricated by electrospinning followed by Ar annealing

in Fig. 8.12. The instrument for electrospinning consists of three main units (a) a high
voltage power supply, (b) solvent dispensing syringe with metallic needle and (c) a
grounded collector. For the fabrication of electrospun fibres, high molecular weight
polymers generally poly vinyl pyrollidone (PVP) [18], polyvinyl alcohol (PVA) [125]
and poly vinyl acetate [126] are used for preparing viscous solvent which will be
filled in the syringe connected to the metallic needle. The needle is connected with
the one lead, and the counter lead is connected to the grounded collector which
is normally aluminium foils or any other conducting substrates selected based on
the application of interest. In the case of preparation of photoelectrode, normally
FTO/ITO coated glass substrates or heavily doped silicon substrates are employed.
A high voltage, typically in the range of a few kV to 30 kV, is applied using the high
voltage power supply. When a high voltage is applied to the viscous solution, the
electric field is generated between the spinneret (metallic needle) and the collector.
Consequently, a droplet is formed at the tip of the needle and when the electrostatic
force overcomes the surface tension of the viscous liquid, the droplet is deformed to
a Taylor cone and start emitting the liquid in the form of a jet from the needle tip.
Due to the electric field and the surface tension effect, the jet stream starts whipping
and the solvent dries subsequently. This lead to the formation of fine fibres having
diameter varying from few micrometres to nanometres deposited on the conducting
collector. The diameter of the electrospun fibres depends on the viscosity of the solu-
tion used and is experimentally confirmed by Baumgarten [127] and He [128] and
the relation is given by the following Eq. (8.14)

d ≈ η0.5 (8.14)
306 R. P. Antony

Similarly, the diameter of the fibres formed is also dependent on the applied
potential as given below

d ≈ E −0.5 (8.15)

These electrospun nanostructures find wide application in the field of sensors

[162, 163], drug delivery [164], medical implants [165], environmental cleaning
[166], energy conversion [18, 63, 167] and storage applications [168, 169]. Coming
back to artificial photosynthesis point of view, the electrospun one-dimensional
semiconductor-based nanostructures have shown promising improvement in the
performance when used as photocatalyst and photoelectrodes. Recently, the elec-
trospinning technique was adopted to fabricate the hematite hollow nanofibers-
based photoanodes by Einert and co-workers [170] using PVP as sacrificial polymer
demonstrating a photocurrent density of 3.4 μAcm−2 . Fabrication of BiVO4 photoan-
odes by electrospinning approach is another effort done by various researchers.
Nanoporous Mo-BiVO4 photoanodes are by fabricated by Antony et al. and inves-
tigated the effect of doping and porosity in improving the charge separation and
hole diffusion length [18]. Similarly, Jung et al. fabricated Mo-BiVO4 photoanodes
by electrospinning route and a photocurrent of ~0.175 mAcm−2 is reported for the
best sample [171]. Recently, nanostructured g-C3 N4 /BiVO4 composite films were
prepared by Wang and co-workers and demonstrated the photoelectrochemical char-
acteristics with an excellent improvement in water oxidation performance on C3 N4
loading [19]. In the case of hematite systems, very few reports are available where
electrospinning route is adopted as a technique to fabricate hematite photoanodes for
solar water oxidation. Si and Ti doped hematite nanostructured films are fabricated
by Santangelo et al. and PEC water oxidation performance was investigated [63].
Mesoporous functional hematite nanofibrous photoanodes were fabricated and the
photocurrent density was reported to 0.55 mAcm−2 with a light intensity of 900
mWcm−2 [172]. An improved PEC water oxidation activity was observed for elec-
trospun ZnO/TiO2 nanostructures [158]. Electrospun black titania nanofibers showed
a water oxidation activity with photocurrent of 0.2 mAcm−2 at 1.23 V versus RHE
[167].
Advantages
1. Complex hierarchical structures can be fabricated
2. Tuning of the nanofiber diameters is possible by optimizing the solvent and
instrument parameters
3. Can be used for large-scale synthesis of one-dimensional nanostructures
4. Can make high aspect ratio and large surface area materials
5. Nanostructures will have narrow size distribution
6. Simple and cost-effective technique
7. Highly reproducible.

Disadvantages
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 307

1. Usage of variety of polymers and solvents are limited

2. Sometimes the metal oxides nanofibers are brittle after calcination process which
limits the performance
3. Inferior performance of the filters fabricated by electrospinning technique
4. Inefficiency in fabricating nanostructures with dimensions less than 20 nm.

8.6.5 Template Assisted (TA) Growth

Template assisted growth is another promising route commonly adopted for the fabri-
cation of one-dimensional ordered arrays. Different types of inorganic and organic
templates are explored to this end, and anodized alumina membranes (AAM) and
etched polycarbonate membranes are the most commonly used as templates for
growing one-dimensional structures. Other templates which are used for the synthesis
of one-dimensional structure are electrochemically etched silica and mesoporous
materials [173–175]. Fabricating one-dimensional arrays using AAM is known as
a hard-templating route wherein there is a good control over composition, size and
dimensions of the nanostructures. The technique is generally combined with elec-
trodeposition, atomic layer deposition (ALD), thermal decomposition and chemical
vapour deposition. Polystyrene beads and life radiation track etched polycarbonate
membranes are another class which comes into the soft template category and is
relatively flexible for fabricating inverse opal semiconductor photoelectrode struc-
tures [176]. This type of fabrication is generally termed as opal template assisted
nanostructure growth. In this, controlled and uniform deposition of colloidal parti-
cles is employed leading to highly ordered and close-packed multi-layered films. The
deposition is normally conducted either by dip coating or a spin coating route. These
films now can be used as templates for growing semiconductor nano architectures.
Generally, polystyrene (PS) beads are used for the preparation of soft templates and
the substrates used are FTO/ITO-based conducting glasses and Si substrates which
are the most common substrates used for the fabrication of photoelectrodes.
The photovoltaic activity of periodically aligned ZnO hemisphere crystals was
studied Kim et al. and was fabricated by photolithographic TA growth [177]. Kim
et al. studied the photoelectrochemical activity of vertically aligned Cu2 ZnSnS4
nanorod arrays fabricated by TA route [178]. Similarly, TA method was adopted for
fabricating photoelectrode which includes hematite [179, 118, 180], BiVO4 [181]
and CIGS [178]-based system (Fig. 8.13).
Advantages
1. Easy fabrication of one-dimensional nanostructured arrays and porous nanos-
tructured assembly
2. Good control over the dimensions by using templates having different diameter
and length
3. The technique can be hyphenated with high temperature synthesis technique
due to the high temperature stability of AAM.
308 R. P. Antony

Fig. 8.13 Schematic illustration of template-assisted fabrication of nanostructured materials

based on anodized aluminium oxide (AAO) and self-assembled opal templates. Reproduced with
permission from Elsevier. Copyright 2015 [182]

Disadvantages
1. Difficulty in removing the templates selectively after synthesis
2. Low yield of materials
3. Predominantly polycrystalline materials are synthesized by this technique.

8.6.6 Chemical Vapour Deposition

Chemical vapour deposition is a well-known technique, which involves the conver-

sion of gaseous molecules to solid form possessing different dimensions. The
technique basically involves different steps and as listed as follows:
1. Introduction of reactant gas molecules in combination with inert gas into the
reaction chamber, where the substrate to be deposited is situated
2. Mass transfer of the reactants to the substrate from the main flow region
3. Adsorption of the molecules on the reaction site of the substrate
4. Reaction, nucleation and growth of the one-dimensional structures by reaction
among the molecules to form an array in the form of thin film
5. Desorption of the by-products from the reaction
6. Flushing the inert gas and removal of the unreacted gaseous products and by-
products from the reaction chamber.
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 309

Fig. 8.14 a Schematic of instrumental setup for CVD reaction and b pictorial representation of
mechanism involved in conventional CVD reaction

The pictorial representation of the CVD synthesis process and the mechanism
involved is shown in Fig. 8.14a, b [183]. Generally, volatile reactant mixtures are
placed in the reaction chamber, where a controlled release is ensured using a mass
flow controller. Crystallinity of the material is achieved by heating the substrate to the
desired temperature during the course of deposition. Highly oriented and high quality
one-dimensional structured thin films can be achieved using CVD technique. Using
hard template such as AAO is a simple and straight forward approach to fabricate
one-dimensional nanostructure [184, 185]. In this case, the template should be kept
as the substrate to be deposited and after CVD growth, the template is etched out by
suitable chemical process. Another approach is to initiate the nucleation and growth
by means of a catalyst. This technique is classified based on the phases involved in
the reaction process and is defined as vapour–liquid–solid growth (VLS), solution-
liquid–solid growth (SLS) or vapour–solid growth (VS) [183]. In both these cases
usually, metal nanoparticle is used as the nucleation catalysts and the semiconductor
to be grown are introduced in the vapour phases. The size of the metal nanoparticle
decides the diameter of the nanowire grown. A large variety of materials can be
fabricated using different forms of CVD techniques for wide range of applications.
310 R. P. Antony

The variations of CVD technique includes plasma enhanced CVD (PECVD), metal
organic CVD (MOCVD), laser induced CVD (LICVD), ALD, etc.
CVD technique is successfully employed to fabricate Q-one-dimensional thin film
photoelectrodes for AP device. Nanostructured anatase–rutile TiO2 heterojunctions-
based photoelectrodes are fabricated using pulsed pressure MOCVD technique, and
the most active samples were reported to have a photocurrent density of ~1.2 mAcm−2
at 1.23 V versus RHE [37]. A direct liquid injection CVD method was adopted
by Archana and co-workers to fabricate BiVO4 thin film photoelectrode to use as
photoanode [186].
Advantages
1. Uniform step coverage
2. Good control over structure and composition as the stoichiometry of the formed
material is controlled by control on the flow rate of the precursor
3. Good reproducibility
4. Epitaxial film formation and ability to fabricate abrupt junctions
5. The pressures in CVD allows to grow three dimensional structures with large
aspect ratios
6. Higher deposition rate due to higher flow rates
7. Simple and can be scaled up to several substrates
8. Ultra-high vacuum is not necessary
9. Change in the type of precursor is easy
10. High purity films can be prepared.

Disadvantages
1. High temperature
2. CVD precursors are often hazardous and toxic and hence the deposition process
may involve evolution of toxic and corrosive gases
3. The precursors need to be volatile at room temperature
4. Some metal organic precursors used as CVD precursors are very expensive
5. Complex processes
6. The films are usually deposited at high temperatures in some derivatives of the
CVD and hence the type of substrate which can be used in CVD process is
restricted. Also, difference in thermal expansion coefficient of materials can
lead to stress in the films deposited thereby causing a mechanical instability in
the film.

8.6.7 Atomic Layer Deposition

Atomic layer deposition technique also known as atomic layer epitaxy (ALE) or
atomic layer chemical vapour deposition (ALCVD) is an advanced synthesis tech-
nique for the fabrication of nanostructured thin films for applications such as PEC
[9, 187, 188], photovoltaics [189] and electrocatalysis [190–193]. For fabrication
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 311

of thin films by ALD route, different steps are involved similar to the conventional
CVD process. The schematic representation of the ALD growth of the nanostruc-
tures is shown in Fig. 8.15. In the first step of ALD process, excess of precursor A is
introduced into the reaction chamber where the substrate to be deposited is situated.
Chemisorption of A at the surface, till a monolayer formed is the second step. Excess
of A is removed by an inert gas purging during the third step. Thereafter precursor
B is introduced for the adsorption and chemical reaction with adsorbed precursor A
(step 4). Finally, in step 5 the unreacted precursors and the by products are flushed
out by inert gas leaving an ALD coated thin film on the desired substrate. In contrast
to CVD technique, in the case of ALD, when one monolayer is formed, adsorption of
precursor is stopped. Thus, the growth of the thin film is independent of the precursor
pulse time. Other conditions to be satisfied in ALD technique are.
1. Precursor should be stable at the decomposition temperature, in order to prevent
the decomposition of the film formed after chemisorption.
2. Reaction rates should be very high to avoid long saturation pulse time.

Fig. 8.15 Typical synthesis steps involved in Atomic Layer Deposition technique
312 R. P. Antony

The technology is now widely used in the manufacture of novel thin films of metal
oxides, as well as passivation layer for minimizing the surface state recombination
in photovoltaic and photoelectrochemical water splitting. In 2008 Hammann et al.
developed ALD coated TiO2 on templated substrate and proved the ability of same as
photoanode in DSSC [189]. WO3 nanostructured thin film electrodes was fabricated
by Liu et al. using ALD technique which demonstrated efficient solar water oxida-
tion performance [194]. APCVD grown quasi-one-dimensional nano structures of
hematite could generate a photocurrent up to 2.3 mAcm−2 at 1.23 V versus RHE, is
a new bench mark material developed by Graetzel and co-workers, and is a highly
efficient photoanode developed by this route [15] (Fig. 8.16a, b). Later, numerous
researches have been carried out to study the physic chemical processes behind ALD
fabricated photoelectrodes. Ultrathin hematite photoanodes were fabricated by Klahr
and colleagues to study the effect in solar water oxidation and physico-chemical
processes behind that [189]. Plasma enhance ALD route was adopted by Kot et al. to

Fig. 8.16 a cross-sectional and surface view of ALD grown thin film [15], b the PEC response
of ALD grown films15 , e CoOx catalyzed BiVO4 photoanode [196] and f ultrathin TiO2 layer on
hydrothermally grown hematite photoanode [191]. Reproduced with permission from American
chemical society. Copyright 2015
8 Synthesis Aspects of Nanoporous and Quasi-One-Dimensional … 313

fabricate titanium oxynitride films which is a promising candidate as photoanode in

AP device [195]. Lin and co-workers use ALD route to fabricate p-type hematite and
successfully introduce n-p junction in hematite films for an improved water oxidation
performance [187]. ALD technique is also used as an efficient route to passivate the
photoanodes to minimize the surface recombination of charge carriers. ALD-coated
passivation layer of ZnO–TiO2 on CuO nanofiber was developed by Kim et al. and
the hydrogen evolution current density was up to −4.1 mAcm−2 [48]. The coating
served the role of both co-catalysts as well as a protecting layer for CuO. Ultrathin
Al2 O3 coating on hematite single crystals are deposited using ALD technique by
Jiao et al. and the photoelectrochemical was improved with respect to water oxida-
tion onset potential and photocurrent compared to pristine hematite electrode [86].
Cobalt oxide catalytic layer on BiVO4 photoanode was deposited by ALD route
by Lichterman and co-workers [196]. The resultant ALD-CoOx /BiVO4 assembly
showed an improved PEC performance compared to the pristine BiVO4 photoanode
(Fig. 8.16c). Li and co-workers used ALD technique to coat ultrathin TiO2 layer on
hydrothermally grown hematite photoanode which showed a better charge separation
and an improvement in the photocurrent. Their studies also revealed that the role of
thickness of ALD coating in minimizing the charge recombination through a surface
state intermediate charge transfer process (Fig. 8.16c) [191].
Advantages
1. Nanometer level control over film thickness
2. Low defect density of the films fabricated
3. Excellent repeatability for the thin films fabricated
4. Good control over the heterojunctions, doping and multilayer processes
5. Excellent adhesion of the thin films.

Disadvantages
1. The ALD precursors are generally costly and storage needs expensive set up
2. Limited precursors are available due to reactivity
3. Longer processing time to fabricate thin films
4. The substrate size with this technology is limited to 15 ×15 × 15 cm
5. Not every material can be coated with this technique
6. Thermal decomposition of the precursor is allowed.

8.7 Conclusions and Future Scope

Artificial photosynthesis is an important field of research which utilizes earth abun-

dant sunlight and water for energy conversion process, to satisfy the future require-
ment where humankind will have a crucial dependence on natural and renewable
energy resources. The concept of utilizing artificial material especially earth abun-
dant semiconducting materials for energy conversion in the form of photoelectrodes
for water splitting is a promising route to achieve this. When the photoelectrodes are
314 R. P. Antony

in the nanostructured form especially in the Q-one-dimensional structure it attains

excellent enhancement in the device efficiency. However, the efficiency of the devices
using these materials is not yet to the commercialization level, and hence extensive
researchers is being carried out all over the world to come up with an efficient
device. This chapter tried to give a brief insight of the different strategies for the
synthesis of Q-one-dimensional materials which are commonly adopted to reduce
the cost of the materials and can stand as a collective reference for beginners or young
researchers to improve their knowledge on synthesis methods used in this field. Elab-
orate schematics and images have been included to provide the readers a visual feel
on the appearance of the nanostructures as well as the various steps involved in the
different nanostructure fabrication processes. Most of the techniques described in
the chapter, except advanced technologies like ALD and CVD (which are generally
available only in research institutes or manufacturing industries), can be adopted in
college or university level experiments for the fabrication of photoelectrodes.

Acknowledgements Authors acknowledge Dr. Bevita K Chandran, Research fellow NTU Singa-
pore, for her involvement in pointing out and correcting the discontinuity, technical errors and gram-
matic mistakes in the book chapter at its different stages of preparation. Author is thankful to Mr
Rajendra Vikhram Singh, SO/C, Chemistry Division, BARC, for his help in correcting subsections
of book chapter.

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Chapter 9
Synthesis Strategies and Applications
of Metallic Foams and Hollow Structured
Materials

Ashis Kumar Satpati

Abstract The porous materials or foams are becoming ubiquitous in various

research fields as they find applications in several important modern devices. The
porous nano structures may be considered as a generalised name of foams which are
generated from both metallic and non-metallic components. Present chapter however
discussed primarily on the metallic foams. After a brief account of the history of the
generation of metallic foams, the synthesis procedures have been discussed, the
chapter has been organised by describing various synthesis procedures of metallic
foams, which leads to the variation in their properties. Since porous nano structure
materials have wide varieties of applications, only some of the important application
are presented in the chapter. In addition to the nano porous foams, the metallic foam
with macro porous structures have widespread large scale commercial applications,
which has been discussed in brief. Some of the important applications of porous nano
structures materials in alternate energy technology, sensors and biosensors and bio-
regenarative medicines are included in the present chapter. Apart from the metallic
foams, non-metallic foams are also very important and associated its signature with
various scientific and technological applications; however, the detailed discussion
on the non-metallic foams are made out of the scope of the present chapter with only
a small discussion on the graphene foams, which has accrued an important place in
various scientific inventions, has been mentioned towards the end of the chapter.

Keywords Porous structure · Metal foam · Hollow structure · Porous noble metal
nanostructures (PNMNs) · Transition metal chalcogenides · Hard template · Soft
template · Self-template · Electrodeposition · Gas template · Kirkindall effect · Li
ion battery · Supercapacitor · Fuel cell · Water splitting · Sensors · Commercial
applications · Regenerative medicines

A. K. Satpati (B)
Analytical Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
Homi Bhabha National Institute, Mumbai 400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 325
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_9
326 A. K. Satpati

9.1 Introduction

The metallic foam was created accidentally through combustion experiments

by Tappan et al., at Los Alamos National Laboratory. While Professor Tappan
was carrying a burning-rate experiment in 2005 to investigate the decomposi-
tion behaviour of iron complex with nitrogen-rich ligands, namely, ammonium
tris[bi(tetrazolato)-amine] ferrate(III). While igniting a small pellet of the metal
complex, with the expectation that the complex material would either be exploded
or it might burn slowly. However, he observed that the smoke filled the reaction
chamber due to which it was impossible to record the progress of the decomposi-
tion of the material. While opening up the reaction vessel to clean for the next set
of experiments he found the resulted materials with long columnar structure. With
curiosity he characterised the materials to find that the mysterious column of mate-
rials was basically a foam composed mostly with iron metal. The porous materials
were having the pore diameters in the range from 10 to 20 nm, which were excep-
tionally good characteristics for metallic foam. This has been considered as one of
the first well reported metallic foam. The metallic foams have several advantages,
“One huge advance with metal foams could be getting a real base metal like nickel
to behave more like platinum or palladium” [1–11].
In older literature, porous metallic materials are in use in the name of powder
metallurgy (PM) materials and served various important purposes due to their high
surface area and superior mechanical properties. For the selection of materials to form
the PM, the most common examples are bronze, nickel and nickel-base alloys. As
non-ferrous metals, copper, aluminium, gold, niobium, tantalum, silver, zirconium
and titanium are fabricated into porous materials, from powder [12]. In order to
obtain the materials of required shape and sizes, PM materials undergo various types
of separations like, sieving, ultrasonic separations, after which the materials undergo
several compaction techniques or sintering processing. In addition to the compaction
and sintering, the materials are produced through the metallurgical procedures like,
centrifugal slurry casting, metal injection moulding, extrusion, direct tapping method
gravity filling of shaped moulds and wet powder spraying to fabricate the materials
in usable forms [12].
Major progress has been made later in the direction of developments of improvised
metals and alloys with suitable pores and surface areas superior to the PM materials,
which are named as metallic foams also called as cellular metals having properties
step ahead compared to the PM materials. Foams find superior application due to the
high porosity, low specific weight combined with excellent mechanical properties
[12]. It has been a challenging task for the materials scientists to design suitable
synthesis protocols to generate PM materials, foams or cellular metals with high
and controllable pore structures. The combustion synthesis procedure is an age-old
synthesis technique to generate porous structured materials [13–17].
In some of the literatures published earlier the synthesis of metal foam has been
mentioned with the combination of foaming agent along with molten metal [18]. The
foaming agent was reported as the powders of metal hydrides, which are decomposed
9 Synthesis Strategies and Applications of Metallic Foams … 327

and formed gases when heated to a temperature above 400 °C. When the foaming
agents come in contact with the molten metal, instant decomposition takes place.
The homogeneous distribution of the gas-forming particles all along the melts is not
possible due to the insufficient time of contact. This has resulted in the difficulty in
controlling the overall reaction and thus controlling the resulted product. Metal foams
are also synthesised from the metal melts for the metal of low melting points and the
utilisation of the eutectic composition further decrease the process temperature [5].
Metal foams are known for their interesting properties having ultra-low density
arises through their highly porous organised network structure. In older literatures
the documented density values of porous structures are between 0.5 and 1 g/cm [3]
which have been improved significantly with the density for metallic foams as low
as 10 mg/cm [1, 1]. The porous nano structure materials are capable in absorbing
significant amount of strain. The stress–strain dependency indicates that the foam
materials has the capacity to absorb large amount of energy [19]. The porous or hollow
nano structures having excellent properties like, large pore volume, high specific
surface areas, high capacity for loading, possibility of various functionalisation,
which leads to their applications in, a few of them are named as lithium-ion batteries
[20–26], catalysis [27–31], drug delivery [32–36], sensors [37–40], water treatment
[41–45], and dye-sensitized solar cells [46, 47].

9.2 Synthesis Procedures Porous Materials

The combustion synthesis process is the conventional route of synthesising of

metallic foams. The combustion synthesis procedures are carried out either in solid
state or in aqueous solution. The solid state synthesis procedure generally proceeds
as self-propagating process, thus calling them as the self-propagating high temper-
ature synthesis procedure [14, 48]. The synthesis is carried out without the use of
any external combustion agents. The simple chemical reaction used to represent the
combustion process is represented in Eq. 9.1.

A + B + G = Pr oduct + G (9.1)

Where A is the metal, which also can be functioned as the fuel, B can be a metal or
metallic oxide (e.g., Ni, Ni(NO3 )2 , Fe2 O3 ), which act as the fuel. G is the gasifying
agent, and these are metal hydrides and carbonates, which on heating liberate gases
like, hydrogen, carbon di-oxide or carbon monoxide. Teflon, borax etc. are also used
as the gasifying agents. Porous metal, bi-metal, metal carbide and silicide are formed
as product in the solid state combustion synthesis. The combustion synthesis without
the use of gasifying agents were also used, be practised, which however generated the
porous structure with only about 30–50% porosity. Use of the gasifying agents during
the synthesis process improved the porosity in the material over 85%. The combustion
process is carried out through the templating or non-templating routes. Mixing of the
reactants are very important in the generation of homogeneous porous structures as
328 A. K. Satpati

the products. The reactants in the nano particles improves the surface kinetics of the
combustion reaction, thus the delay in the ignition process substantially reduced due
to the utilisation of nano particles as reactants. Though the reactant particles with
nano meter size shown better kinetics and also generates hierarchical structures, it is
sometime detrimental in generating the quality of the porous materials. The use of
Al nano particle for the synthesis of NiAl bimetallic system generated the inferior
quality of products. This was explained to be due to the excessive generation of
Al2 O3 passive layer over the Al nano particle surface due to the fast surface kinetics
of the Al nano particles. The problem has been eliminated through the use of organic
passivating agents over the Al nano particle surface, additionally the passivating
agents act as gasifying agents during the combustion synthesis. C13 F27 COOH was
used as the passivating and also as the gasifying agent over the Al nano particle
surface for the synthesis of Ni foam [49]. The optimisation of the pore forming
agents or the gasifying agent is important, the excess use of these reagents though
generates porous materials with higher pore volume, the mechanical stability and the
continuity in the generation of the foams impedes. The energy for the combustion
synthesis process are provided from the mechanical, chemical, electrical or from the
lasers.
In the solution combustion route of synthesis, the metal precursors, which are in
the form of nitrates dissolved in water along with the fuels (glycine, citrate, urea etc.),
sometime complexing agents are also added in the mixture. The mixture is heated
in open air hot plate for complete evaporation first, and then the mixture undergoes
ignition especially through the decomposition of nitrates. The porous materials thus
synthesised has the advantage over the solid state synthesis as the reactants are mixed
well up to the molecular level of mixing. The perovskite type of complex oxides
could be synthesised using the solution based combustion synthesis procedures [50].
Depending upon the requirements, the solution based synthesis process has been
augmented through the sol–gel synthesis, utilisation of micelles, vesicles templates
for generating porous structures with controlled porosity, which are discussed in the
later parts of the chapter.
For better control over the pore size and their distributions, the porous materials
are synthesised through the templating routes. In the template synthesis protocol, the
metallic foams are synthesised using a polymeric template, and metal is deposited
over the template. Several inorganic materials and organic polymers are used as
template. Easily available polymers like melamine, plastic polymer, polyurethane,
polydimethylsiloxane are very commonly utilised in the synthesis process [51]. In
the template route of synthesis, the self-assembly has an important role in gener-
ating nano structured materials with controlled porous structures. The sizes of the
pores and their distributions are important factors in determining the properties of
porous structured materials which would enhance the performance of the mate-
rials in various applications. The assembling of nano structured materials generates
various new chemical, electrical, electronic, magnetic and optical characteristics. The
combinations of high surface area and fast charge transport are the most important
parameters for their advanced scientific applications. According to their pore sizes,
porous nanomaterials are branched out into three different categories: microporous
9 Synthesis Strategies and Applications of Metallic Foams … 329

(pore size < 2 nm), mesoporous (2 nm < pore size < 50 nm), and macroporous (pore
size > 50 nm) materials.
Among various porous materials the porous noble metal nanostructures (PNMNs)
having ordered or non-ordered structures, attracted the scientists to investigate in their
catalytic properties applicable in various important fields [52–55]. In electrochemical
catalysis, most of the catalytic systems require porous materials with different pore
structure for efficient catalytic applications. The porous materials with large effective
pore volumes in the form of electrodes have the advantages from the enhanced surface
area, higher electron transfer rate and the efficient mass transfer process through the
pores. There are several reports dealing with the PNMNs, generated through plenty
of different synthetic procedures. Different synthesis strategies generated several
different ordered or non-ordered porous nano structures and the materials generated
sometime are named as nano foams, aerogels, hollow structures etc. Such materials
have applications in sensors and catalysis [20]. The synthesis procedures of such
ordered and non-ordered nano structures are discussed in the following section of
the chapter.

9.2.1 Synthesis of Ordered Porous Nano Structures Through

Template Route

Various templating routes are adopted for the synthesise of ordered PNMNs, among
them the hard templates and the soft templates routes are practiced the most as these
routes are the most effective in the synthesis of ordered porous nanostructures.

9.2.1.1 Synthesis of PNMNs Using Hard Template Route

The hard templates, which include the assembled colloidal crystals, mesoporous
silica, alumina membranes, zeolites, have been extensively utilised for the synthesis
of several ordered porous nanostructures of metals [56, 57] oxides [58, 59] and other
compositions [60, 61], such templates provide the porous structures with controlled
morphologies. It is worth mentioning that the generation of the mesoporous templates
with the retention of morphology without any deformation is extremely impor-
tant task. Generally, the non-uniformity in the porous structures arises through the
collapse of the pore volume when the chemical procedures are applied to generate the
porous materials. The synthesis protocol following the hard template route has been
the most widespread used method to generate ordered porous materials consisting of
metals, metal oxides and carbon, with well distributed porous structures and defined
morphologies [62, 63].
There are three major steps in the synthesis protocol to synthesise the materials,
with the first step as the synthesis of sacrificial template having ordered porous
structure, then in the second step, incorporation of composite materials inside the
330 A. K. Satpati

template and finally removal of the sacrificial template. Highly ordered mesoporous
or macroporous materials like; KIT-6, MCM-48, MCM-41, and SBA-15 produce the
well-ordered nano structure with highly ordered pores. Controlling the pore parame-
ters would generate PNMNs with properties suitable to include various functionali-
ties for targeted applications. The electrochemical deposition, electroless deposition,
chemical processing, ammonia treatment and hydrogen reduction process could be
included in the generation and modulation of materials through hard templating route.
The 3D close packed crystals of silica and latex having long range ordered struc-
ture generate materials with ordered distribution of pores [64, 65]. Additionally,
different functional groups, like; −NH2 , −SH, and −COOH, could be grafted in
this process of synthesis. Such inclusion of functional groups enhances the appli-
cability of the nano porous materials. The thiol functional groups are useful in the
incorporation of gold nano particles (AuNPs) inside the pores, later through the elec-
troless deposition of metals and heat treatments and finally removal of the sacrificial
template generates the free standing porous gold metal nano porous structures [66].
Similar synthesis procedure has been adopted to fabricate the porous nano structures
of AuNPs and Au/Pt bi metallic nano porous materials [67, 68].
The electrochemical deposition processes combining with the hard templating
process generate efficient routes in the synthesis of porous structured materials with
well-defined and controlled pore structure, additionally the electrochemical method
of synthesis is fast and better controllable through modulation of deposition param-
eters. It was demonstrated about the deposition of ordered porous structure using
electrochemical deposition with varying metal composition [69].

9.2.1.2 Soft Template Method of Synthesise of PNMNs

The controlled pore structure also could be synthesised through the soft template
routes, and the process of the synthesis is diverse in generating the nano structures
[70]. As soft templates, the amphiphilic molecules like surfactants and amphiphilic
block copolymers are used in the generation of the templates. Such molecules
generate the self-assembled structure called micelles in solution at a concentration
slightly higher than the critical micelle concentration (CMC). At even higher concen-
tration of the surfactants, the surfactant molecules form the lyotropic liquid crystals
(LLCs) phases. Both the micelles and the LLCs are utilised in the synthesis of porous
nano structures. Attard and co-workers have developed the synthesis protocols for
the mesoporous platinum nano particles (PtNPs) through chemical and also through
electrochemical deposition routes utilising the LLCs as the templates. The porous
nano structure with pores size less than 4 nm has been reported which are synthesised
using the soft template route [71, 72].
On contrary to the LLCs route of synthesis protocol, the micelle assembly
route requires low concentration of the surfactants, sometimes prove to be advan-
tageous alternative to synthesise mesoporous metal nano structures. Yamauchi and
co-workers established the new approach, through the generation of micelle assembly
through electrochemical route, for assembling mesoporous Pt-based films and the
9 Synthesis Strategies and Applications of Metallic Foams … 331

deposition was carried out at a constant potential [73–75]. Li et al. demonstrated the
electrochemical deposition of Au films with mesoporous structure with controlled
porous assembly using micellar soft templates [76]. The nano structure of porous Pt
nano rods are reported with the 6–8 nm pore sizes using electrochemical deposition
procedures [77]. In addition to the electrochemical deposition process, soft templates
are used for the generation porous structure through the chemical reduction process
where Pt-based nano porous structures are generated [78, 79].
In a different synthesis approach the well-ordered mesoporous nano structures
were generated through the solution based reduction using di-block copolymer
Pluronic F127 soft templates [80]. The block copolymers (BCPs) are a branch of
polymers where the two or more homopolymers coexists, the template preparation
using the BCPs has the flexibility to generate well-ordered nano structure with the
additional advantage of self-degradable nature of the polymers, and thus the use
of block copolymers produces the facile approach of synthesising the porous nano
structure [81].

9.2.2 Synthesis of Non-ordered Porous Nano Structures

After discussion about the ordered porous nano structure, the class of compound with
non-ordered porous nano structure are discussed here, which are more ubiquitous in
nature compared to the ordered porous structures. The non-ordered materials could
be made with large specific surface area, better mass and charge transport property
which are the essential elements to function the materials as efficient catalyst. The
design strategy has been modified in the direction to generate materials with non-
ordered pores for the noble and non-noble metal nano structures and their utilisation
in various catalytic processes [82]. Several different strategies adopted in synthesising
non-ordered nano structures are discussed in the following sections.

9.2.2.1 Synthesis of Nanofoams Using Dealloying Strategy

Dealloying is one of the effective way to generate porous nano foams, in this process
the active component of the alloy is selectively etched out through the chemical, elec-
trochemical or sometime utilising the chemical and electrochemical routes together.
Generation of Raney nickel is an age old material generated through the dealloying
process, discovered by Murray Raney in the year 1926 [83]. The de-alloying process
involves two main steps, the dissolution of the active materials out of the alloy and
the surface diffusion of the other material to form the aggregate. Through the de-
alloying process, the gold nano structure was formed through the selectively etching
out the Ag and Cu from the alloy of Au, Ag and Cu [84].
At this juncture, it is to be mentioned that the chemical etching process has some
inherent drawbacks as it is challenging to have control over the process, the atoms at
the surface of the materials are highly active towards the etching process and undergo
332 A. K. Satpati

random dissolution during the chemical etching step. For better control of the disso-
lution process, stabilising agents and surfactants are required to be added along with
the etching agents to get the materials with controlled characteristics. In one of the
initial reports, Shao et al. reported the generation of porous/hollow palladium copper
nano particle (Pd/Cu NPs) utilising the electrochemical dealloying procedures, the
porous structure was then used to fabricate core–shell nano structure with mono-
layer Pt as the shell [85]. The resulting core–shell nano structure was applied as the
electrocatalysts, which showed 14-fold improvement in the ORR activity over the
commercially available Pt/C catalysts. Such enhancement is observed to be due to
the Pt monolayers at the shell and the synergistic effect from the core of the catalyst.

9.2.2.2 Synthesis Through the Kinetically Controlled Reduction

Method

Synthesis of kinetically controlled materials generated nano structures of facile prop-

erties suitable for catalytic activities. In a report by Eswaramoorthy and co-workers,
the kinetically controlled reduction process using NaBH4 and generation of noble
metal-based nanosponges with significantly high surface area was discussed [86].
Through the selected concentrations of metal precursor and the reducing agents,
various kinetically controlled PNMNs of 3D network structures could be formed.
It was also applied with the bi-metallic and tri-metallic nano sponges which were
utilised as the electrocatalysts in ethanol and methanol oxidation processes [87–
89]. The kinetic controlled reduction process has been extended for the non-noble
materials as well [90–92]. Such kinetic controlled mechanism of reduction process
involving the NaBH4 as the reducing agent which is an efficient procedure to gener-
ator nano sponges within a very short time at room temperature; however, due to
the fast process kinetics the controlling of the shape, size of the nano structures is
limited. Through the modification in the synthesis strategy like lowering of temper-
ature, scavenging the kinetics and slowing down of the network generation process
the overall control of the porosity and sizes have been reported to be improved [93].

9.2.2.3 Synthesis of Non-ordered Porous Nano Structures Through

Dynamic Templates

In addition to the kinetically controlled synthesis procedures, the non-ordered porous

materials are synthesised through soft templates using surfactants. For the synthesis
of Pt based porous network materials, cetyltrimethylammonium bromide (CTAB)
dispersed in water and chloroform phases was successfully used [94].
Electrochemical deposition procedures have been applied using the gas bubble
dynamic template, for the generation of porous nanostructures with controlled and
uniform pore size and distribution. The pioneering work by Liu et al., revealed the
electrodeposition of 3D foam films of non-noble based metals like, Cu, Sn, and
9 Synthesis Strategies and Applications of Metallic Foams … 333

CuSn alloys in acidic solution [95, 96]. In this synthesis procedure the metal elec-
trochemical deposition process is accompanied by the hydrogen evolution process,
where H2 molecule evolves as gas bubbles after reduction of H+ ions, these gas
bubbles act as the dynamic template for the simultaneous deposition of metal nano
particles, the 3D porous nano structures at the surface of the electrode is gener-
ated through these gas bubble templating route [96]. The electrochemical deposition
technique for the generation of porous nano structures is relatively green method of
synthesis compared to the other chemical template based synthesis procedures. The
process is simple as it does not require the preparation of the soft template and its
removal after the synthesis procedure. The H2 template method has been utilised
for the synthesis of 3D noble metal ion foams are Au [97], Ag [98], Pt [99], Pd
[100], using direct electrochemical deposition procedure. In addition to the single
metals, bi-metallic nanostructures are also formed through the direct electrochemical
deposition procedure [101, 102]. The indirect electrochemical deposition procedures
involve the formation of 3D PNMNs through galvanic replacement recation [103–
105]. Underpotential deposition procedure is another method of electrochemical
deposition process through which the porous nano structure could be formed [106]
which is associated with processes like, electrochemical dissolution and reduction
process [107–109]. This synthesis protocol could be adopted with plenty numbers
of modulations, where the morphology of the metal foams could be tuned with the
variation of deposition potential, deposition time, electrolyte compositions and modi-
fication of the condition of the synthesis procedures, the process allows to introduce
various functionalities in the porous materials.

9.2.2.4 Synthesis of Non-ordered Porous Nano Structures Through

Self-Assembly Method

Metal nano sponges are synthesised through the self-assembly derived route, using
surfactant self-assembly and capping agent, citrate ions have the versatile role as
capping agent; however, it is challenging to have the well-controlled nano porous
structure. The solution compositions and the type of electrolyte influences the texture
of the materials to a great extent. Zhang et al. have investigated the impact of elec-
trolytes by introducing the halide ions (F− , Cl− , Br− , and I− ) over the synthesis of
porous AuNPs [110]. The resulting nano sponges of AuNPs are shown in Fig. 9.1. The
difference in the affinities of halide ions with the AuNPs impact critically in tuning
the porous structure of sponge-like Au nano materials. During the synthesis proce-
dure, the citrate ions linked with the surface of AuNPs are replaced by the halide
ions, the replacement process is different which strongly depends on the affinity
between the halide ions and AuNPs. The replacement step modulates the fusion and
aggregation behaviours of the AuNPs, which resulted the generation of nanosponges
with different morphologies.
334 A. K. Satpati

Fig. 9.1 The schematics, depicting the effects of halide ions on the AuNPs and formation of sponge-
like Au nanostructures. Reprinted with permission from Ref. [110]. Copyright 2014 American
Chemical Society

9.2.3 Hollow Nanostructured Materials

Like the metal nano foam or the nano sponges, the hollow metallic nanostructures are
also included in the class of compounds of porous nano structures which are important
in terms of their versatile applicabilities [36, 111]. The hollow nano structures have
the advantage of having the distinctive combination of two or more surfaces. Hollow
nano structure consists of the internal surface and the external surfaces along with
the pores on the wall of both the surfaces. The morphologies of all these pores, and
surfaces could be tuned for generating optimum properties from such materials. Such
materials are advantageous for electrocatalysis and many other catalytic applications.
These materials are divided into two categories, simple and complex nano structures.
Depending on the number of the outer shells, the hollow nano structures are classified
as single, double and multi-shell. The porous hollow nano structures are generally
synthesised through the template based method and also through the self-templating
methods like galvanic replacement and the Kirkendall effect. Such materials have
unique characteristics, like, finely tuned morphology, porous outer walls, hollow
interior walls, the composition may also be tuneable. The synthesise procedures of
the hollow sphere materials are discussed in the following sections.
The hard templating protocol of synthesis of hollow nano structure is one the
most used methods of synthesis, and the methods are effective and simple to carry
9 Synthesis Strategies and Applications of Metallic Foams … 335

out [112]. The process of the synthesis involves four major steps: (a) formation of
the hard template, generally the chemically removable are used for such purposes (b)
modification of the surface of the template through chemical modification; (c) devel-
opment of the distinct structure over the surface of the chemically modified template
(d) selective removal of the template present inside the nano structure. Finally, the
hollow nano structures are formed using the hard templating technique. Similar to
the generation of PNMNs through the hard template route, the hard templating can be
made by using polymer, silica template and carbon based template for the generation
hollow nano structures.
In the polymer based hard template methods, the template is essentially formed
through the covalent linkage between the polymer chains [113]. Some of the polymer
chains commonly used for making the template are poly (methyl methacrylate)
(PMMA) and polystyrene (PS), the most important benefits of using such polymer
based templates is the easy removal of the template, which can be achieved by
dissolving it in organic solvent or through the easy thermal treatment. Li et al. have
reported the hard template synthesis of nearly monodispersed PMMA double shelled
hollow spheres and SiO2 core in double shell hollow spheres [114].
Silica template-based methods are the most important hard template route of
synthesis of hollo nano structure with the morphological uniformity and tunable
particle size, and it is also one of the cost effective method of synthesis proce-
dure [115]. The SiO2 spheres with high nondispersive nature are obtained using
the classical sol–gel method of synthesis, where the silicon alkoxides condensed in
water/alcohol mixture with the addition of ammonia [115]. Jang et al. have used the
synthesis protocol in synthesising TiO2 hollow spheres hard-template with controlled
numbers of shell [116]. The method was also used for the synthesis of hematite (α-
Fe2 O3 ) spindles with a SiO2 layer, through which the ellipsoidal α-Fe2 O3 @SiO2
core–shell particles were formed [117]. The α-Fe2 O3 @SiO2 particles were used as
the hard template, and the hydrothermal procedures were adopted for the synthesis
of shell-by-shell polycrystalline SnO2 . Finally, the SiO2 template was removed, and
the double-shelled hollow SnO2 nanococoons with portable α-Fe2 O3 spindles were
generated.
Carbon based hard template methods are also adopted for the synthesis of complex
hollow structures, and porous carbon hard templates have the additional advantages
as they could sorb various chemical species easily, which would facilitate the shell
formation process [118]. The transition metal oxides, such as α-Fe2 O3 , Co3 O4 , NiO,
CuO and ZnO with multi-shelled hollow microspheres were reported to be formed
using the synthesis technique. The numbers of shells in the core shell structures are
determined from the rate at which the metal ions fed during the synthesis process.
In contrast with the hard template method of synthesis, the soft template based
synthesis procedures has the advantage as it is easy to refill the hollow space inside and
also easy to encapsulate with the dispersed functional species. Based on the strategies
used in the synthesis process, the soft template method can be classified into three
categories, (a) emulsion templating, (b) vesicle/micelle templating and (c) gas bubble
templating. In both the emulsion and micelle based techniques, the parameters such
as the surfactant concentrations, pH, and electrolyte concentration are important
336 A. K. Satpati

in modulating the templating conditions. In the gas bubble template procedures gas
bubbles dispersed over the liquid phase are used as the soft templates. The gas bubble
emulsions are formed using sonication, gas blowing, chemical reactions, etc. Using
the micro-emulsion approach, the Au hollow nano structures having wall thickness
between 2 and 6 nm and the inner diameter between 20 and 40 nm are reported to be
formed [119]. Several micelles or vesicles have also been employed as soft templates
for the synthesis of different hollow nanostructures [120–122].
The self-templating method of the synthesis of hollow sphere materials is impor-
tant as it requires less numbers of synthesis steps which leads to the reduction in
the production cost. Two important self-template based synthesis strategies such as
galvanic replacement and the Kirkendall effect have been discussed in the following
part of the chapter.

9.2.4 Synthesis of Hollow Nano Structure Using Galvanic

Replacement

The galvanic replacement reactions are effective in generating hollow nano struc-
tures by replacing the sacrificial templates of the original metal or metal oxide. The
replacement processes are determined by the difference in redox potentials of the
two metals. The Au hollow nanostructures are formed from AgNPs [123], using
the method, several other research groups later utilised as the synthesis strategy to
synthesise hollow nano structure for several important applications. The galvanic
replacement strategy has been utilised using Ag as sacrificial agent in the Au, Pd, Pt,
and multimetal compositions to synthesise the hollow nanostructures, with geome-
tries such as spherical nanoshells [124], core–shell nano particles [125], nanodots
[126], nanocages [127], nanotubes [128], nanoframes [129], and nanodendrites [130].
In the synthesis process, initially the replacement procedure starts at specific
sites, where the surface energies are relatively large and then a seamless hollow
nanostructure is formed. For example, in case of Au–Ag alloy, Ag dissolves out from
the surface and simultaneously migrate to Au shell which may be called as alloying.
Later the Ag atoms at the shell are selectively further dissolved to form hollow walled
nano structure. The suggested mechanism is applicable in sacrificial templates as long
as there is enough difference in the reduction potential of two metals. Oxides are also
used as the template to synthesis the hollow nano structures, Cu2 O is used as template
for the synthesis of polyhedral hollow structure of Au [131]. In an another important
example of such synthesis procedure, Pt was spontaneously deposited at the Mn3 O4
nano particles surface by the galvanic replacement procedure between Mn3 O4 and
[PtCl6 ] [132]. This new approach of synthesis provided an important procedure to
load metal nano catalystsover metal oxide surfaces to improve the catalytic process
through the generation of hybrid nano composites.
9 Synthesis Strategies and Applications of Metallic Foams … 337

9.2.5 Kirkendall Effect

Apart from the various approaches as discussed to generate the hollow nano porous
structures, the Kirkendall effect is very effective to produce the nanostructures in
broad range of materials. In the synthesis process utilising the Kirkendall effect, a
net inward diffusion is generated due to the difference is ionic diffusion rates of
the core and shell materials, which leads to the nucleation of voids at the core/shell
interface and the void generation leads to the formation of hollow structured mate-
rial. Solid bridges are formed between the core and the shell, which facilitates the
transportation of core materials outward for the generation of the hollow structure.
The Kirkendall effect is a unique self-templating synthesis strategy for the gener-
ation of nanostructures with high yield, high crystal quality, and uniform size and
shape, of metal oxides [133–137], metal chalcogenides [138–146] metal phosphines
[147–149] alloys [150–152] and compound nanocrystals [153–156].
The Kirkendall synthesis strategy has been utilised to generate solid palladium
nanocrystals into hollow palladium nanocrystals, which has been achieved through
the insertion and extraction of phosphorus. The Kirkendall cavitation procedure when
repeated several times gradually inflate the hollow metal nanocrystals, which would
produce the nano shells of targeted thickness. The generation of hollow palladium
nano crystals is shown in Fig. 9.2 [158].

9.2.6 Foams of Metal Chalcogenide

The layered transition metal chalcogenides (TMCs) nanostructures are emerging

as important materials due to their exceptional chemical and physical character-
istics, which are not present in other nanostructured materials, the properties are
sometimes superior even to graphene. TMCs exhibit various anisotropic character-
istics which ranged from the electron mobility, magnetism, intercalation of species,
catalytic activity, and optical properties [159–166]. TMCs exist in two crystallo-
graphic structures; as in octahedral (1 T) and trigonal prismatic (2H). The versatile
physicochemical properties of transition metals generated through the varied char-
acteristics from metallic to semi-metallic or semiconducting with the variation in
the composition and crystallographic structure. The TMC, MoS2 is known for its
unique properties of possibility of nano porous, and layered structures lead to its
excellent applications in optoelectronics, and electrochemical energy harvesting and
storage [167–171]. The modulation of the shape and sizes of the TMCs generate
interesting electrical, electronic, optical, catalytic properties leads to several impor-
tant applications. As the synthesis procedures, the bottom-up chemical synthetic
approaches, chemical vapour deposition (CVD), mechanical/chemical exfoliations
are some of the popular synthesis routes which have been adopted to synthesise TMCs
[172–175]. The uniform mesoporous foam of MoS2 has been synthesised using the
(NH4 )6 Mo7 O24 , where wet impregnation method was used to homogeneously coat
338 A. K. Satpati

Fig. 9.2 Transformation of solid Pd nanocubes into Pd hollow nanocrystals with hollow interiors.
a–c TEM images of Pd nanocubes, Pd-P intermediates, and hollow Pd nanospheres, respectively.
Scale bars in (a to c) are 5 nm. d Snapshots of a Pd nanocrystal at different simulation time.
e Instantaneous diffusion coefficients D of Pd and P atoms during the simulation. f TEM images of
hollow Pd nanospheres at a low magnification. Scale bar in f is 20 nm, Reprinted with permission
from Ref. [158]. Copyright 2017 Springer Nature

the compound onto the pre-synthesized SiO2 nano spheres. The surface chemical
reaction using CS2 at the SiO2 surface converted the Mo precursor into vertically
aligned MoS2 layers around the SiO2 nanospheres. The mesoporous MoS2 foam thus
formed were recovered through the etching of the SiO2 template with an HF solution
[176, 177]. Through another simple synthesis strategy, the hydrothermal reaction
between sodium molybdate and thiourea with P123 as a surfactant at the reaction
temperature of 200 °C. The interconnected and porous 3D honeycomb-like construc-
tions of nano structure with pore size varied from 50 nm to hundreds of nanometres
of MoS2 nanosheets were synthesised. Other than MoS2 , VSe2 nanosheets were
synthesised from of vanadyl acetylacetonate (VO(acac)2 ) as a precursor for V [178].
For the synthesis of WSe2 , nano porous structures trioctylphosphine oxide (TOPO)
is injected rapidly into the solution containing W(CO)6 in TOPO, the diameter of
the WSe2 nano discs are reported to be 5.8 nm and the later is sized in the ranges of
2.5 to 9.7 nm, and the size variation could be modulated through the variation in the
molar ratio between metal precursor and the surfactant [179].
Carbonaceous composites of TMCs
The hetero-structure between carbon and TMC have applications in energy research
owing to the enhanced surface area and reduced mean free path of diffusion for the
9 Synthesis Strategies and Applications of Metallic Foams … 339

charges, which results in the enhancement in the electrochemical performance. The

hollow carbonaceous core is synthesised through multistep change in the composi-
tional and subsequent etching process, over the hollow carbonaceous core, the 2D
layered TMCs are grown using a seed-mediated growth method [180].
In an another synthesis procedure, cube-shaped α-Fe2 O3 is synthesised with
dimensions of 500 nm using co-precipitation method over the cube-shaped α-Fe2 O3
smooth polydopamine layer is generated. Afterwards by the utilisation of the carbon-
isation route in nitrogen atmosphere, the core–shell α-Fe2 O3 @PDA is transformed
into α-Fe2 O3 @C nanocubes. Thereafter the α-Fe2 O3 core is etched out with the HCl
treatment and the carbon nanoboxes were obtained. Over the carbon nano boxes,
MoS2 nanosheets are grown by solvothermal reaction, thus producing C@MoS2
nanoboxes. Using a similar method of synthesis, three-layered TiO2 @C@MoS2
tubular shaped nanowires are generated [181].
For further increase the conductivity and also to improve the catalytic perfor-
mance of the TMCs, TMCs-CNT/Graphene nano structure are synthesised. Inside
the 2D layered TMCs, highly conducting materials such as carbon nanotubes (CNT),
graphene, and conductive polymers are incorporated [182, 183]. The incorporation
of graphene sheets has improved the electrical conductivity, flexibility, and chem-
ical robustness of TMCs. The presence of oxygen containing functional groups like
–COO− , –COOH, and –COH on rGO assist as sites for the nucleation of MoS2
due to their high chemical interactions with Mo precursors. The MoS2 /rGO hybrid
nanosheets are synthesised through the solvothermal protocols [182].
In order to further improve the catalytic performance of the material, the TMCs-
Noble Metals nano porous composite materials are synthesised. The growth of the
metal nano crystals are succeeded over the large surface area MoS2 nanosheets
using the precursors of K2 PtCl4 , K2 PdCl4 , HAuCl4 , or AgNO3 through the chemical,
photochemical reduction or electroless deposition techniques [184–187]. Using mild
reducing agents in combinations of surfactants, such as sodium citrate, PVP and
CTAB, are beneficial in preferential incorporation of noble metal inside the TMCs
sheets by controlling the kinetics of the processes [184].

9.2.7 Synthesis of Porous Structure Through

Electrospinning Route

The electrospinning effect was first explained by Lord Rayleigh in 1882, and he
explained the typical characteristics of the charged droplets and reported about the
maximum amount of charges that a liquid droplet could be able hold after which the
charged droplet would be ejected in the form of a liquid jet [188]. Electrospinning
technique can be considered as different variant of the electrospraying; in both the
techniques high voltage was applied to eject the liquid jets [189]. However, there
is significant difference between the two techniques in terms of the viscosity and
viscoelasticity of the liquid used and their ejection with the application of high
340 A. K. Satpati

voltages. In case of electrospraying process, the jet introduced the liquids in the
form of droplets, whereas in the case of electrospinning the liquid jet is ejected in
continuous mode without breaking.
Electrospinning technique has been utilized to fabricate nanofibers from ranges of
materials. The polymers can be electropsun, and the nano porous network structure
can be formed. Self-assembled molecules may also be electrospun to form several
different structures. Several nano fibres could be formed through electrospinning
method using sol–gel jet [190].
In metal nano foams synthesis, metal nano particles at high concentration is
used as the dispersion media or spinnable media. As an example of this method
of synthesis, Ag nanoparticles (40 ± 5 nm) were dispersed in ethylene glycol with
the metal loading of about 50 weight % [191]. The Ag nano fibres are synthesised
by electrospinning the solution first, then annealing at 150 °C in air, the average
diameter of the Ag nanofibers using this procedure was obtained as 338 ± 35 nm.
The important limiting factor of the process is the inability to increase the metal
nano particle loading. Electrospinning is also utilised for the synthesis of ceramic
nanofibers, though it is difficult to carry the electrospinning using the ceramic melts
as it requires very high temperature for the melting [192, 193]. The electrospinning of
ceramic materials is reported using aged sol, using this procedure, ceramic fibres of
very high density are formed. The silica fibres are obtained using the sol–gel proce-
dures of uniform viscosity [194]. TiO2 nanofibers of anatase phase contained of fused
TiO2 nanoparticles of diameter 10 nm with voids between adjacent nanoparticles
could be formed using the method of synthesis [195].

9.3 Applications of Porous Structured Materials

The porous materials or foams have widespread commercial applications which are
utilised since long time which includes filtration devices, battery electrodes, self-
lubricated bearings, structural components, diesel soot filtrations and flow control
devices [196]. Foams are known to have excellent properties of absorption of energy,
finds important applications in fabrication of sound, pressure and vibration damp-
ening components and used for such purposes in several industries [197, 198]. As
an important application of energy absorption, the German automotive supplier
Karmann uses aluminium foam in the construction of bulkhead and the rear seat wall
for their convertible cars. The foam materials used for such purposes are reported to
be up to 10 times stiffer than the conventional steel parts with 30–50% less weight.
Porous materials are finding very important applications in developing several energy
storage materials either in the form of Li ion battery or supercapacitor [199]. In
the following section the applications of the porous nano structured materials are
mentioned in brief in the field of energy harvesting and storage, sensors, large scale
industrial use and in biomedical applications.
9 Synthesis Strategies and Applications of Metallic Foams … 341

9.3.1 Use of Foams in Li Ion Battery and Supercapacitors

In the verge of rapid industrial developments and increasing wealth of modern soci-
eties requires the development along with the sustainability and the environment
friendliness [200]. The world fossil fuel consumption in 2018 was 11,743.6 million
tons of oil equivalent (Mtoe), which accounts for the 84.7% of the world’s energy
consumption [201]. With the pace of developments, the fossil fuel combustion is set
to increase further, and it is projected that by the year 2040 the expected fossil fuel
consumption would be 17,651 Mtoe. It is therefore required to enhance the consump-
tion of the renewable energy, and it is targeted to use the renewable energy by 20%
of the total energy consumptions. Utilisation of renewable and clean energy requires
efficient storage system, Lithium (Li)-ion batteries (LIBs) has proven track record
as an efficient energy storage system due to their high specific energy, high power
density, and acceptable environmental friendliness. Among all the electrochemical
energy storage systems, LIBs has the largest share, as estimated in the year 2018
about 86% of the total energy stored are in the form of LIBs [202].
Current collector is an important component in energy storage devices. As current
collector, Ni foam is best suited to be used in Li ion battery and it is used for the
efficient transport of charges both from the cathode and the anode side of the Li ion
battery. The superior property of 3D Ni foam over the conventional films or sheets
has been utilised for enhancement in the performance of Li ion battery in terms of
enhancing the capacity at higher current rates. The redox reaction at the junction of the
frame of the Ni foam and the active materials is beneficial in improving the capacity.
The 3D structure and the incorporation of the active material significantly reduce the
diffusion length of the transport of charges, which is the important factor in higher
rate capability. Additionally, the use of Ni foam reduces the swelling of the active
materials on prolonged charge and discharge cycles [203]. Due to such advantages,
Ni foam was used as current collector in Li ion battery. The application of Ni foam
in holding the active CoSn2 material used in Li ion battery is shown in Fig. 9.3. It

Fig. 9.3 The SEM micrographs of electrodes. a Nickel foam before electrodeposition of cobalt and
tin. b After electrodeposition of Co–Sn alloy. Reprinted with permission from Ref. [204] Copyright
2013 Royal Society of Chemistry
342 A. K. Satpati

was shown that the CoSn2 evenly deposited over the Ni foam surfaces, due to such
coexistence of the active material and the current collectors the efficiency of the
charge transport in expected to enhance significantly, which has been reflected from
the enhanced rate capability of the materials through depositing materials directly
over the Ni foam current collectors [204–206].
However, there are several challenges in the use of metal foams as current collec-
tors for Li-ion batteries because the conventional metal foam based current collectors
usually has low tolerance in long term charging or discharging, especially at high
voltages. Though Ni foam is very well suited as current collector in Ni/MH battery
[207], it is vulnerable to corrosion when the foam parts come in contact with the
electrolyte materials of Li-ion battery [208]. In order to improve the corrosion resis-
tance of Ni foam, NiCrAl alloy foam was reported to use as the current collector for
lithium iron phosphate (LiFePO4 ) based battery system. The LiFePO4 is a promising
material due to its low toxicity, high safety, available at low cost, excellent cycle life,
high structural stability, and large theoretical capacity (170 mA h g−1 ); however,
the kinetics of the material is quite slow. Application of Ni foam or NiCrAl alloy
foam improves the kinetics of LiFePO4 , which has reflected in the enhancement of
the rate capability [209]. Similar to the Li ion battery, metallic foams are applied in
other secondary battery electrodes like, Zn air battery, Li oxygen battery and other
secondary battery systems [210, 211].
Like Li ion battery, supercapacitor is a potential energy storage device becoming
more popular in recent times. Supercapacitor is also called as pseudocapacitor or
ultracapacitor and is a highly efficient in storing charges. In conventional capacitors,
the charge is stored through the electrostatic interactions, whereas in supercapacitor
the charge is stored through both redox process and the electrostatic process. Due
to the involvement of the redox process, supercapacitors are called as the pseudo-
capacitor. The fast discharge process in supercapacitor leads to the enhanced gravi-
metric power density compared to the rechargeable batteries, additionally the super-
capacitors can sustain significantly higher numbers of charge and discharge cycles
compared to the rechargeable batteries. Supercapacitor devices are finding applica-
tions in automobiles, small buses, electric drives, UPS, active filters, traction devices
etc. The energy storage through the regenerative braking is an important application
in automobile industry, and supercapacitors are used for this purpose for short term
energy storage. The redox process in the supercapacitor is mainly associated at the
surfaces of the materials therefore the requirement of materials with high surface
area are essential for the constructions of supercapacitor electrodes [212–216].
The current collector function as the electrical linking between the active mate-
rials of supercapacitor with the external terminals. The redox processes essentially
occur at the surfaces of the active electrode materials which requires efficient trans-
port of charges from the active electrode materials to the output terminals through
the current collectors; therefore, the current collectors must provide good electrical
contact with the active electrode materials [217]. Current collectors with porous nano
structures serves the purpose of effective transport of charge without increasing the
mass loading of the device. The porous nano structures with three dimensional geom-
etry have the advantage of having large contact areas with the active materials, which
9 Synthesis Strategies and Applications of Metallic Foams … 343

reduced the requirements of the ions to diffuse the long distances thereby promotes
the transport of charges [218–221]. The improvement in the design aspects and
making better contact between the active materials and current collectors enhances
the charge storage capacity without increasing the material loading [222, 223].
The porous nano structure with controlled pore size is important for the active
electrode material. Pore sizes should be optimum for the electrolytes to seep in for
accessing the redox sites and also should have good numbers of redox sites. It is to
be noted that the unutilised pores are responsible for the decrease in the volumetric
capacitance of the porous materials. The carbon based porous materials along with
metal oxides with porous nano structures have shown significant improvement in
the capacitive property [213]. The mesoporous Co3 O4 has shown the enhanced ion
transport properties, which leads to the enhancement in the capacitive behavior [214].
Wu et al. have formed the hollow nano structured Ni(OH)2 with porous walls; the
electrodes fabricated using the porous Ni(OH)2 provide more efficient paths for the
interaction between the electrode materials, and the electrolyte and the capacitance
increased significantly [215]. The porous nano tube structure of TiO2 was fabricated
as support material, within that the Co or Ni oxides are deposited as redox active
substrate, the combination of porous nano structure of TiO2 and the redox active Co
and Ni oxides has improved the charge storage capacity [216].

9.3.2 Application of Porous Nano Structures in Fuel Cell

Technologies

Nano porous structure finds important applications in fuel cells, considered to be

the most important energy conversion technology. Generation of efficient materials
for the electrodes in fuel cells are very important technological challenge, generally
noble metal based catalytic materials are widely used as both cathode and anode
for the catalytic hydrogen evolution process and also for the catalytic oxidation of
small molecules or in the oxygen reduction [224, 225]. The key requirement of the
electrode materials is to have high electrochemically active surface area (ECSA)
and conductivity. The PNMNs serve both the purposes well. Porous nano structure
reduced the mass of the noble metal catalysts, thus reducing the overall cost of the
catalytic system.
PNMNs are directly used both as the cathode and the anode material for catalytic
electrochemical processes in the fuel cell. Most importantly, PNMNs can be used
without any support, thus eliminating the use of carbon support in the fuel cell
applications. These materials can be directly applied as self-supported nano catalysts
for both the cathodic and anodic electrochemical reactions of fuel cells, which can
eliminate the use of the conventional carbon support to the electrode, thus avoids the
drawbacks of the carbon supported catalysts. Applications of some of the PNMNs
used as the active electrode in the fuels cell research are discussed in the following
section.
344 A. K. Satpati

As anode materials PNMNs are utilised for the oxidation of small molecules like
methanol, ethanol, and formic acid as fuels in the fuel cell. Xiao et al. reported
the synthesis of hierarchically porous Au-Pt nanostructures, where the porous Pt
nano structures are decorated over the surface 3D AuNPs [226]. The nano structured
materials have shown excellent catalytic activity for the methanol oxidation reaction.
Due to the nano porous structure, the mass transfer property has been significantly
improved. The porous nano structure also reduced the tolerance to the intermediate
species generated due to the oxidation of methanol, which are otherwise detrimental
to the catalytic property of the materials. As a non-noble metal, Ni was incorporated
in Pt-Ni–P hybrid system and the porous nano structure of the system was fabri-
cated through the template assisted electrodeposition route. The materials showed
promising results with the additional benefits of decrease in the noble metal require-
ments [227]. In a recent study, Sesu et al. reported the Cu-Ni@rGO foams for the
enhancement in the methanol oxidation reaction. The self-propagation combustion
method was utilised for the synthesis of the non-noble metal based foam nano struc-
ture and rGO was also incorporated for improvement in the conductivity and surface
area further [228].
Several non-noble metal foams are being utilised for the catalytic oxidation of
methanol, in a recent study adopting the self-combustion technique, low density
Co–Cu-Bi ternary foams with three dimensional structures was synthesised and the
catalytic efficiency for the methanol oxidation has been improved significantly. The
catalysis poisoning effect, which is common with the noble metal based catalysts,
has been reduced significantly in this system, the catalytic activity reported to be
retained at 50% even after 10 h of operation [229, 230].
As the ethanol oxidation electrode, Pd based aerogels are reported to increase
the efficiency significantly compared with the commercially available Pd/C catalytic
system. The Pd aerogels have shown the electrochemical surface area (ECSA) values
significantly improved for the various Pd aerogels as reported by Liu et al. [231]
Ni foam as current collector or catalysts support is almost unavoidable in making
efficient electrodes. Apart from the function as current collector, Ni foams are used
for the deposition of active catalysts materials, as an example Au nano particles in
the form 3D nano structure are electrochemically deposited over Ni foam substrate
[16, 232–234]. The catalytic system has been efficient for ethanol oxidation reaction
with significant improvement in the efficiency.
Oxidation of formic acid is also an important reaction utilised as the anode
process in fuel cell. The nanoporous Pd-Cu alloys catalysts were reported to be
fabricated using the de-alloying method of synthesis, and the catalysts electrodes
were fabricated using the porous Pd-Cu based nano structures [235]. Compared to
the nanoporous Pd alone the catalytic activity using nanoporous Pd-Cu system was
improved significantly. Cherevko et al. developed high surface area Pd foams through
the electrochemical deposition route with the roughness factors over 1000 and the
specific surface area of 60 m2 /g, the catalysts has shown high activity towards ethanol
oxidation reaction [100].
The porous nano structures are also utilised as cathode materials for the Oxygen
Reduction Reaction (ORR) at cathode. The ORR is one of the most technological
9 Synthesis Strategies and Applications of Metallic Foams … 345

challenge in fuel cell fabrication, which arises due to the complexity in the reduction
process of oxygen. The requirement of an efficient catalyst is thus very important
for efficient running of the cathode reaction in fuel cell. The porous nano struc-
ture of foams were utilised for the catalytic reduction of oxygen at the cathode.
Investigations revealed that the porous self-supporting network structures enhanced
the electrochemical performance by about 2–3 times than that of the commercially
available standard Pt/C catalytic system. In the report by Strasser et al., the Pt-Ni
bimetallic porous materials are synthesised, the porosity induced catalytic perfor-
mance was investigated, it was observed that porosity below 10 nm is beneficial, and
at higher pore size, remarkable drop in the catalytic performance observed [236].
Oxygen evolution reaction (OER) plays a crucial role in electrolysers, solar cells
and photoelectrochemical water splitting process [237–241]; however, the sluggish
electron transfer kinetics of the process is of considerable concern [242–247]. The
porous nano structured materials have excellent applications in the oxygen evolution
reactions (OER). Building hierarchical hollow structures thus holds promise for
more efficient electrocatalysts, which can render large surface area, better electronic
conductivity and porosity for electrochemical processes [248–250]. Great efforts
have been devoted to develop such porous and hollow nanostructure, which can, not
only enhance the desired activity but also impart new functionalities [249–253].
In a work reported from our group has focused on the synthesis of porous nano
structure of Nix Co3-x O4-y nanocages through a simple metal organic frame work
(MOF) template based fabrication route for non-stoichiometric Ni-Co metal oxide
nanocages with mesoporous structure [254]. The redox centres rich in Ni and Co
have shown as efficient catalysts for the oxygen evolution reaction. The influence of
different compositions of Nix Co3-x O4-y nanocages on their structural and chemical
characteristics is investigated along with tuning of the electrocatalytic OER process.
The SEM images of the nano cages with different ratios of Ni and Co along their
schematic representations are shown in Fig. 9.4. In the nano cage structure, the
best catalytic activity was observed with Ni:Co ratio of 1:1. The combined effect
of 3D porosity, rich redox centres, oxygen vacancies associated non-stoichiometry
and high electrochemical surface area (ECSA) has resulted in achieving a higher
catalytic current at a lower onset potential, faster OER kinetics and a facile mass
transport during oxygen evolution. Such synergistic behaviour imparts exceptional
catalytic activity to Nix Co3-x O4-y porous nanocage system as a cost effective and
viable oxygen evolution catalyst.
Hydrogen evolution reaction (HER) is the process through which hydrogen is
generated from water through electrolysis process. It is essential to have of earth
abundant catalysts in place of the noble metal catalytic system and has generated
the interest in research in the development of materials for the HER. Among several
non-noble metal catalytic system, the molybdenum di-sulphide (MoS2 ) has shown
promising results in generating hydrogen from water through electrolysis [255–261].
The MoS2 with porous or layered nano structure has the advantage of having multiple
reaction sites, and better access to the electrolytes over its surfaces. The conductivity
of the MoS2 is important and 1 T phase serve the purpose better. The surface area and
the charge transport property of MoS2 further improved through making composite
346 A. K. Satpati

Fig. 9.4 a to f FESEM images of the MOF derived catalysts, g to l magnified FESEM image of
the MOF derived catalysts, and m to r TEM images of the respective MOF derived catalysts. The
schematic shown in the bottom of Fig. 9.4 represents the evolution of the Nix Co3-x O4-y catalyst
when Ni is loaded in different concentration, Ni/Co = 0, 0.5, 1, 1.5 and 3. Reprinted with permission
from Ref. [254] Copyright 2016Wiley-VCH GmbH

with graphene oxide (GO) or reduced graphene oxides (rGO). In our investigation we
have observed that the enhanced mass transfer through the fast exchange of protons
from the medium and the functional groups of GO in MoS2 /GO composite shown
improved catalytic activity. The schematic representation of the proton exchange
process between the medium and the functional groups of GO is shown in Fig. 9.5
[182]. The TEM image and the scanning electrochemical microscopy (SECM) scan
of the catalysts surface are also shown in Fig. 9.5. The TEM image showing the
layered structure of the composite. The SECM imaging indicates the current response
from the catalyst surface originating from the catalytic hydrogen evolution process.
The image shows several areas from which high HER current response could be
generated.
The foams with porous structure having large surface areas are especially advan-
tageous in utilisation of electrocatalytic or photocatalytic splitting water to generate
hydrogen and oxygen [262–264]. For photoelectrochemical water splitting the porous
network materials are replacing the conventional indium tin oxide (ITO) or fluorine
doped tin oxide (FTO) as the electrode substrates, which has improved the charge
9 Synthesis Strategies and Applications of Metallic Foams … 347

(a) H+ H+ (b)

Exchange
of proton with
O- H+
bulk solution
H+ O-
O- H+ O=C O-H C=O

O=C + e-
+ e- Had
Had
Had
H-O O-H
H-O O=C
H2
O- H+

½ H2

Fig. 9.5 The Schematic representation of the mechanism of the proton transfer process in the
MoS2 /GO composite during the HER process; Inset a the TEM image of the layered structure of the
composite and b The SECM image of showing the HER current response over the composite modi-
fied electrode surface. Reprinted with permission from Reference [182]. Copyright 2017 American
Chemical Society

Fig. 9.6 SEM images of foam Ni (a), antibody-functionalized foam Ni incubated without (b) and
with (c) SRB culture. Reprinted with permission from Ref. [293]. Copyright 2010 Elsevier
348 A. K. Satpati

transfer property of the cathodes and anodes. The Ni and Fe foams are the better
choice for loading the active materials to fabricate the anodes and cathodes for water
splitting experiments.

9.3.3 Application of Porous Structures in Electrochemical

Sensors and Biosensors

The design and development of electrochemical sensors are fascinating in terms of

their portability and onsite applications [265–267]. Construction of the electrodes
with suitable electrode materials is the most important part in the development of
sensors. The porous nano structure materials with their unique properties of high
surface area, faster transport of charge and the ability to be functionalised with
suitable functional groups are important factors making them suitable in developing
the sensors. PNMNs are generally best suited for the modification of electrodes in
developing electrochemical sensors and biosensors, owing to their enhanced charge
transfer properties in addition to other properties common to all porous materials.
Several PNMNs modified electrodes were explored in developing electrochemical
sensors for the small molecule, toxins, drugs, using enzyme, non-enzyme based
sensors, DNA sensors, immunosensors etc.

9.3.3.1 Application of Porous Nano Structure in Non-Enzyme Based

Sensor

The non-enzyme based sensor offers easy operation, storage and have better long
term usability compared to the enzyme based sensors. Metal foam or the nano porous
materials offers great supports as the electrode materials for the non-enzyme based
sensors. Juska et al. have developed the Cu nano dendrite foams based array sensors
for the detection of glucose. They have demonstrated the enhanced catalytic activity
of the electrochemically deposited Cu foams based miniaturised electrodes as the
electrode materials for the efficient non enzymatic oxidation of glucose. The array
electrodes offered sensitivity much superior to the related literature reports along
with the typical characteristics of the non-interference from the chloride ions, which
is an important interfering agent in glucose sensing [268]. Similarly, the gold nano
rods decorated over the Ni foams are applied for the enhanced electrochemical signal
from glucose, the copper oxide nano wire over the copper foams are also reported
for the glucose sensing. In addition to the copper foams, the gold foams are also
found to be suitable for the electrochemical sensing of glucose [269–271]. Metal
and graphene based composite foams are also reported for the non-enzyme based
sensing of glucose [272, 273]. Other than glucose, the metal nano-porous structures
and foams are utilised for the sensing of H2 O2 , several drugs and biomolecules [274].
9 Synthesis Strategies and Applications of Metallic Foams … 349

Denuault et al. have constructed mesoporous Pt microelectrodes to utilise the

quasi-hemispherical diffusion with large effective electroactive area for the high
sensitive detection of H2 O2 over a wide range of concentrations [275]. Furthermore,
well-defined nanoporous PtNi alloy nanowires [276] and 3D nano porous gold film
[277] were fabricated through the dealloying method of synthesis. Both the materials
showed a remarkable enhancement in the electrocatalytic activity for H2 O2 sensing.
Additionally, Chung et al. have constructed 3DAu nano-dendrites through electrode-
position of Au using a gas bubble dynamic template method [278]. The porous Au
nanostructures with ultrahigh surface area were used as the sensor substrate for the
advanced detection of As(III) at ultralow concentration.

9.3.3.2 Application of Porous Nano Structure in Enzyme-Based

Biosensors, DNA Sensor and Immunosensors

The coupling of enzymatic actions with the electrochemical sensors enables the
appropriate detection of target molecules through the utilization of combined effect
of the high specificity of the enzymes with the high sensitivity of electrochemical
signals generated through porous materials [129, 279]. Several nanomaterials with
variation in sizes, shapes, and compositions have been prepared and employed as
advanced porous electrode materials for the immobilisation of enzymes; thus, the
electrochemical enzyme based biosensors were fabricated. PNMNs with high pore
volume and large surface area, which increase the enzyme loading and also has the
capacity to protect the enzyme from the surrounding environment. Pariente et al.
developed lactate oxidase-based biosensors by fabricating porous Au material with
rough surfaces [280, 281]. The sensor used hydroxyl-methyl ferrocene as the redox
active agent, and the analytical method developed using the modified electrode could
sensitively detect lactate with the detection limit of 21.5 μM and sensitivity of 1.49
μA mM−1 . Additionally, Chen et al. [282] and Huang et al. [283] used Au nanos-
tructure based electrode fabricated from the dealloying technique and used as sensor
for the development of glucose sensor, where glucose oxidase enzyme was used as
modifier. The enzyme based biosensor has the advantage of the superior activity in
terms of specific interaction with the analytes and the inherent fast response; however,
the enzyme based sensors have the issues like high cost and instability with minor
variation in the experimental conditions [284].
The sensing of the biomolecules based on the electrochemiluminescence (ECL)
is an important analytical methods utilises the luminescence signal from a standard
redox probe with the application of suitable potential. However, the ECL based
detection has the issues like weak and broad signal, and intermittent loss in signal
strength, the application of porous nano materials improves the signal strength of
ECL based detection [285]. The modification of Ni-foam with NiO nano structure
has been utilised in the ECL based detection of glucose of in serum sample, where
the ECL signal could be enhanced and stabilised [286].
DNA biosensor sensors are known for their high specificity and extremely high
sensitivity up to the femtomolar concentration, which leads to their applications in
350 A. K. Satpati

genoassay, suitable for the clinical diagnosis, forensic and the environmental anal-
ysis. Gold has special application in DNA based sensors due to their compatibility;
gold in the form of nano porous structure is termed as the nano porous gold (NPG)
and is very well suited for the electrochemical DNA biosensor [287, 288]. The elec-
trochemical DNA biosensor fabricated using the NPG electrodes has been utilised
for the determination of retinoic acid receptor α(PML/RARα) fusion genes in the
case of acute promyelocytic leukemia, where the electrochemical signal from the
methylene blue (MB) is used for the detection. The signal was typically enhanced by
about 10 times especially due to the use of NPG modified electrode. Mehrgardi et al.
have used the NPG as the electrode in DNA biosensor where ferrocene carboxylic
acid was used as the redox probe. In this case the redox probe, ferrocene carboxylic
acid was attached covalently on the top of the probe DNA, and the signal is generated
while the probe DNA undergo hybridization when comes in contact with the target
DNA. The significant enhancement of the electrochemical signal due to the NPG
electrode leads to the development of detection strategy up to the detection of single
base pair mismatch in DNA [289].
The early detection of the microorganisms is extremely important in deciding
the treatment procedures in all diseases, which guide the medical system for the
early decision on treatments with minimal use of antibiotics. Immunosensing is
an important procedure in detecting the microorganisms responsible for various
illnesses [290]. The porous nano structures are used in the fabrication of electrodes
in the immunosensing applications. The porous gold films are utilised as the elec-
trode materials in developing label free immunosensor for the determination of C-
reactive protein, the resistance signal was generated from electrochemical impedance
spectroscopy measurement for the impedance based sensor [291].
Additionally, the copper foam nano wire arrays are utilised in developing the elec-
trochemical immunosensor for prostate specific antigen. [292] It was also reported
about the immunosensors for the sulphate reducing bacteria (SRB) using Ni foam
and gold nanoparticles as the substrate, which provides effective trapping plat-
form for the bacteria. The sensor was utilised in the detection through the impe-
dometric detection techniques [293]. The typical structure of the Ni foam used in
the immunosensing purposes of SRB and the Ni foam modified with rabbit antibody
used for the sensing of SRB along with the SRB embedded over the sensors substrate
are shown in Fig. 9.4. The instant decrease in the charge transfer resistance form the
electrochemical impedance measurements was utilised in the determination of SRB.
In a recent study the metal–organic framework (MOF) based Ni foam supported
three-dimensional (3D) immunosensor was constructed and utilized for the specific
recognition of troponin (I), acardiac biomarker. Ni was amine functionalised, which
was interfaced with the biologically active materials anti-troponin (I), the sensor
electrode was thus fabricated and utilised. Analytical measurements were carried
out using impedance measurements by electrochemical impedance spectroscopy.
The sensor generated high sensitive measurements procedures with limit of detection
13 fg/mL with improved specificity [294].
9 Synthesis Strategies and Applications of Metallic Foams … 351

9.3.4 Applications Porous Materials in Concentrating Solar

Power (CSP)

Solar energy is the most abundant renewable resource available on Earth. About
430 EJ (1 EJ = 10 19 J) of sunlight energy impact on the Earth per hour, which is
much more than the total annual world energy consumption [295]. There are several
methods targeted to harvest solar energy into usable form, out of which the one
of the important solar energy harvesting protocol is through the high temperature
thermochemical storage, which can be utilised in large scale. This process contains
a heliostat field and a solar receiver generally located on the top of a tower, due its
presence over a top of a tower such plants are called as tower plants. The heliostats
are mirrors with large dimensions, which are used for the reflection of sunlight and
concentrate it on the receiver placed at the centre [296].
The solar receivers are the heat exchangers, used for the transformation of concen-
trated solar energy into thermal energy by heating up a fluid, the hot fluid flows
through the radiation absorber components. Metallic foams are best suited as the
receiver materials for the solar energy concentrators, the porous structure helps to
expose large area materials by allowing the solar radiation to enter inside the mate-
rials, also the high temperature corrosion of such materials could be reduced through
the utilisation of bi-metallic foams. Ni foams has been used as the receiver materials,
and the bi-metallic foam of Ni with Al reduces the corrosion at high temperature
[297–299].
The solar heat is also stored through the redox processes, and the materials placed
as the receiver can be utilised for receiving the solar radiation along with conversion
and storage through the redox processes. The foams of cobalt oxide are best suited for
such purposes. Agrafiotis et al. have reported the use of porous foams of Co3 O4 with
good structural stability, which does not show any significant loss of redox activity
after 30 cycles [300, 301]. However, due to high cost and scarcity, and also the known
toxicity of Co, several other metal are incorporated with Co3 O4 such as Mn, Fe, Ni,
Cu and Zn to reduce the requirement of Co for the purpose, at the same time keeping
the capacity of the material unchanged. The Mn-doped Co oxides showed that the
material performed better as the density of energy storage was decreased with the
incorporation of Mn with Co3 O4 [302]. However, with low Fe concentrations (about
5%), the long term cyclability of the materials along with density of energy storage
turn out to be high [303]. The Co3 O4 based foams used for the high temperature
redox process, and the device form of the materials before after use are shown in
Fig. 9.7 [304, 305].

9.3.5 Commercial and Large Scale Applications of Foams

The porous structure with macroscopic pores is having several industrial appli-
cations. There are large number of manufacturing technologies for the synthesis
352 A. K. Satpati

Fig. 9.7 a Picture of Co3 O4 /Al2 O3 with 90/10 wt. % based honeycombs (freshly made before use).
b the sample after 104 cycles. Reprinted with permission from Ref. [305]. Copyright 2016 Elsevier

of foams, sponges and porous materials with macroscopic pores. The commercial
synthesis process utilises the powder metallurgy route or the melting route for the
large scale generation of such materials. The direct and indirect foaming methods
are also utilised for the large scale synthesis of foams which are very well described
in the literature [306–308]. The porous materials offer important applications in the
automotive industry, in the electric car, as the lightweight construction becoming
mandatory. Additionally, the safety is another important factor, where a light and
effective crash protection system is essential. The example of such application is
shown in Fig. 9.8, where the metal foam is sued as the crash protector. Metal foam
parts developed by the Technical University Berlin and Pohltec are shown in the
prototype of an ultra-light electric vehicle developed in the frame of the European
Project Evolution [309]. In another example Alulight manufactures the metallic foam
shock absorber and manufacture millions of such units for high end vehicles, the per
unit mass requirements of such foams is significantly low, only about 7 g of mass is
used per device. Exploiting the property of high energy absorption capability of the
metallic foams, Foamtech (Daegu, Korea) provided crash elements for a guardrail at
the Massan-Chanwon Bridge in Korea. The Al-foam as a protection element in A-
pillars was investigated for its suitability in the crash protection [310]. The Al-foam
reinforcement for the A-pillar of a Ford passenger car provides an improvement of
30% in crash energy absorption achieved with only a 3% increase in the weight [311].
In addition to the structural material and shock absorbing applications, metallic
foams have application in silencers, mufflers, diesel, particulate filters, support for the
selective catalysis reduction, etc [312]. Several companies like Exxentis (Wettingen,
Switzerland) and Mott Corporation (Farmington, CT, USA) manufacture filters for
the gas filtration and liquid filtration [313], several other manufacturing companies
have products in their line for catalyst carrier, filtration fluid control or anti-sloshing
purposes [314]. The nonporous gold foams have important applications as cata-
lysts [315]. Pictures of the components used in filtration and different functional
components are shown in Fig. 9.9.
Due to the high stability at high temperatures good thermal conductivity and
excellent surface area, metallic foams have important applications in heat exchangers
9 Synthesis Strategies and Applications of Metallic Foams … 353

Fig. 9.8 Crash absorber box of the electric car prototype in the frame of the European Project
Evolution made with rectangular Al-profiles filled with Al-foam; and CAD design of the body
in white. (product of Cidaut, Valladolid, Spain, Pinningfarina, Cambiano, Italy and Pohltec metal
foam, Collogne, Germany). Reprinted with permission from Ref. [309]. Copyright 2016 MDPI AG

Fig. 9.9 Pictures a large number of filters from Alantum, Korea, Reprinted with permission from
reference [309]. Copyright 2016 MDPI AG

used as passive cooling devices [316, 317]. The pictures of different heat exchangers
from M-pore, Germany [318], are shown in Fig. 9.10.
For application even in larger scale metallic foams have application as structural
materials in several constructions, as an example the foam from Alusion used the
354 A. K. Satpati

Fig. 9.10 Diverse types of heat exchangers based on Al- and Cu-foams manufactured by M. pore
and Mayser GmbH, Reprinted with permission from Reference [309]. Copyright 2016 MDPI AG

entrance of a souterrain and a bell tower monument, the pictures of such structures
are shown in Fig. 9.11.

Fig. 9.11 Translucent entrance of a souterrain and bell tower monument made of Alusion foam,
Reprinted with permission from Reference [309]. Copyright 2016 MDPI AG
9 Synthesis Strategies and Applications of Metallic Foams … 355

9.3.6 Application of Foams in Regenerative Medicines

The regenerative tissue engineering is an important application where porous nano

foams works in the regeneration and controlling the growth of human tissues having
large defects. The porous scaffold required to be placed at the defect sites to provide
mechanical stability and promote the cell growth. The porous foams are used as the
scaffolding structural materials, and the pores are utilised for (a) allowing and control-
ling cell attachment, migration and infiltration; (b) they provide improved nutrient
and transport of metabolite to and from the cells respectively; (c) also facilitate
vascular infiltration; and (d) control the orientation of extracellular matrix molecules
produced and laid down by cells [319–321]. Electrospun generated collagen nano
porous materials are applied for the nerve regeneration [322]. The 3D nanofibril scaf-
folds fabricated through an improvised electrospinning technique has been reported
to regulate the proliferation and critical functions of rabbit corneal cells, and the
investigation has demonstrated the suitability of the technique in the treatment of
injuries of ocular tissues [323].
As a material of choice titanium is the most widely used materials for orthopaedic
implants, dental implants, and hip replacements. The biocompatibility of titanium is
one of the best, in spite of having very good stability some titanium implants fails. For
the improvement in the life time of titanium based implants, the surfaces of such mate-
rials are modified with porous nano structures. Self-assembling peptide has been used
as potential templates for nanofabrication in bio regeneration, direct mineralisation of
hydroxyapatite [324, 325]. The self-assembled nanofibers of lipopeptide have been
used as bio-regenerative materials, coated over the Ti-6Al-4 V foam bone implant. It
was reported that the nanofibers occupied the nano pores of the metallic foam with
the bioactive matrices encapsulating the cells for their growth. The nanofibers in the
implants facilitate the mineralization of hydroxyapatite, which facilitates the bone
formation without deformities [326–328].
Dental caries is one of the most widespread infectious diseases in the world.
Currently, it has been handled through replacement of decayed part along with
implantations of some materials [329]. With the advancement of the tissue engi-
neering, it has been targeted to generate the hole tooth using tissue growth through
nano structured scaffolding and incorporation of stem cells.
With the advancement of the stem cell research and the tissue engineering the
cardiac tissue regeneration through the self-assembled systems has shown promising
results in the engineered growth of cardiac tissue. As reported by Lee et al. [330] the
self-assembled nano structure of peptides works as scaffold for the embryonic stem
cells for mice. It was reported that the self-assembly of peptide scaffold provides
supports and promote vascularization. The foams provide the large surface area and
porosity for the cells to attach, migrate and communicate while growing, generate
a suitable platform for the cell engineering, collagen based nano structured scaffold
has been investigated for the engineered cardiac tissue growth [331–333].
356 A. K. Satpati

9.4 Graphene Foam

This book chapter has focused mainly on the metallic foam; however, a small intro-
duction about the graphene foam has been mentioned at this part of the book chapter
due to the impulse it has been created in the research fields. In non-metallic foams,
the polyurethane (PU) foam has significant commercial applications. It is worth
mentioning that the PU foam is being synthesised from the natural sources showing
superior properties mechanical properties [334–337].
The 2-dimentional graphene (2D graphene) was synthesised in 2004 and has
opened up new research domain worldwide. The fascinating properties of graphene
like the large surface area, high thermal conductivity and also the electrical conduc-
tivity has led to its several applications in medical, engineering, energy, sensing
and environmental related fields [338]. The 2D graphene sheet however undergoes
severe deformation in properties due to the agglomeration arises due to the strong
π-π interaction between the graphene sheets. The generation of macroscopic object
from the 2D graphene sheets would reduce the issues related to the agglomeration,
additionally it would provide mechanical strength and enhance the applicability due
to the 3D network structure in 3 dimensional graphene (3D graphene).
The 3D graphene assemblies are synthesised through the solution based gelation
of graphene oxide sheets, after the gelation process assemblies are subjected to the
chemical reduction process or pyrolysis [339–341]. In addition to the solution based
synthesis, chemical vapour deposition or powder metallurgy routes have been utilised
for the synthesis of 3D graphene, which might be used for the large scale applications
also [342–344]. There are several applications of 3D graphene based foams which
includes Electronic devices [345–347], energy storage devices [348, 349], Electro-
catalytic applications [350–352] to sensors [353–356], and thermal managements
[357–359].
For its application in electrochemical sensor, the 3D porous structure has several
attractive features well suited in the electrochemical sensor applications. A large
electroactive surface area makes the access of the analyses through several channels.
The good mechanical strength and the exceptionally good conductivity leads to its
application as free standing electrode without the requirements of any support. Addi-
tionally, the possibility of the formation of composites with several other metallic
and non-metallic substances will generate highly sensitive and selective analytical
methods based on 3D graphene. 3D graphene can undergo several types of function-
alisation, it can be attached with biologically active molecule like enzymes, and it has
wide electrochemical potential window, capable in monitoring the electrochemical
oxidation and reduction of several analytes [356, 360]. In our recent investigation the
3D graphene composites of noble metals like Pt, Pd, Au and Ag, which were named
as Pt/3D-G, Pd/3D-G, Au/3D-G, Ag/3D-G respectively, were utilised in the investi-
gation of HER activity [352]. The catalytic current of the respective noble metals Pt,
Pd, Au and Ag are increased significantly while their presence as composite with 3D
graphene. The schematic representation of the synthesis of the catalytic system and
the comparison of the catalytic activity are shown in Fig. 9.12. It can be seen that
9 Synthesis Strategies and Applications of Metallic Foams … 357

1. Freeze in dry ice

1. Noble metal salts 2. Dialysis
3. Freeze drying
2. Ascorbic acid

Graphene oxide
dispersion
Noble metal/3D-graphene
nanocomposite

Fig. 9.12 The schematic representation of the synthesis process and the evaluation of the catalytic
activity of the 3D-G and Pt, Pd, Au, Ag composites (Pt/3D-G, Pd/3D-G, Au/3D-G, Ag/3D-G,
respectively). Reprinted with permission from Ref. [352], Copyright 2019 Elsevier

the HER catalytic response from the Pt/3D-G is higher than the commercially avail-
able Pt/C catalytic system. For the overall comparison of the catalytic responses, the
plots with and without the iR compensations are shown. High conducting and porous
network of graphene sponge provides the excellent charge transfer and diffusion of
ions through highly porous materials, which improve the HER catalytic activity in
addition to proving support to the noble metal nano particles in improving the stability
of the catalysts.
Graphene foam composites are utilised in the next generation super capacitors,
and the graphene at the gelation state which are known as the graphene hydrogels
are utilised for the enhancement of the super-capacitive property of due to excellent
interfacial surface area [361–365]. Graphene hydrogels have improved intercon-
nections among various graphene sheets. The effective acquaintances of graphene
hydrogels with the metal oxide redox active materials further improves the charge
storage property of such composite materials. In bio-regeneration the 3D graphene
foams are serving as promising candidate by mimicking in vivo environments. The
nano structural scaffolds of 3D graphene provides easy access for the efficient cell
attachment, proliferation, and differentiation during the regenerative medical appli-
cations. The efficient mass and the charge transport through the porous graphene 3
dimensional structures provides the physical and chemical stimulations to cells for
the required growth [366].
358 A. K. Satpati

9.5 Summary

In this book chapter, the brief history of the porous metal nano structure has been
discussion citing some of the initial journal publications and books. The porous
materials used to be practiced in the name powder metallurgy materials, and a brief
introduction about that has been included in the chapter. The book chapter then
primarily discussed about the metallic foams and hollow nano structures, which are
most sought-after materials, finding several important applications. The strategy for
the conventional synthesis along with some of the templated synthesis protocols are
discussed. The hollow nano structured materials are a special type of porous struc-
tured materials finding important applications in sensors and in catalysis. The process
of the transport of charges through the inner and out spheres make the hollow nano
structured materials special. The discussion about the synthesis procedure through
self-templating route and electrospinning is some of the non-conventional synthesis
process should be explored further, would find several important applications of
the materials synthesised using such routes. The porous or layered transition metal
chalcogenides are important class of materials being discussed as an alternate to the
graphene, and the materials have enormous potential in catalysis. Applications of
porous nano structured materials starting from the reachargeable battery, superca-
pacitor, fuel cell technology are presented. The applications in sensors and biosensors
are discussed in the line of non-enzymatic and enzymatic routes utilising metallic
foams. In biomedical field, foams are utilised in tissue engineering as regenera-
tive medicines, and the field is expected grow further to support several modern
medical treatment protocols. In addition to the meso or nano porous structures, the
forms with macrospores have important large scale industrial applications, and some
related examples are presented in the book chapter. Though present book chapter has
focused on the metallic foams, a brief account of the graphene foams is presented
towards the end of the chapter. The research potential in graphene foam is large
enough to sought interest in another chapter mentioning the synthesis strategy and
application of the composites of graphene foam. Overall, the author has discussed a
brief account of the porous structured materials in the chapter, though several related
researches are missed out. Consideration has been given to the topic which are futur-
istic and strategically advance in the synthesis protocols and applications. The author
is hopeful that the content of the book chapter finds significant interest among the
fellow researches.

Acknowledgements The author thanks Prof. A. K. Tyagi, Director, Chemistry Group, Bhabha
Atomic Research Centre for his encouragement, support, and guidance in writing the book chapter.
The author also thanks Shri. Abhishek Sharma for his help in assembling the references.
9 Synthesis Strategies and Applications of Metallic Foams … 359

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Chapter 10
Exfoliation Routes to the Production
of Nanoflakes of Graphene Analogous 2D
Materials and Their Applications

N. Padma

Abstract In the past decade, with the discovery of graphene, two-dimensional

(2D) graphene analogous materials like nanolayers of transition metal dichalco-
genides (TMDCs), monoelemental Xenes (like phosphorene, antimonene etc.) and
MXenes (like Ti2 C, Mo2 C etc.) have attracted much attention owing to their high
mobility of charge carriers, accompanied by other useful and unique electronic,
optical, and mechanical properties. The thickness-dependent electronic properties of
these materials demand isolation of the nanolayers from their corresponding bulk
layered solids. An attempt is made in this chapter to discuss the exfoliation of some
of these nanolayers and their thickness identification, with a brief description of
their structure and band energy diagrams. Layer isolation is generally carried out by
mechanical exfoliation or by liquid phase exfoliation (LPE). While the former does
not result in scalable production that is required for various device applications, the
latter offers improvement in this aspect The yield and the efficiency of dispersion of
the nanoflakes in the LPE method depend on the choice of good solvents, i.e., the
solvents having matching surface energy with that of the material to be exfoliated.
The mechanism governing such surface energy-dependent exfoliation is discussed.
Since most of these good solvents exhibit high boiling points hindering the device
performance, the discussion is also made on the exfoliation by cosolvent method
where a mixture of two low boiling point so-called bad solvents is used. Alkali
metal ion and surfactant intercalation methods that are employed to improve the
concentration of the dispersion are also mentioned here. Identification of the layer
thickness and verification of the thickness-dependent electronic properties by some
of the techniques like optical microscope, atomic force microscope (AFM), Raman
and photoluminescence (PL) spectroscopy etc. are highlighted. The potential appli-
cations of these graphene analogous layered materials in the areas of nanoelectronics,
photovoltaic devices, supercapacitors, etc. are briefed.

Keywords 2D materials · Mechanical exfoliation · Liquid exfoliation · Layer

thickness · Thickness identification

N. Padma (B)
Technical Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 377
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_10
378 N. Padma

Abbreviations

D Dimensions
L Layer
LPE Liquid Phase Exfoliation
TMDCs Transition metal dichalcogenides
CMOS Complementary metal oxide semiconductor
MOSFET Metal oxide semiconductor field-effect transistor
GO Graphene oxide
RGO Reduced graphene oxide
BP Black phosphorous
HSP Hansen’s solubility parameters
LED Light emitting diode
FET Field-effect transistors
NMP N-methyl pyrrolidone
DMF Dimethyl formamide
IPA Isopropyl alcohol
DMSO Dimethyl sulfoxide
AFM Atomic force microscope
PL Photoluminescence
ITO Indium tin oxide
FTO Fluorine doped Tin oxide
HTL Hole transporting layer
P3HT Poly 3-hexyl thiophene
PCBM Phenyl-C61-butyric acid methylester
PDMS Poly dimethylsiloxane
EDLC Electric double layer capacitance
VBM Valence band maximum
CBM Conduction band minimum
IL Ionic liquid
SC Supercritical
SCF Supercritical fluid
PANI Polyaniline

10.1 Introduction

Ever-increasing societal demands for the high performing appliances related to low
power electronic devices, sensors, and health-related equipment, energy sectors,
etc., which require faster transport of data and processing capabilities, have been
constantly moving the technology world towards miniaturisation of the devices.
This motive to scale down the devices has accelerated the global development in
nanotechnology in the last three decades. Nanotechnology is basically a field in
10 Exfoliation Routes to the Production of Nanoflakes … 379

materials science dealing with nanomaterials having at least one dimension in the
nanometers scale, offering advantage of providing a large surface to volume ratio.
When two dimensions are limited in size, one-dimensional nanowires are formed
whereas restriction in all the three dimensions results in 0D quantum dots. When
dimension is restricted to only one side, it results in two-dimensional materials.
The continuous scaling down process using conventional silicon-based electronic
devices has reached a limit due to various reasons such as short channel effects
caused by degradation in electrostatic control, processing and economic limitations,
etc. [1]. Apart from miniaturisation of the devices, wearable equipment such as roll-
up displays, bendable mobile phones, e-skin applications, etc. have begun to take
an important place in our daily life. These applications require stable and reliable
performance after many cycles of bending and stretching. This demands the employ-
ment of materials exhibiting high mechanical flexibility. Therefore, developing the
next-generation electronic and optoelectronic devices strongly demand new mate-
rials with different dimensionality, functionality, mechanical strength and flexibility,
especially high performing semiconductors exhibiting excellent transport property
and good sensitivity to incident photons.
Though layered materials have been of scientific interest for the past 150 years,
only for the past one decade, their potential for advanced technological applications
has been recognised, after the discovery of graphene in 2004 by Novoselov and Geim
and after the awarding of Nobel prize to them in 2010 [2]. Even though the word
graphene was coined by Boehm in 1962, Geim’s group was able to practically isolate
a monolayer of graphene from the van der Waals solid only in 2004 [3]. Graphene
is basically a two-dimensional (2D) material with carbon atoms in a single sheet,
possessing unique properties such as high optical transmittance of about 97.7%,
a high charge carrier mobility of around 200,000 cm2 /Vs, high thermal conduc-
tivity and excellent mechanical flexibility with Young’s modulus of about 0.5–1 TPa
[4]. In a layered crystal, the electronic wavefunction exceeds in three dimensions
while in the 2D layers, there is a strong quantum confinement of electrons with
their wave functions constrained to adopt a two-dimensional form. This imparts
the 2D materials with new electronic band structures and with unique and fasci-
nating physical/electrical/electronic properties [5–7]. The above-mentioned inter-
esting properties of graphene have been usefully exploited for technological devel-
opment in next-generation devices in the areas of electronics, optoelectronics, energy
storage applications, etc. The disadvantage of graphene lies in the fact that it lacks
intrinsic bandgap making it unsuitable for certain logic applications like transistors
requiring high ON/OFF ratio. Band gap engineering, like functionalisation, doping,
introducing defects etc., has been adapted to open a band gap in graphene without
considerable modification of the pristine sheet. Unfortunately, during such processes,
the conductivity of graphene reduces drastically [8–12].
The success and the exotic performance observed in this material have fuelled
increasing interest and intense effort to search for alternative 2D materials having
more versatility, tunability, flexibility and functionality. 2D materials are defined to be
those one atom thick sheets isolated from bulk as free-standing layers and do not need
a substrate to exist. Often, layers with up to 10 atom thick sheets are also considered as
380 N. Padma

2D sheets [13]. Classical physics predictions hinted that lattice thermal fluctuations
do not allow 2D materials to be thermodynamically stable at finite temperatures [14].
Interestingly, a closer examination and finer studies of graphene revealed the presence
of ripples, which were found to distorting the 2D lattice. This was considered to be
making graphene sheets 3D like, thereby resolving the controversy over 2D materials.
2D materials basically possess neutral atoms covalently or ionically bonded with
their neighbours in a plane/layer while the layers are held together by van der Waals
coupling along the third axis. The weak van der Waals energies (~40–70 meV) allow
the facile exfoliation of these layers from their parent bulk material [7, 15]. This
search towards new materials has forced the research community to turn towards more
exotic layered materials like silicene, germanene, hexagonal boron nitrides (hBN)
and transition metal dichalogenides (TMDCs) etc. Some, like graphene, have truly
extraordinary properties like tensile strength 200 times greater than steel combined
with high flexibility, astonishingly high conductivity, tremendous energy storage
capacity etc. These planar materials exhibit different electronic structures and hence
varying band gaps depending on their thickness and stacking order [7, 12, 15, 16]. In
many of the TMDCs, there is a transition from indirect band gap in the bulk to direct
band gap in the monolayer. Such thickness and stacking order-dependent band gaps
and photoluminescence make these materials usable in the optoelectronic devices.
Larger interlayer spacing, high specific capacity and power density make them highly
suitable for flexible energy storage applications [16].
Layered materials cover a wide range of materials including clays, layered
oxides, halides, carbides, nitrides, hydroxides, phosphates, phosphonates, etc. apart
from the above-mentioned TMDCs and mono-elemental materials. Though most
of these materials are binary layered compounds, ternary compounds can also be
possible (CuSbS2 ) candidates [7, 14, 17]. Layered materials can be further classi-
fied depending on the nature of interaction between the layers. This interaction is
governed by hydrogen bonds, interstitial cations or van der Waals forces. This chapter
will be dealing with graphene and other van der Waals-based graphene analogous
inorganic layered materials, their nanoflakes production, characterisation and some
of their applications such as field-effect transistors (FETs), photovoltaic and energy
storage devices, etc.

10.2 Classes, Structure of 2D Materials and Their Band

Structures

In this section, a brief overview of the structure of some of the commonly used 2D
materials will be shown. It is well known that the energy band structure is an important
factor through which knowledge about the properties of a solid-state material can
be acquired. The electronic band structures are mostly represented along the high
symmetry points (-M–K-) in the Brillouin zone [18]. Though this chapter will
10 Exfoliation Routes to the Production of Nanoflakes … 381

not deal with theoretical band structure calculations, a brief mention of the same for
some of these common graphene analogous materials will be made.

10.2.1 Graphene

Graphene, the father of 2D materials, is an atomically thin single-layer sheet of

sp2 hybridised carbon atoms arranged in a honeycomb lattice with adjacent π –π
stacked layers having a spacing of 0.34 nm and held together by weak van der
Waals force (Fig. 10.1). The corresponding Brillouin zone and the band structure are
shown in Fig. 10.1c, d, respectively [8]. The four valence electrons of each of the
carbon atom are exactly enough to fill all of the bonding electronic orbitals [11, 17].
The homogenous electron distribution allows graphene to be chemically very stable.
Graphene exhibits a semi-metallic property with zero band gap, but with density of
states zero at its Fermi level. Electronic bands cross the Fermi level at the six corners
of the two-dimensional hexagonal Brillouin zone, making the dispersion relation (the
change of electron energy of a band within the Brillouin zone) linear or conical at
these points. This causes the electrons or holes to behave like relativistic particles
with zero effective mass making this material highly conductive. The electrons and
holes are called the Dirac Fermions and the six corners of the Brillouin zone as the
Dirac points [13, 14].

10.2.2 Transition Metal Dichalcogenides (TMDCs)

Layered metal oxides, double hydroxides, layered silicates or clays and mica are the
well-known examples of layered materials [7]. Transition metal trichalocgenides like
NbX3 , TiX3 , TaX3 (X = S, Se or Te), transition metal dihalides like MoCl2 , metal
halides like CrCl3 , PbCl4 , transition metal oxides such as TiO2 , Nb3 O8 , V2 O5 , MoO3,
MnO3 , WO3 and hexagonal boron nitride (h-BN) etc. are the different families of
2D materials where metal oxides are considered to be falling into the category of
2D family only modestly. Group III-VI materials like InSe, GaS etc. and group V-VI
chalcogenides such as Bi2 Te3 and Sb2 Se3 are tending to become prominent members
in the layered materials family.
Transition metal dichalocogenides (TMDCs) of the form MX2 , where M is a
transition metal element from group 4 to group 10 (M = Mo, W, Re, Ti, Ta etc.),
and X represents a chalcogen element (S, Se or Te) are the most focussed class of
layered materials. TMDCs with M=group 4–7 are mostly layered structures while
some with group 8–10 M atoms are found in non-layered structure [17, 19]. The
metal atoms provide four electrons to fill the bonding states of TMDCs such that the
M and X atoms are in the oxidations states of + 4 and −2, respectively [19]. The
termination of the surface layers with the lone pair electrons of the chalcogen atoms
and the absence of the dangling bonds ensure the stability of these layers to reactions
382 N. Padma

Fig. 10.1 a graphene top view, b multilayer graphene or graphite (Guo, Y.; Wei, Y.; Li, H. and
Zhai, T. Layer Structured Materials for Advanced Energy Storage and Conversion. Small. 2017.
1,701,649(1–22). Copyright Wiley–VCH Verlag GmBH & Co. KGaA. Reproduced with permis-
sion), c typical Brillouin zone of graphene and d band structure of graphene, solid red lines are σ
bond and dotted blue lines are π bonds (d—“Reprinted (figure) with permission from (Boukhvalov
D. W.; Katsnelson M. I.; Lichtenstein A. I.; Phys. Rev. B.,77, 035,427, 2008). Copyright (2018)
American Physical Society”)

against species in the environment. TMDCs occur as 40 different types depending

on the combination of chalcogen (S, Se or Te) and transition metal among which
MoS2 is the most common and well-studied material [7, 17]. The structures of some
of these TMDCs are shown in Fig. 10.2.
The metal atoms in the layered TMDCs are mainly sandwiched between two
layers of chalcogen atoms through covalent bonding, forming X-M-X units with the
tri-layer like structure. The combined trilayer is considered to be a monolayer in
TMDCs with adjacent such layers held by van der Waals force [12, 19]. The inherent
weakness of the van der Waals forces in these materials can cause the mutual sliding
of the adjacent layers and introduce stacking faults, thereby resulting in different
stacking sequences. Therefore, the MX2 solids crystallise in different polymorphs
depending on the varying stacking orders and the metal coordination, with the latter
being either trigonal prismatic or octahedral. Varying stacking sequences modify the
crystal symmetry, which, in turn, alters the coulomb interaction between the layers
10 Exfoliation Routes to the Production of Nanoflakes … 383

Fig. 10.2 Structure of TMDCs—a 2H and 1 T structure of MX2 (M = Mo, W, and X = S, Se) in
top and side views and b side view of WTe2

leading to different interlayer distances [20]. The different types of stacking of a

bilayer of MoS2 are shown in Fig. 10.3a. Bilayer, which is the first multilayer with
van der Waals interaction, can be considered to exist in five possible high-symmetry
stacking order along the z axis, almost exhausting all conceivable combinations,
as explained here: (1) AA—eclipsed stacking with atoms of the same type being
superimposed, i.e., M over M and X over X of the two layers, (b) AA’—eclipsed
with one atom type above the other (M over X), (c) A’B–M atoms superimposed
and the X atoms in the top layer over the hexagon centres in the bottom layer, (d)
AB’—X atoms are superimposed and the M atoms in the top layer over the hexagon
centres of the bottom layer, (e) AB—X atoms in the top layer over the M atoms
in the bottom layer and M atoms in the top layer over the hexagon centres of the
bottom layer [20–25]. Interestingly, one stacking can be changed to another by simply
sliding the layers horizontally and/or by rotation around the vertical axis. Varying the
stacking sequence also forms an additional pathway to tune the optical and electronic
properties where the band gap can be easily tuned by varying the twist angle [26].
For example, the band gap of a bilayer MoS2 varies from 1.49 to 1.62 eV for twist
angles of 0 and 30º between the two layers. This change is attributed to the effect of
interlayer coupling, which varies with the angle between the two layers [24, 26].
The TMDC layers exist in different electronic structures such as the 1T, 2H or
3R phases, where the numbers indicate the number of X-M-X units in the unit cell
and T, H and R represent the trigonal, hexagonal and rhombohedral configurations,
respectively (Fig. 10.3b) [12, 17–19]. The 2H phase has hexagonal symmetry with
two layers per repeat unit with trigonal prismatic metal coordination, the 3R phase
has rhombohedral symmetry with three layers per repeat unit and trigonal prismatic
coordination, the 1T phase has tetragonal symmetry with one layer per repeat unit
and octahedral coordination [12]. Natural or synthetic MX2 crystals generally exist in
two different polytypisms, namely, the 2H or 3R phase, both with trigonal prismatic
384 N. Padma

Fig. 10.3 a Different stacking of MoS2 (Reprinted (adapted) with permission from (J. Phys.
Chem. C, 2012, 116, 21,556). Copyright (2019) American Chemical Society”) and b different
polymorphism-2H, 1T and 3R structures
10 Exfoliation Routes to the Production of Nanoflakes … 385

coordination [19, 20]. In both phases, the M atom in one layer is aligned above the
X atom in the layer beneath, but with a different lateral registry. The X atoms are
fully eclipsed in the 2H phase while they are staggered in the 3R phase with one X
being eclipsed by the Mo atom above and the second one being located below the
hexagonal hollow site [20, 22]. In the case of hexagonal MoS2 , the 2H MoS2 and 1 T
MoS2 phases are mainly formed in multilayer and monolayers, respectively, where
the 2H MoS2 is a semiconductor and 1 T MoS2 is metallic. Among them, the most
stable configuration is the semiconducting 2H phase where the A layer is rotated by
60º with respect to A’ layer with inversion symmetry [5, 20, 27]. If one of S atoms is
shifted out of order, the structure is denoted as metallic 1 T-MoS2 [28, 29]. Similar
to MoS2 , MoSe2 , WS2 and WSe2 also have a hexagonal crystal structure, in which
Mo and W are found to be in trigonal prismatic coordination with sulphur atoms,
and hence similar stacking order [18, 30].
Though most of the TMDCs show such similarities in their structures, they simul-
taneously exhibit minor variations also. For example, while most of the TMDCs have
hexagonal symmetry with trigonal prismatic coordination, MoTe2 and WTe2 have
the distorted octahedral coordination [18, 19, 31, 32]. Depending on the coordina-
tion and oxidation state of the metal atoms or doping of the lattice, TMDCs can be
metallic, semiconducting or semi-metallic and even superconductors [7, 12, 17, 19].
The type of coordination and the phase preferred by the TMDCs depend on the d
electron count of the transition metal [19]. Group 4TMDCs with d0 transition metal
centres adopt octahedral structure. Group 5 TMDCs with d1 electron count are seen
in octahedral and in trigonal prismatic structure. Group 6 TMDCs with d2 electrons
are found primarily in trigonal prismatic phase and group 7 TMDCs with d3 electrons
are in a distorted octahedral structure. All group X TMDCs with d6 transition metal
centres adopt in octahedral structure. This difference in the transition metal’s coordi-
nation environment and its d electron count is mainly responsible for the difference
in their electronic properties. The non-bonding d bands are located within the gap
between the bonding (σ) and antibonding (σ* ) bands of the M-X bonds. These d
bands are either degenerate or they are split depending on whether the transition
metals are octahedrally coordinated or with trigonal prismatic coordination, respec-
tively. Difference in the filling of these bands from group 4 to group 10 species is
observed reflecting in change in their electronic properties. When the orbitals are
partially filled, as found for 2H-NbSe2 , 1 T-ReS2 , they exhibit metallic conductivity.
When the orbitals are fully occupied, as for 2H-MoS2 , 1 T-HfS2 etc., they become
semiconductors. Though the electronic structure is majorly decided by the metal
atoms, the change in the same is also observed for the change in the chalcogen
atoms. Mainly, decrease in the band gap is observed for increasing atomic number
of the chalcogen atoms. For example, the band gap reduces gradually from 1.3 to
1.0 eV in the order 2H MoS2 > 2H-MoSe2 > 2H-MoTe2 . For change in chalcogen
atoms from S to Te, the electronegativity decreases and the orbital radii increase.
Due to these changes, the effect of ligand field of the chalcogen atoms on the metal
atom d states becomes more and more prominent. This leads to broadening of the d
bands and hence decreases in band gap. Difference in the semiconducting nature was
also observed for different chalcogen atoms, where MoS2 shows n-type behaviour,
386 N. Padma

MoSe2 is bipolar and MoTe2 exhibits p-type. Among the n-type MoS2 and WS2 ,
the carrier density is reported to be higher in MoS2 [33]. Similarly, the bond length
M–M, where M is the transition metal, is similar for MoS2 (3.16) and WS2 (3.15),
and it is slightly larger for WSe2 (3.28). Also, the interlayer gap is higher for WSe2
than that for WS2 due to the larger size of Se atoms [34]. Such variations imply that
many of these TMDCs are yet to be explored thoroughly.
While the band structure of most of the semiconducting TMDCs (MoS2 , WS2
etc.) is similar, as shown by first principles and tight binding approximations as well
as measured using many spectroscopic techniques, they differ from that of the zero
band gap graphene [18, 30, 32, 33]. A typical case of MoS2 is discussed here. The
occupation of the sub-lattices by Mo and S atoms at different planes, unlike that of
the C atoms in graphene, lifts the degeneracy in the electronic structure at K (K’)
point in the Brillouin zone while the existence of this degeneracy was responsible for
Dirac-cone like dispersion relation in graphene [15]. Band structure calculations of
MoS2 shown in Fig. 10.4 reveal the indirect band gap of bulk MoS2 where the bottom
of the conduction band lies at the midpoint along  – K symmetry lines and top of
the valence band is located at  point. Several groups have predicted and observed
a transition from the indirect-band gap to a direct band gap at the K point of the
Brillouin zone for thinning of the flake thickness from bulk to a monolayer, with the
conduction band bottom and the valence band top getting located at same point K
in the wave vector axis for monolayer. The first principle calculations carried out by
different groups on the electronic structure of bulk and the monolayer MoS2 shows
that the density of states around Fermi level is due to molybdenum d states [12, 18,
19, 26, 32]. The conduction band states at the K point were suggested to be composed
of strongly localised d orbitals of the Mo atoms. Since Mo atoms are located in the
middle of S-Mo-S structure, they experience minimum interlayer coupling. Hence
layer thinning makes K states remain unaffected. However, the states near the 
point are predicted to be due to the presence of strong hybridisation between the Mo
d orbitals and the antibonding pz orbitals of the chalcogen atoms. They are subjected
to strong interlayer coupling and hence become sensitive to layer thinning [5, 18, 26,
35]. The transition from indirect to direct band gap with layer thickness reduction
is said to be due to the quantum confinement and to the change in this hybridisation
happening at the  point [12, 15, 19]. Similar transition from indirect to direct band
gap is also shown in Fig. 10.4 for WS2 and MoSe2 [12, 18].
Among these TMDCs, ReS2 and ReSe2 have attracted special attention because
of their interesting electronic properties different from that of MoS2 . They stand
out from other TMDCs due to their distorted 1T crystal structure (Fig. 10.5) with
triclinic unit cell where Re atoms are displaced from the hexagonal lattice and form
diamond chains along the b axis [31, 36–42]. The distorted structure is explained as
follows: Compared with the 2H structure of classical TMDCs, an additional valence
electron in Re atom impacts energy balance by forming covalent bonding between
the neighbouring Re atoms. This leads to the formation of Re chains along the b-axis
of the crystal. The superlattice structure of Re chains thus formed tends to distort the
crystal from the more symmetric 1T phase, drastically reducing its symmetry. The
low crystal symmetry results in highly anisotropic optical and electrical transport
10 Exfoliation Routes to the Production of Nanoflakes … 387

Fig. 10.4 a Brillouin zone for hexagonal lattice of MoS2 , band structure calculations of b MoS2 and
c WS2 b and c—Reproduced with permission from Springer Nature [12], and d MoSe2 (Reproduced
with permission from Springer Nature [18])

properties, adding an additional degree of freedom for applications in sensor and

electronic devices. The distorted structure tends to weaken the interlayer coupling
preventing an ordered stacking of the layers and minimising the overlap of the wave-
functions. Therefore, unlike MoS2 , bulk ReS2 and ReSe2 electronically behave like a
decoupled monolayer due to weak interlayer interaction, maintaining the direct band
gap of around 1.5 eV from bulk to monolayer [36–38]. In pristine ReS2 , the valence
band maximum is determined by 5d orbitals of the Re atoms and 3p orbitals of the S
atoms. The conduction band minimum is composed of 5d orbitals of the Re atoms.
Like MoS2 , ReS2 is also an n-type semiconductor with its Fermi level about 0.07 eV
below the bottom of the conduction band.
Density functional theory calculations predict a interlayer coupling energy as low
as 18 meV per unit cell, which is about 8% of that observed for MoS2 [36, 37].
Due to this, though the band structure of most of the TMDCs is similar, it varies
clearly for ReS2 . A typical band structure calculation shown in Fig. 10.6a reveals the
decoupled nature of ReS2 . The figure shows a very small change in band gap when
thinned down from bulk to monolayer. But recently, some studies have contradicted
this conclusion and suggested the existence of significant interlayer coupling in ReS2
and also in ReSe2 [39, 40]. A very recent study by Gehlman et al. indicated the indirect
band gap nature of bulk ReS2 [39]. Interestingly, their GW-based calculations suggest
that transition to direct band gap occurs for bilayer ReS2 , while it becomes indirect
again for monolayer, making the former better for device applications than the latter.
The typical band structure calculations shown by them are given in Fig. 10.6b along
388 N. Padma

Fig. 10.5 a Top and side views of undistorted ReSe2 , b top and side views of distorted ReSe2
(“Reprinted (adapted) with permission from (Nano Lett, 2017, 17, 3202). Copyright (2018)
American Chemical Society”)

with the 3D k-space with positions of the selected directions in Fig. 10.6c. They have
also concluded that the indirect band gap is only very faintly observed, which could
be the reason why some studies found indications of both direct and indirect band
gap.

10.2.3 Monoelemental Graphene Analogous Materials

Another class of 2D materials, closely related to graphene, are the zero-band gap
semi-metallic mono-elemental 2D X-enes made of group IVA elements, i.e., silicene,
germanene, stanene etc. when X = Si, Ge, Sn, respectively. Their large interatomic
distances result in up and down buckling of the atoms about a honey-comb lattice.
Unlike carbon, group IVA silicon, germanium or stannum do not have allotropic
layered structures that can be exfoliated into monolayers [17]. Their freestanding
2D layers are not very stable, as their 3D cluster formation is more favoured. To
date, 2D nanosheets of silicene, germanene and stanene have been grown only on
certain metallic substrates while their freestanding form is yet to be realised [11,
17]. Several allotropes and compounds of group 3 (Boron) and 5A elements in
the Periodic Table (phosphorous, arsenic, antimony and bismuth) have also been
identified as potential members of graphene analogous materials where theoretical
predictions have shown them to exhibit 2D like characteristics. However, like silicene
and germanene, hexagonal boron (borophene) nanosheets are theoretically predicted
to be unstable in the freestanding form and can be stabilised only by the interaction
with the substrate.
10 Exfoliation Routes to the Production of Nanoflakes … 389

Fig. 10.6 a Calculated band structure showing direct band gap for bulk ReS2 (Reproduced with
permission from Springer Nature [36], b band structure showing indirect to direct band gap with layer
thickness and c) Brillouin zone representation for band structure shown in Fig. 10.6b (“Reprinted
(adapted) with permission from (Nano Lett. 2017, 17, 5187). Copyright (2018) American Chemical
Society”)

These elemental 2D materials possess simple composition and structure but offer a
huge treasure of electronic properties. Though they all share similar buckled honey-
comb like structure, they vary in their electronic structures and properties signifi-
cantly. Phosphorous has a stable allotrope in the layered fashion called black phos-
phorous (BP), which is thermodynamically more stable than the red and white phos-
phorous [17]. According to various reports, Phosphorene, a 2D analogue of black
phosphorous (BP), is the only elemental semiconducting 2D material with the theo-
retical and experimental investigations revealing the band gap to be direct for the bulk
as well as monolayer and ranging from 0.36 to around 1.8 eV [11, 43, 44]. The top
view of a typical monolayer phosphorene with thickness around 2.1 Å. is shown in
Fig. 10.7a while the side view of the multilayers structure is shown in Fig. 10.7b. The
single layer black phosphorous consists of two atomic planes with P atoms having
sp3 orbitals hybridisation and a lone pair of electrons. Due to the out of plane orbitals,
the overlap between the lone pair electrons in adjacent layers leads to interlayer van
390 N. Padma

der Waals interactions [44]. This results in two kinds of P–P bonds where the shorter
one connects the nearest atoms in the same plane and the longer one connects P atoms
located in the top and bottom of the layer, with anisotropic bond angles caused by
puckered structure. Each P atom has three equidistant (2.18 Å) nearest neighbours,
two in-plane and one out of plane at bond angles of 99° and 103°, respectively. This
arrangement gives rise to armchair (AC) and zig-zag (ZZ) configurations along the
x and y directions, leading to highly anisotropic mechanical, electrical, optical and
thermal properties within ab plane. For multilayers, the AB stacked layers of sp3
hybridised phosphorous are at an interlayer distance of 5.2–5.3 Å. This relatively
larger spacing, as compared with that of graphene, is due to its puckered structure
as well as the AB stacking in the unit cell [17, 44]. Such large spacing makes the
phosphorene layers held together by a weak van der Waal interaction (~20 meV
atom−1 ) and hence can be easily separated. Due to its p-type behaviour with large
hole mobility > 1000 cm2 /Vs, its tunable band gap with near/mid-infrared region
absorption and its orientation-dependent properties, phosphorene was considered
as the most suitable material for nanoelectronics, photonics, optoelectronics like
photovoltaic devices and LEDs, high-frequency electronics operating in multi GHz
frequency range, sensing and energy storage applications [11, 44].
A few groups have carried out band structure predictions of bulk and few layer
phosphorenes using the first-principle calculations, where at  point, the conduction
band and the valence band consist of a mixture of s and p orbitals (pz component)
[44, 45]. This is different from graphene whose bands are solely composed of pz
orbitals. Cai et al. have carried out systematic band structure calculations for bulk
BP as well as for layer thickness varying from 5 layers to 1 layer. The former along
with the corresponding Brillouin zone representation is shown in Fig. 10.8a and b,
respectively, and the latter is shown in Fig. 8c [45]. The variation of band gap is
plotted as a function of number of layers in Fig. 8d.
The disadvantage with phosphorene is that the mono or few layer thick phospho-
rene is highly reactive and hence degrades within a few hours in air. Very recently,

Fig. 10.7 a Top view of monolayer phosphorene and b side view of multilayer phosphorene
10 Exfoliation Routes to the Production of Nanoflakes … 391

Fig. 10.8 Electronic band structure calculations of black phosphorous a bulk, b corresponding
Brillouin zone, c for different layer thickness from monolayer (1L) to 5 layers (5L), d Variation of
band gap with layer thickness. Reproduced with permission from Springer Nature [45]

arsenene and antimonene are the two new members of group VA elements with indi-
rect band gaps, joining the 2D family. They were predicted to show a buckling struc-
ture different from that of phosphorene. With reducing thickness up to monolayer,
their band gap was expected to be opening up to 2.49 and 2.28 eV, respectively,
for As and Sb. In contrast to phosphorene, antimonene was recently predicted to
exhibit good stability in air [46, 47]. The top view of a monolayer antimonene and
the side view of the multilayer antimonene stacking are shown in Fig. 10.9. Theo-
retical calculations have shown that antimonene can transform from semi-metal in
the bulk form to a topological insulator when the number of layers is below 22 and

Fig. 10.9 a Top view and b side view of multilayers of antimonene

392 N. Padma

becomes semiconducting with an indirect band gap of 2.28 eV, exhibiting high hole
and electron mobilities, when thinned down to one atomic layer [48]. Though reports
on theoretical predictions are multiplying very fast, experimental studies on the same
are still scarce.
All 2D monoelemental materials are buckled/puckered except graphene enabling
the applied electric field perpendicular to the surface to produce a potential difference
on lattice sites above and below the plane. Therefore, the applied electric field can
act as a parameter to tune the electronic structure of these 2D materials [11]. The
interest in theoretically predicting 2D form of different materials was also recently
extended to group 6 elements (S, Se, Te) of the Periodic Table, named as selenene
for Se and tellurene for Te. The studies on these materials are in infancy and mostly
at theoretical stage.

10.2.4 MXenes

Apart from the above-mentioned layered materials, transition metal

carbides/carbonitrides/nitrides of the form of the MXenes (first reported by
Gogotsi’s group), where M is a transition metal (Ti, V, Cr, Nb etc.) and X is carbon
or nitrogen, are emerging to gain primary importance [4, 17, 49–53]. They are of
the form Mn+1 Xn derived from Mn+1 AXn precursors where A refers to mostly group
IIIA or IVA elements (Al, Si, Sn, In etc.), and n = 1, 2 or 3 (Fig. 10.10) MAX
precursors basically possess hexagonally close-packed strongly bonded MX layers
held together by weakly bonded A layers. MAX phase cannot be exfoliated into
layers due to chemical bonding by A layer. But upon etching with hydrofluoric acid
(HF), A layers are etched away as they are highly reactive, leaving behind the MXene
layers. Structures of some of the MXenes are shown in Fig. 10.10 b–d. During
this synthesis, functional groups like -OH, -F or -O get attached to MXene layers
(Fig. 10.10e) which would be influencing their physical and chemical properties.
Due to their excellent structural stability, flexibility and high electrical conductivity,
they are useful for many applications like supercapacitors, Lithium-ion batteries,
oxygen evolution reaction, electromagnetic interference shielding, transparent
conductive coatings, etc. MXenes nanosheets are reported to be highly useful for
applications in water purification with a water permeance of around 1000 Lm−2
h−1 bar−1 , much higher than that for most of the membranes studied under 90%
rejection rate [50].
10 Exfoliation Routes to the Production of Nanoflakes … 393

Fig. 10.10 a Schematic showing formation of MXene layers from MAX precursors, b–d structures
of some of the MXenes, e Structure of MXene with surface termination groups

10.3 Synthetic Routes to 2D Layers

The process of thinning down of the bulk materials to a few/multi layers is called
exfoliation. The main reason to exfoliate these layered solids into thinner sheets is
to increase the accessible surface area. For surface-active and catalytic materials as
well as for devices depending on the reactivity at the surface, like gas sensing, such
exfoliation assures an increase in efficiency. Additionally, the strong layer thickness-
dependent electronic properties emphasise the necessity for developing strategies to
produce reliable and high-quality ultrathin sheets of these 2D materials from their
bulk counterpart. The success of exfoliation is gauged by the layer thickness, lateral
dimensions, size dispersity, crystal quality, etc. The synthesis of 2D nanosheets is
mainly based on two major approaches, namely, top-down and bottom-up strategies.
The nanosheets are exfoliated from the 3D bulk by mechanical or chemical methods
in the former. In the latter case, they are prepared starting from the basic building
blocks which upon chemical reactions complete the formation of covalently linked
large area 2D sheets. Some of the commonly methods relevant to bottom-up approach
394 N. Padma

are chemical vapour deposition (CVD), pulsed laser deposition (PLD), sputtering
method, atomic layer deposition (ALD), physical vapour deposition (PVD), etc. In
this chapter, we will be reviewing the different exfoliation routes in the top-down
approach for the production of nanosheets of the layered materials.

10.3.1 Top-Down Approach

Over the decade, many methods have been attempted to exfoliate thin layers down
up to monolayer thickness, from bulk layered solids. Such exfoliation resulted in
high aspect ratio flakes with large surface area, enough to process them for device
applications and other surface-related activities.

10.3.1.1 Mechanical Exfoliation

Scotch Tape-Based Mechanical Exfoliation

Mechanical exfoliation of graphene from graphite using scotch tape, that was the
first one to be attempted, has allowed the production of flakes in which many novel
properties were discovered [2, 3, 54]. The success observed in graphene has allowed
this method to continue to be the primary route for producing ultra-thin flakes. Due to
the strong in-plane and weak out of plane bonding, layered materials can be sheared
parallel or expanded normal to the in-plane direction. This can overcome the van
der Waals forces and result in a process called exfoliation, producing nanometer or
even atomically thin sheets or nanosheets. Figure 10.11 illustrates the various steps
involved in the mechanical cleavage method using adhesive tape. In mechanical
exfoliation, the competition between the intersheet van der Waals forces in a layered
solid and that between the substrate and the outermost sheet plays a crucial role in
efficient thinning of the solids [54]. Typically, a well-cleaned SiO2 /Si substrate is
used for transferring the flakes. The adhesive tape is contacted with the bulk crystal
and then removed such that multi-layered flakes are transferred onto the tape. During
the few times repetitive process of contacting the flake loaded tape with fresh tape, the
flake thickness reduces with each contact. After considerable thinning of the flakes,
the adhesive tape is brought in contact with the substrate and peeled off, leaving the
high quality ultra-thin single-crystal flakes on the substrate, suitable for fundamental
studies. Many materials like MoS2 , ReS2 , WSe2 , TaS2 , TaSe2 , BP etc. have been
successfully exfoliated into thin sheets using this method and have been employed
for developing FETs, phototransistors etc. [35, 37, 56–61]. One main disadvantage
of this method is that it leaves contaminants from the adhesive tape. Some studies
have introduced an additional step where the substrates with flakes are dipped in
acetone for about 5 min, in order to remove the residues of the tape [61].
Some studies have reported the use of polydimethylsiloxane (PDMS) stamps to
transfer flake onto the substrate instead of the adhesive tape, in order to avoid the
10 Exfoliation Routes to the Production of Nanoflakes … 395

Fig. 10.11 Schematic of the steps involved in mechanical exfoliation

Fig. 10.12 Schematic of steps involved in gel mediated mechanical exfoliation

contaminants from the adhesive tape [62]. Another study has used a gel film as an
intermediate step in mechanical exfoliation [63]. Here, they have fixed a gel film
on a glass slide, carefully removing the air trapped between the two. They have
then brought the tape with exfoliated flake in contact with the gel film such that
the flakes are transferred onto the latter. The gel film with the flakes is now pressed
against the SiO2 /Si substrate such that the flakes are available on the SiO2 substrate.
They have claimed that with this method, they have obtained large area flakes, free
of contaminants from adhesives, better than that with the scotch tape. A schematic
depicting this procedure is shown in Fig. 10.12.

Metal-Assisted Mechanical Exfoliation

A useful modification in mechanical exfoliation is metal-assisted exfoliation, espe-

cially Au facilitated mechanical cleavage from the bulk, which has been attempted
by some groups [64, 65]. This method has reportedly brought about improvement,
producing large size flakes. A schematic showing the various steps mentioned above
is shown in Fig. 10.13.
Javey group has deposited gold film of thickness about 100–150 nm on bulk
MX2 crystals. Due to the strong bonding occurring between gold and the chalcogen
atom in the top-most layer, much stronger than the van der Waals forces existing
between the layers, this layer was selectively cleaved using a thermal tape, which
was later brought into contact with the SiO2 /Si substrate. The tape was then removed
by heating the substrate at about 130ºC and the residues further cleaned by exposing
396 N. Padma

Fig. 10.13 Schematic of various steps involved in Au-mediated mechanical exfoliation

the substrate to mild O2 plasma, taking care not to etch away the gold. The gold film
is later etched using KI/I2 wet etch, which does not affect the flakes underneath. After
further cleaning with acetone and isopropyl alcohol, large area flakes are obtained
for further processing for device applications. Another study has reported a similar
procedure using nickel and copper-assisted exfoliation in the place of gold film [64].
Ottaviano et al. have recently modelled the mechanical exfoliation by the scotch
tape peeling off process as random vertical exfoliation and lateral fragmentation
phenomena and demonstrated a relation between the number of iterations in the
scotch tape peeling and the layer thickness transferred on the substrates. They
have taken into account the layer–layer interaction (which is always the same) and
the layer–tape interaction (which is different from layer–layer interaction) in their
modelling. They report that the occurrence of monolayers becomes most probable
by the second peeling itself. They also mentioned that by increasing the number of
iterations, the lateral dimension decreases drastically [57].
One of the disadvantages of the mechanical exfoliation is that it suffers from
difficulties in reproducibility since the quality of flakes produced is subject to human
skills thereby resulting in random errors at every step [66]. It also does not allow
systematic control over the layer thickness and size. Most importantly, for prac-
tical applications of these materials to act as active materials for displays, solar
cells, energy storage and water splitting applications etc., large-scale production
of 2D nanosheets is required. The yield of 2D materials by mechanical exfolia-
tion is very low making it unsuitable for large-scale production and hence for the
above-mentioned applications [4, 12, 66].
10 Exfoliation Routes to the Production of Nanoflakes … 397

10.3.1.2 Liquid Phase Exfoliation (LPE)

Liquid phase exfoliation of layered materials, where the bulk layered solids are
exfoliated in liquids mostly under ultrasonication, is a highly promising route for
large-scale production of 2D nanosheets. LPE basically involves three steps—(1)
dispersion of the bulk material in a liquid medium, (2) exfoliation of the nanosheets by
the use of ultrasonic waves and (3) purification and isolation of the exfoliated sheets.
LPE method permits hybrids and composites by simple mixing of the dispersions of
the two materials [52, 67, 68]. Large area thin films can also be formed by coating the
resultant dispersions by spray coating, inkjet or screen printing, spin coating, doctor
blading, etc.

Ultrasonic Waves

To overcome the van der Waals forces or electrostatic interactions binding the layers
in 2D solids, a sufficiently large input energy is necessary, which is provided by ultra-
sound waves [7, 69–73]. Ultrasound is basically the sound wave transmitted through
any material (solid, liquid or gas) possessing elastic properties. As the acoustic wave-
lengths are much longer than the molecular dimensions, no direct interaction takes
place between the sound waves and the chemical species in the liquid. When ultra-
sound of frequency above 20 kHz is transmitted through a liquid, they produce
alternating high- and low-pressure cycles, depending on the frequency. During the
low-pressure cycle, high-intensity small vacuum bubbles are created, which oscillate
with the alternating pressure cycle. Such oscillating bubbles can accumulate ultra-
sonic energy, thereby growing to a certain size (typically tens of μm) by rectified
diffusion and coalescence. As they grow beyond a certain size, they collapse during
a high pressure cycle, subsequently releasing the concentrated energy stored in the
bubble within a very short time (with a heating and cooling rate of > 1010 Ks−1 ).
This process is called cavitation. A schematic of the process of bubble formation,
their growth and implosion are shown in Fig. 10.14.
This implosion creates a high temperature and high pressure of about 5000 K and
1000 bar locally along with a high-speed liquid jet. During implosion, the speed of the
bubbles’ wall exceeds that of the sound in the gaseous interior, thereby creating shock
waves with shear and normal force. These forces overcome the attractive interactions
taking place between the layers, thereby resulting in breaking of the bulk into fine
particles and to efficient delamination of the nanosheets. The defects produced either
in the edge or in the basal planes during prolonged exposure to ultrasound result in
providing surface polarity to the nanosheets, thereby improving the dispersibility
of the same in the liquids. The schematic showing the delamination of the layered
material into nanosheets due to the shear and compressive forces produced by the
shock waves is shown in Fig. 10.15.
Ultrasound sonication can be performed using a variety of designs, such as bath
sonicators, direct immersion ultrasonic horns and flow reactors. The delamination
398 N. Padma

Fig. 10.14 Schematic representation of transient acoustic cavitation

Fig. 10.15 Schematic showing the cavitation induced exfoliation of flakes

efficiency depends on the solvent density, pressure, sonication probe shape, ultra-
sound frequency, etc. Increasing the density and or the pressure of the solvent is said to
increase the cavitation threshold. Cavitation occurs under the frequency range of tens
of Hz to tens of MHz. Beyond this frequency range, intrinsic viscosity of the liquids
prevents the occurrence of cavitation. Under ultrasonic exfoliation, flakes of size
ranging from 50 nm to about 10 μm can be produced. Increasing the ultrasonic time
was found to enhance the yields of exfoliated sheets, though increasing time would
10 Exfoliation Routes to the Production of Nanoflakes … 399

cause more defects and reduce the lateral dimensions of the flakes. Coupling ultra-
sonication with magnetic stirring was observed to expedite exfoliation in graphene,
resulting in a yield of around 95% [4].

LPE Using Organic Solvents

There are various ways to carry out LPE involving oxidation, surface passiva-
tion by solvents and use of intercalation compounds. One of the methods applied
much earlier was to oxidise the layered crystals and then disperse them in suit-
able solvents. For example, graphene was exfoliated from graphite by ultrasonica-
tion using Brodie’s, Staudenmaier’s or Hummer’s method [7, 73]. Here, graphite
was treated with sulphuric acid and potassium permanganate resulting in addition
of hydroxyl and epoxy groups. This caused graphene sheets to turn hydrophilic
allowing easy intercalation of water, leading to well-exfoliated graphene oxide layers
and stabilised against reaggregation due to the negative surface charge, yielding a
concentration up to 1 mg/ml. But this procedure disrupts the electronic structure of
graphene where the graphene oxide (GO) produced exhibited loss of conductivity.
The functional groups were then removed by reducing the GO to produce the reduced
graphene oxide (RGO). The disadvantage of this method is that a large number of
holes and sp3 defects are produced during the oxidation and the removal of functional
groups. Additionally, interfering heteroatomic species like S and metal-containing
impurities like K, Mn etc. can get covalently attached to the nanosheets altering their
properties [4, 68].
Ultrasonic-based exfoliation can also be carried out by using appropriate solvents
where the bulk material is dispersed in a suitable solvent. The basic requirements
for a solvent to be suitable are that (1) it should efficiently be able to delaminate the
flakes from the bulk to the highest concentration possible and (2) it should prevent
reaggregation of the exfoliated flakes and stabilise the same for the longest duration
possible. Re-aggregation of the exfoliated sheets is prevented generally by solvation
where a good solvent prevents this re-aggregation while a bad solvent allows the
same, as shown in Fig. 10.16 [7, 12, 74].
It is a common fact that the interfacial tension between a solid and a liquid plays
a crucial role in the interaction between the two. An ideal solvent will minimise the
potential energy between the two adjacent layers in a solid to overcome the van der
Waals forces between them and offer a balancing solid-nanosheet attractive force to
stabilise the dispersion of the nanosheets in the liquid [67, 68, 74–76]. The energy
required to exfoliate the layers depends on the surface energy, which is the energy per
unit area required to overcome the van der Waals forces to peel off two layers apart.
Coleman’s group demonstrated exfoliation of graphite into graphene with concentra-
tions up to 0.01 mg/ml using the solvent N-methyl pyrrolidone (NMP) for dispersing
graphite layers. They took the cue from the fact that carbon nanotubes could be effi-
ciently exfoliated in solvent like NMP, as demonstrated in an earlier study, brought
about by the excellent interaction between the solvent and the nanotubes. Though they
could also obtain success using some other solvents like N–N-dimethylacetamide
400 N. Padma

Fig. 10.16 Schematic showing liquid phase exfoliation under ultrasonication, with good and bad
solvents

(DMA), γ-butyrolactone (GBL), 1,3-dimethyl-2-imidazolidinone (DMEU) etc., they

concluded the best result to be with NMP. They observed that the surface energy of
NMP that is around 70 mJ/m2 was matching well with that of graphene (68 mJ/m2 ).
Such an observation led to the investigation of the mechanism responsible for higher
efficiency of certain solvents. They suggested that the exfoliation is maximum when
the net energetic cost is minimum. The detailed explanation offered by them for
exfoliation of graphene is as follows [4, 74–76]:
It can be stated that the mechanism governing the exfoliation of 2D materials in
liquid is based on solution thermodynamics. Assuming the entire dispersion to be a
solution, the free energy of mixing (Gmix ) is given by [76]

Gmix = Hmix − TSmix (10.1)

where Hmix is the enthalpy of mixing and Smix is the entropy of mixing. Though
large Smix will result in negative Gmix , favouring thorough mixing, the large size
of 2D nanosheets will lead to smaller Smix . Alternately, by minimising the enthalpy
of mixing, better dispersions can be obtained. The energy balance, expressed as the
enthalpy of mixing (per unit volume), can be given by the following expression
[4, 73, 75]:

√ G √ sol 2
Hmix /Vmix = 2/Tflake ( E sur − E sur ) ϕ (10.2)
10 Exfoliation Routes to the Production of Nanoflakes … 401

Fig. 10.17 Concentration of

exfoliated graphene obtained
for various solvents with
a different surface tension
and b Hildebrand solubility
parameter (“Reprinted
(adapted) with permission
from Langmuir, 2010, 26(5),
3208). Copyright (2018)
American Chemical
Society”)

G sol
where E sur and E sur are the surface energy or surface tension of graphene and
the solvent respectively, Tflake is the thickness of the graphene flake and ϕ is the
graphene volume fraction. The surface energy is correlated to surface tension, γ, by
the expression γ = E sursol sol
-T Ssur sol
where Ssur is the surface entropy of the solvent having
a universal value of around 0.1mJK m−2 . Coleman group exfoliated graphene in
−1

a variety of solvents and observed that maximum yield was obtained for those with
surface tension around 40–50 mJ/m2 , equivalent to surface energy of about 70 mJ/m2
(Fig. 10.17a). This shows that the enthalpy of mixing is minimum when the surface
energies of the solvent and the material are very close. Therefore, it was suggested
that the lower the difference between the surface energy of the solvent and that of
the layered solid, the better was the efficiency and yield of the exfoliation. But it was
also pointed out that using surface tension alone could not be justified as differences
in concentration of graphene for solvents with similar surface tension were also
observed.
Coleman group used the solubility theory, where the solubility of a molecular
solute is said to closely depend on its cohesive energy density EC,T /V. Here, EC,T is the
total molar cohesive energy and V is the molar volume of the solvent. The Hildebrand
√
solubility parameter, δT , which is the square root of cohesive energy density, EC,T /V,
was also used for solvent screening (Fig. 10.17b). Again, different solvents with
402 N. Padma

similar Hildebrand solubility parameters were observed to yield different efficiency

of exfoliation.
It was realised later that considering only the surface energy factor was not suffi-
cient and that the use of Hildebrand solubility parameter to screen the solvents was
only a weak approximation as this parameter was mainly valid for non-polar solvents.
In order to widen the range of solvents including the polar solvents, the criterion was
further widened. It is well known that in a solvent–solute system, the intermolecular
interaction can be divided into three components of the cohesive energy—polar (P),
dispersive (D) and hydrogen bonding (H) components. The square root of each of
these components is a Hansesn’s solubility parameter, δ i . The expression relating the
three components with δT is as given below [4, 74, 76]:

δT2 = δ 2D + δ 2P + δ 2H (10.3)

Hansen has suggested the enthalpy of mixing to be.

Hmi x
≈ [(δ D,S − δ D,G )2 + (δ P,S − δ P,G )2 /4 + (δ H,S − δ D,S )2 /4]φ (10.4)
V

where the subscripts S and G represent the solvent and graphene, respectively. This
expression now indicates that for maximum dispersion of the solute in the solvent, all
the three solubility parameters of the solvent have to be close to those of the solute.
It was reported that graphene was exfoliated more efficiently in NMP than in
pyridine though the latter had closer Hansen’s solubility parameters. The above
expressions are generalised for a solvent and a molecular solute while graphene is
a layered nanomaterial. For such materials, interaction with the solvent takes place
at well-defined surfaces. Because of this reason, the use of surface energy-based
Hansen like solubility parameters would be more appropriate, considering surface
energy also to be divided into polar, dispersive and hydrogen bonding components.
However, such solubility parameters are available only for very few solvents while
Hansen’s solubility parameters are available for more than 1000 solvents. Surface
tension components of the mixtures are not accessible even if those of the individual
solvents are available. Estimating precisely the surface tension of the 2D layers is a
difficult task. Because of these reasons, the screening of the solvents is carried out
using the latter, where the concentration of graphene sheets is plotted as a function
of δ D , δ P , and δ H as shown in Fig. 10.18.
As per the second criterion for a good solvent, high dispersions for a long duration
should be obtained, preventing re-aggregation. This necessitates the wetting of the
exfoliated layers by the solvent, by causing surface modification if necessary, thereby
blocking the process of re-aggregation. Spontaneous wetting of the solvent on the
solid surface (2D layer) occurs when the spreading coefficient S SOL/2D is positive [4].
The spreading coefficient is given by the expression as shown below:

SS O L/2D = γ2D − γ S O L − γ2D/S O L > 0 (10.5)

10 Exfoliation Routes to the Production of Nanoflakes … 403

Fig. 10.18 Concentrations

of exfoliated graphene
(dispersibility) tested for
various solvents as functions
of Hansen solubility
parameter for a dispersive,
b polar and c hydrogen
bonding components.
(“Reprinted (adapted) with
permission from (Langmuir,
2010, 26(5), 3208).
Copyright (2018) American
Chemical Society”)

where γ SOL is the surface energy of the solvent, γ 2D is the surface energy of the 2D
material and γ 2D/SOL is the solvent/2D layer interfacial energy. The above expression
can be rearranged as follows:

γ2D > γ S O L + γ2D/S O L (10.6)

Texter proposed that the best solvent that would maintain the dispersions by
wetting thoroughly would satisfy this inequality. The extent of wetting of the solvent
on the layer surface can be estimated using the Young’s equation given by.

γ2D/S O L = γ2D − γ S O L cos(θ ) (10.7)

404 N. Padma

where θ is the contact angle that the solvent makes at the solid surface and which can
be measured. γ SOL can be available from the literature and since γ 2D will remain the
same irrespective of the solvent used, the interfacial energy and hence the wettability
of the solvent can be estimated from the measured contact angle. It has to be noted
that for a given 2D layer, the term γ 2D/SOL is not tunable. Recently, Ajayan group
proposed a universal method to identify good solvents for all 2D materials like
graphene, MoS2 , WS2 , h-BN, MoSe2 , TaS2 , SnS2 , etc. based on surface tension
components [68]. They obtained precise surface tension components of more than
40 solvents by detecting minute tension changes using commercial equipment. They
determined the polar and dispersive components of the surface tension for each
solvent. Since determining the absolute value of the surface tension of 2D materials is
difficult, they obtained the ratio of the polar and dispersive components by combining
OWRK (Owen Wendt, Rabel and Kaelble) theory with Young’s equation—0.471 for
graphene, 0.563 for WS2 , 0.449 for MoS2 and 0.450 for h-BN. They also noticed that
apart from exfoliation, surface tension also had a role in the dispersibility. By plotting
the dispersibility with surface tension components ratio, a strong correlation between
the dispersibility and the ratio of the components was observed, with the dispersibility
peaking when the ratio matches with that of the 2D materials (Fig. 10.19). For
example, the polar/dispersive component ratios of the best solvents for exfoliation
of graphene and WS2 were found to be around 0.48 and 0.52, respectively, which
are close to the values 0.471 and 0.563 for graphene and WS2 , respectively.
The concentrations obtained using these methods were found to be very low with
the flakes existing as mostly multilayer stacks and only with few monolayer sheets,
thereby requiring large improvement in the same. A simple explanation for low
concentration could be that the solvent radicals get attached to the basal plane of
the nanosheets and become a nucleation site for other solvent molecules, thereby
stabilising the flakes in the dispersion [4]. Coleman group attempted to increase
in sonication time and obtained improvement in the concentration of the graphene
flakes from 0.05 mg/ml to around 1 mg/ml. They had observed that the concentration
scaled well with square root of the sonication time (Fig. 10.20). Unfortunately, the
flake dimensions were also found to reduce with increasing sonication time as t −1/2 ,
probably due to sonication induced scission, along with generation of new defects
[75, 77].
They also attempted size selected exfoliation of graphene by conducting controlled
centrifugation [78]. Here, they successively reduced the centrifugation speed from
4000 to 500 rpm in various steps. Between each step, they removed the supernatant
and added NMP to the sediment to proceed with the centrifugation. They observed
that the flake length at higher centrifugation speed is much smaller than that at lower
speed. They did another study on the yield of MoS2 where they varied the initial
mass and the starting concentrations of the same ranging from 5 to 200 mg/mL in
NMP [79]. They observed the dispersion concentrations to scale linearly with the
starting concentration. Their sonication time-dependent yield measurements revealed
that after 23 h sonication, the concentration was about 3.2 mg/mL, which increased
to 40 mg/mL after 140 h sonication. They also carried out controlled centrifugation
measurements, similar to that carried out for graphene in their previous study. Though
10 Exfoliation Routes to the Production of Nanoflakes … 405

Fig. 10.19 Dispersion for a graphene, b WS2 , c MoS2 and d h-BN. (“Reprinted (adapted) with
permission from (Nano Lett. 2015, 15, 5449). Copyright (2018) American Chemical Society”)

Fig. 10.20 Concentration of

exfoliated and dispersed
graphene sheets in NMP
solvent, as a function of
sonication
time—(“Reprinted (adapted)
with permission from
(Accounts of Chemical
Research, 2013, 46, 14).
Copyright (2018) American
Chemical Society”)
406 N. Padma

the reduction in the flake size with sonication time showed a similar relationship as
observed for graphene, concentration of the dispersion did not show a dependency
on square root of sonication time, as observed for graphene. This suggests that the
exfoliating kinetics to be varying for different materials. They made an attempt to
explain the variation of flake thickness with its size as follows: At high concentrations,
large flake size will have a relatively small volume of the solvent, which could
be driving aggregation phenomenon such that the volume of the solvent per flake
increases to an appropriate level. Similar observations were also made for carbon
nanotubes [80, 81]. A relationship between the dispersed concentration and the mean
flake dimensions was suggested as below [79]:

C∞ < w >< t > / < L >2 (10.8)

where L is the length, w is the width and t is the thickness. This suggested that at
high concentrations, large-sized flake should become thicker than those dispersed
with lower concentrations. By lowering the concentration, though the flakes had
become marginally thinner, they had also become smaller in size. Hence such a
direct correlation could not be proved. Qiao et al. have investigated the effect of
varying the ultrasonic power on the yield of exfoliation of MoS2 in NMP solvent
[77]. A monotonic increase in concentrations of the flakes with ultrasonic power was
not observed. Rather, the maximum concentration was found at an optimum value of
320 W, which decreased with further increase in the power. The size of MoS2 flakes
was around 300 nm with narrow size distribution.
Experimental results on exfoliation studies as well as from inverse gas chromatog-
raphy measurements reveal the surface energy of h-BN, MoS2 , WS2 and MoSe2 to
be in the range 65–75 mJ/m2 , which is similar to that of graphene (65–120 mJ/m2 ).
This suggests that inorganic layered compounds can also be exfoliated through liquid
phase method [12]. Shen et al. have made efforts to identify best solvents for exfoli-
ation of MoS2 , WS2 , MoSe2 etc. [68]. Lee et al. have reported a yield of 0.3 mg/mL
of MoS2 nanosheets of thickness in the range 3–17 nm with the lateral dimensions
around 1 μm, when exfoliated in N-vinyl-2-pyrrolidone using probe sonication [82].
Bourlinos and his group used electron-withdrawing fluorine group-based compounds
as organic solvent and demonstrated successful exfoliation. They proposed that apart
from surface energy, donor–acceptor interaction between the solvent and the layered
material also could be influencing the exfoliation [83]. Hanlon et al. have exfoli-
ated black phosphorous (BP) in the solvent N-cyclohexyl-2-pyrrolidone (CHP) and
in NMP, even in ambient conditions [84]. They have claimed size-selective exfoli-
ation through controlled centrifugation. For exfoliating BP, apart from the criteria
mentioned earlier for other 2D materials, the solvent must also form a solvation shell
acting as a barrier to oxygen and water. Kang et al. investigated structural stability of
BP flakes after exfoliation in NMP and concluded that this solvent enhances stability
towards ambient conditions [85]. They compared exfoliation yield of BP in different
solvents like NMP, acetone, chloroform, hexane, isopropyl alcohol and dimethylfor-
mamide (DMF). Among these, they obtained the highest yield with NMP solvent.
10 Exfoliation Routes to the Production of Nanoflakes … 407

Fig. 10.21 Concentrations

of exfoliated graphene for
different solvents and
centrifugation rate
(Reprinted (adapted) with
permission from (J. Phys.
Chem. C, 2011, 115, 5422).
Copyright (2018) American
Chemical Society”)

Ren et al. also exfoliated BP flakes in NMP and the yield was good enough that
they could coat a film of these flakes on ITO (indium tin oxide) and demonstrate
a three-electrode photoelectrochemical cell [86]. Best performance in exfoliation
of BP in terms of yield for various solvents was reported in the order formamide
> dimethylsulfoxide (DMSO) > DMF, NMP, IPA > ethanol, methanol > acetone >
tetrahydrofuran (THF), water [66, 85].
Some studies mention that liquid exfoliation of ReS2 in organic solvents is scarcely
attempted as there are not many solvents, which have matching surface energy for
this 2D material [37].
Liquid phase exfoliation was modified by changing the liquid from the high boiling
point solvents like NMP, DMF etc. to the low boiling point solvents like methanol,
ethanol, isopropyl alcohol, acetone, etc. This was because (1) solvents like NMP
were toxic and could pose safety issues and (2) as they are high boiling point, they
did not evaporate easily, thus remaining on the surface of the exfoliated flakes and
hindering the use of these flakes in practical applications [51]. Coleman group has also
demonstrated exfoliation of graphene in low-boiling point solvents like chloroform,
isopropanol, acetone along with cyclohexanone, NMP and DMF. Concentrations
of graphene for various solvents under different centrifugation rates are shown in
Fig. 10.21 [87].
The study showed that they could exfoliate in isopropanol and chloroform to a
concentration of 0.5, 0.2 and 0.07 mg/ml at centrifugation rates of 500, 2000 and
5000 rpm, respectively. Acetone showed poorer results with yield of 0.08, 0.025 and
0.01 mg/ml for 500, 2000 and 5000 rpm, respectively. They obtained these results at
a sonication time of around 30 min only. They also observed that these dispersions
remained stable up to about 80% even after 100 h. The average size of the flakes was
around 1 × 0.35 μm and about 10 layers. Choi et al. could exfoliate graphene in a
volatile solvent, propanol, to a concentration of about 1 mg/mL [88]. The advantage
of using these volatile solvents is that they can become ready for use in device
applications without the solvent sticking on them as well as prevention of restacking
of the flakes when deposited on a substrate, ensured by the fast evaporation of the
solvents.
408 N. Padma

LPE Using Cosolvent Method

Due to the disadvantages of using high-boiling point solvents and that of the low
boiling point poor solvents, Zhou et al. arrived at an improvement in LPE using
cosolvency method where they have used a mixture of two poor solvents in which
the nanosheets exhibit poor exfoliations individually [89]. As discussed before, the
dispersibility of a material in a liquid is predicted by Hansen’s solubility parame-
ters (HSP). Though they are mostly employed for single solvents, Zhou et al. have
extended these HSP parameters to a mixture of solvents in which each of the three
HSP parameters for a solvent mixture is a linear function of composition as given
below:

δblend = φn,comp δn,comp (10.9)

where φ is the volume fraction for each composition. Using this expression, in
combination with Eq. 10.4, the solubility of various nanolayered materials in different
solvent mixtures can be estimated, thereby allowing the engineering of an ideal
solvent mixture for each 2D material. Zhou et al. have employed alcohol and water
mixture to exfoliate different graphene analogous systems like MoS2 , WS2 and BN.
They have investigated the efficiency of exfoliation of each of these materials by
varying the volume fractions of ethanol in water where the HSP of water are—δD
15.5 MPa1/2 , δP 16 MPa1/2 and δH 42.3 MPa1/2 and that of ethanol are—δD 15.8
MPa1/2 , δP 8.8 MPa1/2 and δH 19.4 MPa1/2 . The photograph below shows that high
concentrations of dispersed flakes are obtained for MoS2 at 45%, WS2 at 35% and BN
at 55% (Fig. 10.22). The major advantages in using these liquids are that they are of
low cost, easily volatile so that they do not hinder the fabrication and performance of
the devices and are toxic free. Though the concentrations of 0.032 and 0.018 mg/mL
obtained for WS2 and MoS2 , respectively, were much lower than that reported by
Coleman using high-boiling point solvents, these results provided positive indications
that such unharmful and low-cost methods can be used for exfoliations.
Halim et al. have shown successful exfoliation of graphene and MoS2 in different
alcohols and water mixture with weight fraction of alcohols varying from 0 to 100%
of each of them [90]. They observed maximum exfoliation occurring for IPA was
at around 30% in water. They have attempted to explain the mechanism behind
such cosolvent-based exfoliation in their study. They have suggested that the alcohol
molecules in the mixture behave similar to surfactant molecules due to their tendency
to aggregate in water. While they mix macroscopically well with water, they tend to
microscopically form aggregates to hide their hydrophobic groups. This aggregate
formation is similar to micelle formation in surfactants varying only with the degree
of hydrophobicity. While the highly hydrophobic surfactants mostly have around 1%
critical micelle concentrations, alcohols require a much higher concentration with
weight percentage around multiples of 10 to form their aggregates. In the case of
tetra-butyl alcohol, these aggregations were found to vary with the concentration
and their size could be as large as around 40 Å. These aggregates are highly mobile
10 Exfoliation Routes to the Production of Nanoflakes … 409

Fig. 10.22 Photograph

showing various
concentrations of dispersed
flakes at different
combinations of
ethanol/water mixtures for
a MoS2 , b WS2 and c) BN
(Zhou, K. G.; Mao, N. N.;
Wang, H.X.; Peng, Y. and
Zhang, H. L. A
Mixed-Solvent Strategy for
Efficient Exfoliation of
Inorganic Graphene
Analogues. Angew. Chem.
Int. Ed. 2011. 50.10839.
Copyright Wiley–VCH
Verlag GmBH & Co. KGaA.
Reproduced with
permission)

and they fluctuate. As most of the nanoflakes are hydrophobic, the non-polar (-CH3 )
groups interact with the surface of the nanoflakes while the polar (-OH) groups
point out and interact with water thereby solvating the entire system. The optimum
weight fraction of alcohol arises due to the fact that with increase in the same,
the competition between aggregate formation and dispersion of flakes occur, where
the addition of too much alcohol would allow mainly aggregates formation and
prevent them from settling on the layer surface. This would result in lesser exfoliation
and dispersion. This could be the reason behind the observation of different critical
concentrations for different alcohols, i.e., 80% for methanol, 50% for ethanol, 30%
for isopropyl alcohol and 10% for tetrabutyl alcohol. They have also observed that
the peak exfoliation yield is increasing with the molecular weight of the alcohols
with minimum for methanol and maximum for tetrabutyl alcohol suggesting that the
cosolvent molecular size has an influencing role in exfoliation. They correlated this
observation with steric repulsion, with the larger size offering higher steric repulsion
and hence better dispersion. When two nanolayers are separated by less than a critical
distance of around 5 Å, the attractive forces between the layers are strong enough
to expel the trapped molecules. But if their separation increases beyond this critical
410 N. Padma

distance due to the larger size of the cosolvent molecules penetrating between or
intercalating the layers, the weakened attractive forces are unable to expel the trapped
molecules, thereby improving dispersion and stability. Yao et al. have employed a
transfer technique where they have initially grinded the bulk TMDC powders in
NMP and further have sonicated the same in ethanol/water mixture to obtain a yield
of around 26 mg/mL [91]. Wang et al. have attempted a novel technique to pre-treat
the bulk powders in liquid nitrogen followed by sonication in alcohol/water mixture.
They claimed that such pre-treatment aided in the initial peeling off of the layers
from the bulk [92].

LPE Using Supercritical Fluid (SCF)

Gulari’s group developed a new method using supercritical fluids (SCF) to exfoliate
nanoflakes of layered silicates [93]. Supercritical fluids, the substances in the middle
state between gas and liquid phase and becoming fluid state above their critical
temperature, share the properties of both the phases. They have much more empty
space than ordinary liquids and are highly compressible. As a result, the density
and the strength of the solvent can be tuned to change them from gas-like to liquid-
like state, just by applying pressure, temperature etc. Such tunability, accompanied
with low interfacial tension, excellent wetting of the surfaces and high diffusion
coefficients, make them best-suited solvents for penetrating between the layers for
exfoliation. Rangappa et al. and some others have used supercritical ethanol and DMF
to exfoliate graphene nanosheets from graphite crystals [94]. Here typically, the initial
bulk powder was dispersed initially in a solvent and the dispersion is subjected to
high temperature and pressure in a stainless steel reactor. Pu et al. recently modified
slightly where they have used supercritical CO2 (SC CO2 ) to exfoliate graphene
instead of using supercritical organic solvents [95]. This method offers a simple and
clean route to exfoliate graphene in large quantities. Following this path, Qi et al.
have exfoliated MoS2 using a green route using ethanol and water with SC CO2 [96].
Here, they have dispersed MoS2 in an aqueous solution of ethanol and subsequently
exposed them to CO2 under supercritical condition. Due to the compatibility of SC
CO2 with ethanol, two phases were formed, i.e., SC CO2 –ethanol and MoS2 –water.
Initially, due to hydrophobic properties of MoS2 , they disperse at the interface of
water and SC CO2 –ethanol. The pickering emulsion droplets are formed due to the
synergetic effect of SC CO2 , ethanol and high-speed mechanical stirring. The SC
CO2 can also intercalate between the MoS2 layers and weaken the van der Waals
forces between the adjacent layers. Ethanol molecules are carried along with CO2
molecules and get inserted between the layers, thereby weakening the van der Waals
further. Under continuous high-speed stirring, the existing shear force between the
SC CO2 and MoS2 –water phases forces the exfoliation of the MoS2 sheets layer by
layer.
Though liquid exfoliation using organic solvents is insensitive to ambient condi-
tions and hence environment friendly, it suffers from a low yield. Different methods
of liquid exfoliation were focused on to increase the yield.
10 Exfoliation Routes to the Production of Nanoflakes … 411

Ion Intercalation-Based Exfoliation

As said in the above sections, the first step in exfoliation is to weaken the attractive
force between the adjacent layers by physically increasing the distance between them
as the van der Waals force is proportional to 1/r6 where r is the distance between the
layers [97]. The van der Waals force is also expected to vanish for interlayer spacing
above 5 Å. The distance between the layers can be increased by intercalating the layers
using external species like ions, salts, surfactants, organic molecules and polymers,
etc. Layered materials generously allow the external species like ions, molecules
etc. to enter into the spacing between the layers, forming what is called inclusion
complexes. Intercalation, mostly by ionic species, increases the spacing between the
layers, which weakens the van der Waals forces and reduces the energy barrier to
exfoliation. Intercalation of TMDCs by lithium and further exfoliation were demon-
strated in 1970s by Morrison, Frindt and co-workers [12]. Such exfoliation methods
were reported to produce microgram quantities of monolayers. In this technique, the
bulk powder is submerged in a lithium-containing compound like n-butyllithium for
sufficiently long time to allow lithium ion to fully intercalate into the material. This
is then followed by exposure to water where the lithium ion reacts vigorously with
water causing hydrogen gas to evolve between the layers. This release of gas causes
the layers to be separated resulting in exfoliation in water. Eda et al. have attempted
exfoliation of MoS2 by immersing the bulk crystals of the same in butyllithium solu-
tion in hexane for 2 days [97]. The resultant Lix MoS2 was filtered and washed with
plenty of hexane to remove excess lithium. The remaining Lix MoS2 was dispersed in
water and subjected to ultrasonication. The mixture was further centrifuged several
times to remove the excess lithium in the form LiOH and the unexfoliated material.
The entire reaction can be represented as below [97–101]:

MoS2 + BuLi → LiX Mos2 + 1/2Bu − Bu (10.10)

X
Lix MoS2 + xH2 O → MoS2 (monolayer) + xLiOH + H2 (10.11)
2
Similarly for WS2 , a similar reaction is valid:

WS2 + BuLi → Lix WS2 + 0.5 Bu − Bu (10.12)

X
Lix WS2 + xH2 O → WS2 (monolayer) + xLiOH + H2 (10.13)
2
The schematic of the Li intercalation into the layered bulk and subsequent
exfoliation in water is shown in Fig. 10.23 below:
412 N. Padma

Fig. 10.23 Schematic showing Lithium intercalation and exfoliation

The majority of the exfoliated sheets were found to be mono-disperse with 300–
800 nm in lateral dimensions and 1–1.2 nm thickness. Thin film was then prepared
by filtering the diluted suspension through a 2.5 μm pore mixed cellulose membrane.
The filter membrane with thin film was slowly introduced into water allowing the film
to get delaminated from the membrane and floating freely on the surface of water. The
floating film was scooped and transferred onto a substrate. Eda et al. have observed
that the thermodynamically stable 2H MoS2 undergoes phase transformation upon
Li intercalation to the metastable octahedral 1 T MoS2 , which becomes metallic.
After mild annealing at around 200ºC, they could retrieve the 2H phase partly,
which becomes semiconducting again. Gu et al. have also reported a concentration of
1 mg/mL of MoS2 , obtained after lithium intercalation, when diluted with isopropyl
alcohol [100]. Some other groups have also demonstrated Li–ion intercalation-based
exfoliation for MoS2 , WS2, MoSe2 and SnS2 [12, 99–101]. The major advantage of
Li intercalation is that it results in high yield of monolayers. But unlike exfoliation in
organic solvents, they are sensitive to ambient conditions where the flammability of
the lithium compounds poses serious safety issues and hence requires the entire work
to be carried out in inert atmosphere. Since this requirement makes whole process
expensive, alternate ways for liquid exfoliation were explored.
Zheng et al. have attempted different techniques for ion intercalation [102].
Compared to Li, other alkali metal ions like Na and K are less explored for exfoli-
ation studies. The ionic radius of Na and K is much larger than that of Li implying
that Na and K intercalating between the layers can expand the gap between these
layers to a larger extent that Li, thereby even strongly weakening the van der Waals
forces. They also react with water more violently than Li and hence can be expected
to aid in exfoliation. They have used a two-step expansion and intercalation method
as shown in Fig. 10.24.
In the first step, the bulk powders are exposed to hydrazine vapour leading to the
intercalation of N2 H4 molecules. Decomposition and gasification of these molecules
result in a significant expansion of the interlayer gap, causing the volume of the bulk
to increase by more than 100 times. They are then intercalated by alkali naphthalenide
(Li, Na and K) solution. Upon dipping in water, strong dispersion of layered TMDCs
is obtained with much larger sized flakes of about 5–10 μm, than that obtained
using solution-phase butyllithium intercalation. They have successfully applied this
method to exfoliate various TMDCs like TiS2 , TaS2 , NbS2 , NbSe2 , TiSe2 , MoSe2 ,
etc.
10 Exfoliation Routes to the Production of Nanoflakes … 413

Fig. 10.24 Schematic representing a expansion of TMDs under exposure to hydrazine vapour and
b intercalation of alkali naphthalenide and exfoliation, c photograph of bulk single-crystal MoS2 ,
d photograph of pre-exfoliated MoS2 , e photograph of Na exfoliated single-layer MoS2 dispersion
in water. Reproduced with permission from Springer Nature [102]

Surfactant-Based Intercalation

Though ion intercalation method has been successful in exfoliating layered mate-
rials, it suffers from some disadvantages—(1) the resulting monolayers are highly
defective and highly distorted from 2H structure and (2) upon removal of the ions,
there is strong restacking of the layers and they are sensitive to ambient conditions
[12, 52, 103]. As mentioned before, the alternate route of exfoliation in organic
solvents did not provide a high yield. Therefore, for large-scale production, the use
of environment friendly alternate liquid medium route would be preferable. Some
studies have dispersed layered materials in surfactant–water medium and demon-
strated good success [103, 104]. Coleman group has dispersed graphite in sodium
docecylbenzene sulfonate (SDBS) solution prepared in water [103]. They sonicated
this dispersion in low power bath sonicator for 30 min followed by centrifugation.
The large aggregates of the surfactants were allowed to settle and the supernatant
was used for further analysis. Most of the graphene sheets were less than 5 layer
thickness with a small amount of them with monolayer thickness. They observed
high stability of the dispersion without reaggregation for a long duration. This was
suggested to be due to the large potential barrier created by Coulombic repulsion
between the surfactant coated sheets. Smith et al. have used an ionic surfactant to
exfoliate MoS2 , which acts as ideal stabiliser due to its van der Waals binding to
the exfoliated nanosheets and due to the electrostatic stabilisation [105]. They have
estimated the number of layers to be within 2–9 layers. The obtained flake length was
around 280–430 nm. They have extended this method also to exfoliate WS2, MoTe2 ,
414 N. Padma

MoSe2 , NbSe2 , TaSe2 and BN. Though the concentrations obtained are less than that
for Li intercalation method, the disadvantages with the latter method are not encoun-
tered here. Kang et al. have carried out exfoliation of ReS2 in aqueous surfactant
solution of sodium cholate (SC) in deionised water, by usual sonication followed by
centrifugation [104]. The resultant ReS2 nanolayers were polydisperse with respect
to layer number and thickness. In order to improve this to sort out layer by layer,
they adopted a novel isopycnic density gradient ultracentrifugation (iDGU) method
as a follow-up procedure. They have modified the procedure to make them suitable
for high-density 2D materials where they have added cesium chloride (CsCl) to the
commonly used iodixanol to increase the maximum buoyant density. This enhanced
the layer by layer dispersion of SC encapsulated ReS2 nanosheets.
Besides the above intercalants, exfoliation through intercalation of organic
molecules/polymers/biomolecules, etc. have also been attempted successfully
[106–108].

Electrochemical Exfoliation

Electrochemical route is an efficient and mild method to intercalate and exfoliate

layered materials into nanosheets and has been well explored by many groups [109–
116]. The bulk material to be exfoliated is exposed to positive and negative cycles
of voltage and hence subjecting it to oxidation and reduction reactions. This cycle
of opposite polarity would facilitate the intercalation of opposite charged electrolyte
species into the bulk materials. The basic setup required for this kind of exfoliation is
a two-electrode system consisting of the bulk layered material acting as the anode, a
counter electrode (mostly platinum) acting as the cathode, the electrolyte and a suit-
able power supply. Depending on the potential applied, electrochemical exfoliation
can be divided into two categories, i.e., anodic and cathodic exfoliation [4, 110]. In
anodic exfoliation, positive potential is applied to the electrode with the layered solid
following which the anions of the electrolyte or that created during the electrolysis
would intercalate into the layered material under the applied electric field. In the case
of cathodic exfoliation, negative potential is applied to the electrode with the bulk
material causing cations to intercalate into them. In the former aqueous solutions of
acids like H2 SO4 , H3 PO4 etc. and some ionic liquid–water mixtures are used as elec-
trolytes. In the case of the latter, organic solvents like DMSO, propylene carbonate
etc. containing lithium, alkylammonium salts etc. are generally used as electrolytes.
The use of aqueous electrolytes has made the anodic exfoliation more preferable
than the cathodic exfoliation. Different groups have adopted different architectures
where bulk materials are used as electrodes in some studies while they are added to
the electrolyte solution with platinum acting as the electrodes in some other studies.
Electrochemical exfoliation of graphene from graphite has been successfully
demonstrated using ionic liquids and aqueous acids of H2 SO4 or H3 PO4 [112]. Liu
et al. have used both the graphite rods for both the electrodes in their set up, dipping
them in the ionic liquid/water solution. By applying a potential of 10–20 V for 30 min,
the anode graphite rods got corroded and exfoliated to graphene nanosheets, forming
10 Exfoliation Routes to the Production of Nanoflakes … 415

a black precipitate, which turned into homogenous solution [110]. An elaborate study
on the performance of various ionic liquids and different concentrations of these ionic
liquids was carried out in their study. Lu et al. also carried out one pot synthesis of
graphene nanosheets in a similar setup by using ionic liquids/water mixture elec-
trolytes [111]. In their study, platinum was used as counter-electrode while graphite
rods and highly oriented pyrolytic graphite (HOPG) were used as anodes. Parvez
et al. have shown the anodic exfoliation from graphite using aqueous electrolytes
of inorganic salts like ammonium sulfate (NH4 )2 SO4 , sodium sulfate (Na2 SO4 ) and
potassium sulfate (K2 SO4 ) [112]. Their study concluded that graphene sheets with
the lowest defect density could be produced using this configuration. Zeng et al. have
successfully exfoliated few layers of BN, NbSe2 , WSe2 , Bi2 Te3 , etc. using lithium
intercalation [113]. Here, the slurry containing a mixture of layered materials, acety-
lene black and poly (vinylidene fluoride) (PVDF) binder are coated on copper foil
acting as the cathode. Lithium foil was used as the anode with 1 M LiPF6 in a mixture
of ethylene carbonate (EC) and dimethyl carbonate (DMC) as the electrolyte. The
whole lithium battery assembly with polypropylene (PP) film separator is assembled
inside an Argon-filled glove box. Ejigu et al. have reported successful production of
metallic 1 T-MoS2 nanosheets by intercalating lithium into the bulk material through
electrochemical route [114]. Here they have used an inert Li salt (LiClO4 ) in a mixture
of DMC and EC, MoS2 pellets or MoS2 crystals as working electrode and platinum
mesh as counter electrodes. The 1 T-MoS2 sheets produced were demonstrated to be
useful in hydrogen evolution reaction (HER) and for supercapacitor applications.
Similar to lithium intercalation, electrochemical exfoliation also proceeds through
two main steps—(1) the bulk material swells macroscopically producing an expanded
structure due to the intercalation of electrolyte followed by the production of gas
and (2) exfoliation of the nanolayers due to the eruption of gas and the subsequent
dispersion into the solution. The thickness of the nanosheets and the defect density
produced, oxygen content, etc. can be controlled by varying the parameters and/or
the electrolyte species [112]. Liu et al. also have exfoliated MoS2 nanosheets using
Na2 SO4 salt as electrolyte [115]. They have claimed the production of large-area
nanosheets of size about 50 μm with high quality, low degree of oxidation and with
intrinsic structure. In their setup, the bulk MoS2 crystal, platinum wire and 0.5 M
Na2 SO4 were acting as the working electrode, counter electrode and the electrolyte,
respectively, with positive potential applied to the bulk crystal. A low potential of +
2 V was initially applied to wet the crystal for about 10 min, which was then increased
to about + 10 V to exfoliate the nanosheets that became suspended in the solution.
They have reported a yield of about 5–9% with the concentration in the range of
0.007–0.014 mg/mL. This study has suggested that by applying a positive bias to the
working electrode, the •OH, •O radicals and/or SO4 2− anions insert themselves into
the bulk crystal and weaken the van der Waals forces between the layers. Oxidation
of the radicals and/or the anions results in the release of O2 and/or SO2 , which would
largely expand the layers. The erupting gas would then delaminate the nanosheets,
which remain suspended in the solution. Leong et al. have exfoliated WS2 nanosheets
electrochemically where glassy carbon and platinum are used as electrodes, and
Na2 SO4 is directly added to the aqueous dispersion of WS2 [116].
416 N. Padma

Fig. 10.25 Schematic

showing the principle of ball
milling based exfoliation

Ball Milling and Shear Milling Methods

A ball mill is a type of grinder used to grind and blend materials in the industries,
laboratory researches on materials science, etc. Ball milling is a mechanochemical
exfoliation method combining mechanical forces followed by ultrasonication, which
has been successfully employed to isolate nanolayers of graphene, h-BN, MoS2 ,
WS2 , etc. [4, 17]. Ball milling imparts two kinds of forces, i.e., shear as well as
compressive forces on the layered solids. Shear forces cleave off the layers from the
top/bottom surface whereas the compression forces peel off the layers from the edges.
Subsequent sonication breaks the bigger crystallites into smaller size (Fig. 10.25).
This method employs either high energy or low energy ball milling where the former
dominantly causes through plane fracture than the delamination of the flakes, and
hence causing severe defects in the exfoliated layers. Control of the defect production
is attempted by modifying the milling conditions and the interactions of correct guest
molecules. Ball milling can be of different types—planetary ball milling, wet (liquid)
ball milling, etc. In liquid ball milling, the ball to bulk powder ratio, the size of the
milling balls, milling duration, the type of liquid chosen etc. affect the efficiency of
exfoliation.
By using a combination of low energy ball milling and ultrasonication in surfactant
solutions of sodium dodecyl sulfate–water (SDS) and by tuning the duration of
ball milling, Yao et al. have reported high concentrations of about 0.9 mgmL−1 for
graphene, 0.8 mgmL−1 for MoS2 and 1.2 mgmL−1 for BN [117]. SDS surfactant
is also used by Knierke et al. to exfoliate graphene successfully [118]. Damm et al.
have shown that stirred milling is an improved version of planetary ball milling where
the smaller bead size (mostly 1 mm or smaller) allows a better temperature control
during processing [119]. By using stirred media milling for exfoliation of graphene
in surfactant-free NMP liquid, a yield of about 73 mg/h is obtained for graphene,
which is higher than the quantity 33 mg/h obtained using ultrasonication. Lee et al.
prepared hydroxyl group functionalised BN nanosheets by ball milling the bulk BN
10 Exfoliation Routes to the Production of Nanoflakes … 417

Fig. 10.26 Schematic showing the synthesise of MXene sheets from MAX phase

powder in the presence of sodium hydroxide [120]. They reported the production of
OH-BN nanoplatelets with an average size of 1.5 μm, with negligible damage and a
yield of around 18%.
Though ball milling is an alternate cheap and effective method for large-scale
synthesis of nanosheets, it suffers from the disadvantage of introducing impurities.
It also requires long processing hours, even up to 24 h, and mostly a follow up by
ultrasonication. Yao et al. further improved the exfoliation procedure by employing
a combination of grinding and sonication [91]. In their study, less energy shear
forces are applied on the bulk MoS2 by grinding them in NMP solvent, followed by
ultrasonication in ethanol/water mixture. The grinding time is varied from 30 min to
3 h. They have reported concentrations of monolayer and few layer MoS2 in aqueous
solutions as high as 26.7 mg/mL. Nguyen et al. have modified this procedure by
grinding in a variety of solvents with boiling points and surface tension lower than
that of NMP, due to the problems faced using high boiling point solvents [121].
The solvents investigated are acetone, acetonitrile, hexane, cyclohexane, benzene,
isopropyl alcohol, methanol and toluene. They have ground bulk MoS2 in 0.5 mL
of the chosen solvent using a mortar and pestle for about 30 min. The evaporated
solvent during grinding was replenished by adding additional solvent in doses of
about 0.1 mL. The powder was left to dry in a vacuum oven overnight at around
60ºC. The dried powder was then re-dispersed in ethanol and probe sonicated along
with stirring, for about 90 min. The well-dispersed solution was centrifuged at around
4000 rpm for about 30 min, in about two steps. The supernatant containing nanoflakes
was collected. Verification of the concentration of the flakes for all solvents showed
that the use of isopropyl alcohol, acetone, methanol, benzene and toluene did not
lead to measurable values. Their results further suggest that even though larger size
and best quality flakes were obtained for NMP, acetonitrile (ACN) can be considered
to be an alternative for NMP for exfoliating MoS2 , yielding the high concentration.
Added advantage was that ACN was found to be removed from MoS2 surface after
grinding, unlike the case of NMP, which was found to be sticking on the surface of
MoS2 . Nguyen et al. observed that the grinding step and the solvent used for grinding
play a crucial role in determining the yield. Xu et al. have carried out shear exfoliation
of BP in NMP by using a kitchen blender and a laboratory shear mixer at a shear
418 N. Padma

rate higher than 1.25 × 104 s−1 . They have obtained high quality, highly crystalline
phosphorene nanoflakes [122]. Application of shear force on MoS2 bulk powders
in ethanol/water cosolvent followed by subjecting them to 1 hour of turbulence in a
laboratory mixer with four rotating blades was reported by Yuan et al. [123]. They
focused on ethanol in order to choose a green route to the exfoliation process. They
have reported the best yield at 45% volume ratio of ethanol/water and at the initial
concentration of 10 mg/mL of bulk MoS2 powder. Their study concluded that with an
increase in shearing mixing to a speed of 10,000 rpm and the number of cycles to 10,
they obtained a yield of around 30%. Woomer et al. have investigated the efficiency of
BP exfoliation in 18 solvents and have validated the same using HSP and Hildebrand
parameters. They have demonstrated a large-scale production of monolayer, bilayer
and few layer phosphorene to about 10 g scale [124]. Black phosphorous crystals
were initially ground in a mortar and pestle and sonicated them for 13–16 h in a low-
power bath sonicator under inert atmosphere. They have reported the best result while
using benzonitrile achieving a mean concentration of about 0.11 mg/mL. From the
measurements of concentrations of BP flakes for various solvents, they have inferred
that the optimum conditions of the solvent necessary for BP are almost similar to
other 2D materials like TMDCs and BN.

Synthesis of MXenes

Titanium carbide MXene was prepared in a typical procedure as follows [125]: A

mixture of titanium hydrate, aluminium and graphite powder was thoroughly mixed
in a required stoichiometric ratio using ball milling for about 20–80 h, and pelletised.
The pellet was then sintered at high temperature of around 1350 ºC in argon atmo-
sphere. The resulting pellet in MAX phase was pulverised, immersed and stirred in
hydrofluoric acid (HF). The mixture was then centrifuged and washed with DI water
for about 20 h. Gogotsi group has used different raw materials like TiC, Ti and Al
to synthesise T3 AlC2 precursors [49, 126]. There are reports synthesizing Ti3 AlC2
using Ti, Al and C, Ti, Al4 C3 and C or even TiO2 , Al and C. Though in the initial
studies, pressure was applied on MAX powders to get fully dense samples, this step
was removed in the later studies as the powder samples were even advantageous for
further milling processes. In some studies, the A layer from the MAX phase was also
etched using LiF/HCl combination [126]. Under this condition, delamination of the
MXene sheets can occur simultaneously due to the intercalation of Li in between the
MXene layers. MXenes can also be intercalated with different organic compounds
such as dimethyl sulfoxide (DMSO), tetraalkylammonium hydroxides, etc. or inor-
ganic salts, to exfoliate and produce the MXene sheets. A schematic showing the
synthesise of MXene sheets from MAX phase is shown below (Fig. 10.26):
10 Exfoliation Routes to the Production of Nanoflakes … 419

10.4 Characterisation Methods

Though many techniques like scanning electron microscopy (SEM), energy disper-
sive X-ray analysis (EDAX), transmission electron microscopy (TEM), X-ray
diffraction measurements (XRD), X-ray photoelectron spectroscopy (XPS) are used
to characterise the exfoliated flakes, UV–vis absorption spectrometry, atomic force
microscopy (AFM), optical imaging, Raman spectroscopy and photoluminescent
spectroscopy (PL) are the most important techniques that are used for estimating the
layer thickness and the concentration of the yield. Hence only these techniques will
be discussed in this chapter.

10.4.1 Atomic Force Microscopy (AFM) and Optical Imaging

Locating and identifying the nanolayers and estimating their layer thickness are
the primary steps to be executed after exfoliation before proceeding into device
fabrication. AFM is a primary tool to estimate the layer thickness as it physically
measures the step height produced by the nanolayers. Verification of the morphology
of the flakes on a substrate provides the roughness profile from which the step height is
determined. The layer thickness values and, hence, the number of layers are estimated
from the step height. Some examples of the AFM images of MoS2 and WSe2 are
shown in Fig. 10.27a, c along with their corresponding optical images in Fig. 10.27b,
d [55, 127].
Optical imaging is the simple and non-destructive step to characterise the
nanolayers. It basically depends on the variation in the optical contrast between
a nanolayer and the substrate brought about by the change in the layer thickness. The
choice of the substrate is one of the major factors influencing the optical contrast.
The SiO2 /Si substrates are most commonly used to locate and visualise the mono-
layer to few layer flakes [15]. The optical contrast is calculated within the Fresnel’s
formalism, as a function of SiO2 thickness and the wavelength of the light used for
illumination. The thickness of the SiO2 wafer has to be around 270 nm or 90 nm
such that a clear optical colour contrast of the flakes is obtained [57, 128, 129].
The 2D/dielectric/Si structure produces multiple reflections of light at the air-2D,
2D-dielectric, dielectric-Si interfaces, as shown in Fig. 10.27e. The colour of the
dielectric-coated substrate depends on the interference effect from the reflections at
the two surfaces of the dielectric. The presence of the mono/few layer thickness flakes
modifies this interference effect thereby introducing optical contrast. Several methods
have been applied to improve the optical contrast and to estimate the thickness, such
as the use of narrow band illumination, collection of reflection spectra, measurement
of total colour difference, ratio of colour difference, etc. [57, 128, 129].
Li et al. have demonstrated a simple technique to estimate the layer thickness.
They have shown that the optical contrast between the nanolayers and the substrate
can be obtained from the brightness profiles of their colour images or the grayscale
420 N. Padma

Fig. 10.27 a Optical imaging of a few layer MoS2 flakes with a box marked of area 8 μm × 8 μm
and btheir AFM image (shown in box in this figure with corresponding step heights (“Reprinted
(adapted) with permission from (ACS Nano, 2010, 4, 2695). Copyright (2018) American Chemical
Society”), c optical image of 1L WSe2 and d AFM image of the area shown in red square in
(c) (Li, H.; Lu, G.; Wang, Y.; Yin, Z.; Cong, C.; He Q.; Wang, L.; Ding, F.; Yu, T. and Zhang, H.
P. Mechanical Exfoliation and Characterization of Single- and Few-Layer Nanosheets of WSe2 ,
TaS2 and TaSe2 . Small. 2013. 9. No. 11. 1974. Copyright Wiley–VCH Verlag GmBH & Co. KGaA.
Reproduced with permission), e Schematic showing the multiple reflections at each interface

images of red, blue and green (R, G, B) components. The optical contrast C of the
nanosheet and that of the substrate C S was obtained from the images using a free
software (image). The contrast difference C D is obtained by taking the difference
between C and C S . Similarly, for grayscale images, the contrast difference C DR , C DG
and C DB for R, G, B channel can be obtained from the difference between the contrast
C R , C G and C B of the nanosheet with C SR , C SG and C SB of the substrate. They have
obtained contrast values of 162.3 and 118.6, respectively, for a six layer (6L) and
eight layer (8L) MoS2 nanolayers, and about 120.4 for 90 nm thick SiO2 /Si substrate.
Hence a contrast difference of 41.9 for 8L and –1.8 for 6L MoS2 flakes (Fig. 10.28a,
b). They have further made elaborate studies for estimating the dependency of optical
contrast on the exposure times. Their study also estimates systematically the contrast
difference of MoS2 flakes with thickness ranging from 1 to 5 L, on a 300 nm SiO2 /Si
substrate (Fig. 10.28c–q). Detailed analysis of estimation of the number of layers in
the flakes is also carried out by Ottaviano et al. and Benameur et al. [57, 129]. A
similar optical microscope image of 1 to 6 L of MoS2 flakes is shown in Fig. 10.29a.
It can be clearly seen that a monolayer is almost transparent with minimum contrast
with the substrate while the thicker layers showing increasing contrast. Ottaviano
et al. have plotted the optical contrast for the red, blue and green components and
their average values as a function of thickness for a few layers MoS2 , as shown in
Fig. 10.29b–e. This result shows that the contrast is not a monotonic function of the
10 Exfoliation Routes to the Production of Nanoflakes … 421

Fig. 10.28 a Optical images of a few layer MoS2 flakes on 90 nm thick SiO2 substrate, b their
contrast profile c–o optical images of 1L-15 L MoS2 on 300 nm SiO2 /Si, p) C D values and q) C DR ,
C DG and C DB values of these layers on 300 nm SiO2 , (“Reprinted (adapted) with permission from
(ACS Nano, 2013, 7, 10,344). Copyright (2018) American Chemical Society”)

layer thickness. It shows clear change from a monolayer to a few layer thickness,
beyond which the distinction in the contrast appears to vanish.

10.4.2 Raman Spectroscopy

Apart from AFM and optical imaging, Raman spectroscopic measurements have been
considered to be a major tool to estimate the layer thickness. They can also be used to
identify crystal phases and they are very sensitive to the angle between the crystalline
orientation and the incident Raman laser light. A typical Raman analysis for layer
thickness measurement is shown in Fig. 10.30. Non-resonant Raman spectrum of
1
MoS2 is only characterised by two Raman active modes—the E 2g mode at around
−1
383 cm in the bulk corresponding to the in-plane vibrations of two S atoms with
respect to Mo atoms, and the A1g mode around 408 cm−1 representing the out-of-
pane vibrations of the S atoms above and below the MoS2 basal plane (Fig. 10.30a,
c) [59, 127, 130, 131]. Many studies have reported that these peak positions are
1
very sensitive to layer thinning where the E 2g mode is observed to stiffen and the
A1g mode to soften (Fig. 10.30b). The difference between the two peak frequencies
is reduced from about 25 cm−1 in the bulk to about 19 cm−1 in the monolayer.
For MoS2 , this has become a reliable measure to identify monolayers. Lee et al.
have systematically measured the peak shift with an increase in layer thickness from
monolayer and have shown the saturation of this shift beyond a certain number of
422 N. Padma

Fig. 10.29 a Optical image of a few layer MoS2 flakes (“Reprinted (adapted) with permission from
(Nano Lett. 2010, 10, 1271). Copyright (2018) American Chemical Society”) and b, c, d and e red,
blue, green components and their average contrast values respectively, estimated theoretically for a
few layers thick MoS2 nanoflakes. (Reproduced with permission from IOP Publishers [57]

layers with no change in the difference in the peak frequencies (Fig. 10.30b) [127].
According to classical harmonic oscillator model, when layer thickness increases
from monolayer to bulk, both the modes should stiffen as the stacked layers are
expected to hinder the vibrations and thereby increasing the force constant. Though
the out-of-plane vibrational mode follows this expectation, the in-plane vibration
mode behaves opposite, showing softening, indicating that stacking of the layers
affects the intralayer bonding and their vibrational modes. It was suggested that
the stacking induced structural changes in the intra-bonding in combination with
the strong dielectric screening of the long range Coulombic interactions could be
1
causing a redshift of the E 2g modes [30, 59, 127, 130–133].
Similar studies were made for other TMDCs like WS2 etc. A typical thickness-
dependent Raman spectrum for WS2 is shown in Fig. 10.31a [30]. In the case of ReS2 ,
Rahman et al. report no change in Raman peak frequencies for these vibrational
modes, due to the weak interlayer coupling between the layers that is mentioned
before in this chapter (Fig. 10.31b) [37]. There are 18 vibrational modes for ReS2
as shown in Fig. 10.31b, out of which the peaks 1 and 2 at 136.8 and 144.5 cm−1
are the out-of-plane Ag like vibrations of Re atoms. The peaks numbered 3, 4, 5
and 6 at 153.6, 163.4, 218.2 and 238.1 cm−1 are the Eg like in-plane vibrations
of Re atoms. Their measured Raman spectrum shows negligible peak shift with
change in layer thickness. On the contrary, some others demonstrate the presence
of interlayer interaction accompanied by the observation in shift in Raman peak
frequencies (Fig. 10.31c) [42]. The change in intensity and/or the intensity ratio of the
10 Exfoliation Routes to the Production of Nanoflakes … 423

Fig. 10.30 a Raman spectrum of MoS2 monolayer to bulk, b shift in peak frequencies and their
difference as a function of layer thickness (“Reprinted (adapted) with permission from (ACS Nano,
2010, 4, 2695). Copyright (2018) American Chemical Society”) and c In-plane and out-of-plane
vibrational modes of MoS2

peaks and the change in the peak width are also indicators of layer thickness. Raman
spectrum is also sensitive to stress, strain and pressure applied to these nanolayers.
In this chapter, these points are not discussed as the focus is only on the identification
of layer thickness using Raman spectrum.

10.4.3 UV–Vis Absorption Spectrum

UV–vis absorption spectrum is a main tool employed to estimate the concentration of

the dispersions of nanoflakes that are exfoliated through the liquid phase, using Beers
law. As the band gap gets modified with number of layers for most of the layered
materials like TMDs, the absorption spectrum also shows bands corresponding to
the layer thickness. A typical transition from valence band to conduction band corre-
sponding to different excitonic peaks is shown in Fig. 10.31a. The absorption spectra
for LPE of MoS2 for different centrifugal forces are shown in Fig. 10.32b with the
excitonic positions marked, corresponding to that seen in Fig. 10.32a [77]. The lack
of inversion symmetry together with strong spin–orbit interaction and the interlayer
424 N. Padma

Fig. 10.31 a Peak positions of WS2 (Reproduced with permission from [Nanoscale 2013, 5, 9677–
9683]—Published by The Royal Society of Chemistry, b Raman spectrum of ReS2 (Rahman, M.;
Davey, K. and Qiao, S. Z. Advent of 2D Rhenium Disulfide (ReS2 ): Fundamentals to Applications.
Adv. Funct. Mater. 2017, 27, 1,606,129(1–21) copyright Wiley–VCH Verlag GmBH & Co. KGaA
Reproduced with permission) and c peak position shift of ReS2 peaks, all with change in number
of layers (n) (Reprinted (adapted) with permission from (Nano Lett. 2015, 15, 5667). Copyright
(2019) American Chemical Society”)

coupling lift the degeneracy between in spin levels in the valence band and conduc-
tion bands at K point in the Brillouin zone [134, 135]. For MoS2 , two clear bands
at 627 nm and 670 nm are observed corresponding to direct excitonic transitions
between the two valence band maximum levels to the conduction band minimum
at the Brillouin zone K point, as shown in Fig. 10.32a. These two resonances are
known as A and B excitons. The energy difference between the two excitons defines
the valence band splitting at this point. Similarly, the two bands around 460 and
410 nm, respectively, are the C and D excitons due to the direct transition from deep
valence band to conduction band [121, 136–139]. Jia et al. have shown the shift in
peak positions of A, B and C excitons to lower energies, with an increase in layer
thickness, showing thickness-dependent behaviour (Fig. 10.32c) [136]. Similarly, the
10 Exfoliation Routes to the Production of Nanoflakes … 425

Fig. 10.32 a Schematic showing A and B exciton transition, b absorption spectrum of MoS2 flakes
varying as a function of ultrasonic power (Reproduced with permission from [RSC Adv., 2014,
4, 50981]—Published by The Royal Society of Chemistry, c layer thickness-dependent optical
absorption spectrum of BP flakes at different centrifugal rates (Reproduced with permission from
[J. Mater. Chem. C, 2016, 4, 8822]—Published by the Royal Society of Chemistry, d absorption
spectrum of phosphorene at different centrifugation rates (Reprinted (adapted) with permission
from (ACS Nano, 2015, 9, 8869). Copyright (2018) American Chemical Society”).

typical absorption spectra of BP after liquid exfoliation under different centrifugation

rates and hence different layer thicknesses are shown in Fig. 10.32d [140].

10.4.4 Photoluminescence (PL) Spectroscopy

Another optical method that can offer signature changes with change in layer thick-
ness is photoluminescence (PL) spectroscopy. Figure 10.33a shows the PL emission
corresponding to A and B excitonic transitions of MoS2 for varying thickness from
monolayer like to bulk like, under excitation with 532 nm laser [97].
Due to direct band gap transition, there is enhancement of PL emissions for MoS2
for lowest thickness (monolayer like) while it is seen to be negligible for larger
thickness (approaching bulk) due to its indirect band gap. This shows a clear and
strong response of PL to layer thickness change. Similar observations are made by
other studies also [35]. On the contrary, it can be seen from Fig. 10.33b that the PL
emission is maximum for bulk ReS2 which reduces with thinning of the layers [31].
This is because of the direct band gap for bulk and the weak coupling between the
layers. Liu et al. have shown an increase in PL signal of monolayer phosphorene
426 N. Padma

Fig. 10.33 PL change as a function of a MoS2 layer thickness, inset-energy of A exciton as a

function of thickness (Reprinted (adapted) with permission from (Nano Lett., 2011, 11, 5111).
Copyright (2018) American Chemical Society”), b ReS2 layer thickness. Reproduced with permis-
sion from Springer Nature [35]), c monolayer phosphorene and of bulk BP (Reprinted (adapted)
with permission from (ACS Nano 2014, 8, 4033). Copyright (2019) American Chemical Society”)
and d theoretical and PL based change in band gap with layer thickness measured for phospho-
rene (Reproduced with permission from Springer Nature [npj 2D Materials and Applications 2017,
5(1–13)]

compared with that of the bulk BP when the former is mechanically exfoliated from
the latter (Fig. 10.33c) [141]. The PL spectra also help in the estimation of the band
gap that is varying with thickness. The inset in Fig. 10.33a, d shows the variation in
band gap with layer thickness of MoS2 and BP, respectively [97, 142].
10 Exfoliation Routes to the Production of Nanoflakes … 427

10.5 Applications of 2D Nanolayers

Some of the common applications of 2D materials are in the areas of nanoelec-

tronics like field-effect transistors (FETs) and in energy-related applications like
photovoltaic devices/solar cells and supercapacitors, which will be discussed in this
chapter.

10.5.1 Field-Effect Transistors (FETs)

FETs are three-terminal devices that act like switches and are operated by the electric
field applied to the gate electrode. For practical purposes, devices with ON/OFF
ratio above 104 with a high saturation drain current are necessary for power gain in
radio frequency (RF) FET [56]. For this purpose, semiconductors that offer currents
with good ON/OFF ratio are required. At room temperature, many semiconductors
possess relatively low charge density that is not sufficient to produce high output
currents required for FETs. In this point, the 2D materials score high over other
semiconductors because, the 2D nature of the layered materials confines the charge
carriers to atomically thin surface and prevents scattering observed in 3D solids,
thereby allowing high mobility. The absence of dangling bonds on the surface of
2D semiconductors providing sharp band edges with minimal trap states and their
flat topography are ideally suited for compatibility with the present complementary
metal-oxide semiconductor (CMOS) technology that drives the electronic industry
[1, 12, 19]. These factors enable them to be considered as ideal candidates for active
materials in FETs, allowing transistors to push their scaling limits and operation
speeds beyond Si-based transistors [9].
The basic requirement for the fabrication of FET device is the formation of channel
on these flakes. After the isolation of the flakes, channels of the size in the range
of a few microns are generally formed with the help of electron beam lithography
techniques, followed by deposition of metal pads to act as source and drain electrodes.
The devices can be fabricated either in the bottom gate or in the top gate configurations
[56, 143]. In most of the studies on bottom gate FETs, mostly heavily doped Si itself
is used as the gate electrode with SiO2 acting as the dielectric. In the case of top gate
configurations, polymer dielectrics or any high k dielectrics are deposited over the
nanolayers above which the metal electrodes are coated to form the gate electrode.
Radisavijevec et al. have employed a top gate structure with HfO2 dielectric on
a single layer of MoS2 which is shown in Fig. 10.34a with its optical image in
Fig. 10.34b and the corresponding transfer characteristics in Fig. 10.34c [56].
The transfer characteristics clearly show the n-type behaviour of MoS2 FET. The
advantage of using a top gate configuration is that they can also act as passivating
layers for the nanoflakes, preventing them from degradation due to ambient exposure.
The electron mobility of around 200 cm2 /Vs and a ON/OFF ratio as high as 1 × 108
are reported for this device. In another study, they could improve the mobility to 380
428 N. Padma

Fig. 10.34 a Schematic of a top gate FET with MoS2 monolayer, b its optical image and c typical
transfer characteristics of this FET(inset-output characteristics) (Reproduced with permission from
Springer Nature [56]), d schematic and e transfer characteristics of a bottom gate FET with
phosphorene flakes (Reproduced with permission from Springer Nature [143]

cm2 /Vs where they have demonstrated a small signal power amplifier using MoS2
transistors [10]. Wang et al. have also reported a mobility of around 320 cm2 /Vs
at 77 K, using a h-BN tunnelling layer between the Ni/Au contacts and the MoS2
flakes [9]. Krasnozhon et al. have reported a mobility of around 70 cm2 /Vs and
have demonstrated the use of this transistor at GHz frequencies [144]. Li et al. have
demonstrated a bottom gate p-type FETs with hole mobility of around 1000 cm2 /Vs
using 10 nm thick phosphorene nanolayers [143]. The typical bottom gate device
configuration and the transfer characteristics using BP are shown in Fig. 10.34d, e,
respectively. Studies are also reported on the use of these FETs for many applications
like gas sensing, radiation detection, bio-sensors, photodetection, etc. [60, 62].
When the exfoliated flakes are large enough, channels can be formed by simply
masking through shadow masks, instead of employing the tedious lithography tech-
niques. Optical image of a typical MoS2 flake exfoliated through the scotch-tape
method is shown in Fig. 10.35a, across which a 25 μm wire is fixed under optical
microscope to act as shadow mask. Electrical characteristics are measured across
this channel by applying suitable potentials. A typical I–V characteristics measured
across such a flake are shown in Fig. 10.35b [145].
10 Exfoliation Routes to the Production of Nanoflakes … 429

Fig. 10.35 a Optical image of a MoS2 flake with a 25 μm channel across it (“Reprinted from [J.
Appl. physics 2015, 117, 135,701 (1–9)] with the permission of AIP publishing”), b I–V measured
across this flake

10.5.2 Photovoltaic Devices/Solar Cells

Due to their tunable band gap with layer thickness, 2D materials have recently
enrolled as interesting members of the materials that are used for solar
cell/photovoltaic device applications. Layered materials like MoS2 , phosphorene,
indium selenide (InSe) etc. are tending to become prominent members in this field.
Tunability in the band gap with layer thickness allows them to be useful in harvesting
solar radiations in desired wavelengths, especially in the IR and near-IR regions,
where 40% of the solar spectrum is available. Many studies have used them in
combination with other materials that are harvesting in the visible region to act as
complementary to them. The high conductivity of these materials enhances the charge
carriers to reach their respective electrodes to flow as high current, thereby increasing
the efficiency of the solar cells. Graphene has even shown to be performing like a
transparent conductive oxide. Wang et al. have shown that by using graphene as
anode, they could obtain around 83% of the efficiency of the solar cells that could
be obtained using ITO [146]. Many studies deal with the large area deposition of 2D
materials like CVD, PLD, sputtering etc. for solar cell applications. Since this chapter
deals with exfoliation routes for 2D nanolayers, we will focus on the photovoltaic
cells incorporating nanolayers of 2D materials prepared by exfoliation routes.
There are a number of studies on application of MoS2 nanolayers for solar cells.
Capasso et al. exploited few layer MoS2 flakes as buffer layer in a lead halide
perovskite solar cell as per the configuration glass/FTO/compact TiO2 /mesoporous
TiO2 /CH3 NH3 PbI3 (perovskite) /MoS2 /Spiro-OMeTAD/Au [147]. MoS2 plays dual
role to act as protective layer, preventing shunt contact with perovskite and Au elec-
trode as well as the hole transporting layer from the perovskite to spiro-OMeTAD.
The efficiency obtained was about 13.3% with MoS2 . Though the efficiency reported
was comparable for the devices with and without MoS2 buffer layer, they observed
a stable performance of this device over about 550 h. They also confirmed the hole
transporting property of MoS2 by constructing a device without Spiro-OMeTAD, i.e.,
glass/FTO/compact TiO2 /mesoporous TiO2 /CH3 NH3 PbI3 (perovskite)/MoS2 /Au
430 N. Padma

and compared the performance of this device with that without hole transporting layer
(HTL). They found that the efficiency increased from about 1.5% for the latter to about
4.5% for the former. As stability in the performance is a major issue of concern with
perovskite solar cells, the stability reported here is highly useful as it can pave the way
for improving the same without losing the performance. MoS2 nanolayers are also
used as hole transport layers in bulk heterojunction polymer solar cells with the device
structure as shown in Fig. 10.36a [148]. They have reported a J sc of 15.9 mA/cm2 ,
V OC of 0.72 V, fill factor (FF) of 71% and an efficiency of 8.11%. Yun et al. fabri-
cated a bulk heterojunction solar cells with P3HT:PCBM and PBDTTT-CF:PCBM
composites, using exfoliated and partially oxidised MoS2 nanosheets as hole extrac-
tion layer, showing an efficiency of around 6.8% [149]. Yue et al. have obtained about
7.9% efficiency using MoS2 /carbon nanotube composite as counter electrode in a
TiO2 /N719-based dye sensitised solar cell [150]. Liu et al. have demonstrated about
6.0% efficiency on a dye sensitised solar cell with MoS2 /graphene composite as
counter electrode [151]. Many studies are also focussing on to employ phosphorene
as active layers. Yang et al. have synthesised ultra-small BP nanosheets, named as
BPQDs, and incorporated them in polyaniline layer (PANI), to act as photocathode
(Fig. 10.36b) [43]. This photocathode exhibited NIR absorption, acting comple-
mentary to the visible region absorption by TiO2 /N719 dye photoanode and hence
exposed to illumination on both sides, i.e., 100 mW/cm2 in the front and about
45.6 mW/cm2 at the rear. Such NIR absorption is expected to enhance efficiency.
The typical energy level diagram of this device and the electron transfer process
are shown in Fig. 10.36c. Under illumination, the photogenerated electrons in the
N719 dye are transferred to the conduction band of TiO2 . The oxidised dye then
gets reduced by accepting electrons from the donor in the redox couples. The photo-
generated electrons in the BPQDs are transferred to BPQDs/electrolyte interface to
oxidise the acceptor in the redox couples. They have reported an efficiency of about
6.8% and the short circuit current (J sc ) of 24.31 mA/cm2 (Fig. 10.36c). This J sc is
about 120% higher than that obtained without BPQDs.
Deng et al. have attempted a p–n junction diode by forming heterostructures
of mechanically exfoliated phosphorene layers with CVD grown MoS2 monolayer
[152]. They have demonstrated that this heterostructure can work as photovoltaic
device with external quantum efficiency of 0.3%, when illuminated with 633 nm.
Though this value is very low, it shows the potential of these materials for such
applications. Chen et al. have employed the synthesised BPQDs as hole-transporting
materials (HTM) in a hybrid perovskite solar cell as shown in Fig. 10.37a [153].
The energy levels of BPQDs are well suited to act as HTM as shown in Fig. 10.37b.
They have reported improvement in efficiency from 14.1% for the device without
BPQDs to 16.69% with BPQDs. The J–V characteristics of this device are shown in
Fig. 10.37c.
10 Exfoliation Routes to the Production of Nanoflakes … 431

Fig. 10.36 a Device structure using MoS2 HTL, b Device structure of a BPQD/PANI-based DSSC
and c corresponding energy level diagram and d J–V characteristics of this device under illumi-
nation. b, c and d Yang, Y.; Gao, J.; Zhang, Z.; Xiao,S.; Xie, H.; Sun, Z.; Wang, J.H.; Zhou, C.
H.; Wang, Y. W.; Guo, X. Y.; Chu, P.K. and Yu, X. F. Black Phosphorus Based Photocathodes in
Wide band Bifacial Dye-Sensitized Solar Cells. Adv. Mater. 2016. 28. 8937. Copyright Wiley–VCH
Verlag GmBH & Co. KGaA. Reproduced with permission).

10.5.3 Supercapacitors

Supercapacitors, basically electrochemical capacitors, have caught the global atten-

tion as potential energy storage and power devices, especially in smartphones, hybrid
electric vehicles, smart grids, etc.[32]. They have earned this attention due to the high
power density, fast charging/discharging and excellent stability in the performance
over increased number of cycles they offer. Here, the solvated ions from the elec-
trolyte accumulate at the electrode–electrolyte interface due to polarisation, forming
a double electric layer resulting in the electric double layer capacitance (EDLC). The
absence of chemical reactions unlike battery leads to the fast charging/discharging
cycles. A typical assembly of a two-electrode symmetric supercapacitor is shown in
Fig. 10.38a. High conductivity and large surface area are the basic requirements of
the electrode materials in a supercapacitor to deliver best performance. Due to the
capacity to offer large surface to volume ratio and to exhibit excellent electrochem-
ical properties, 2D materials are the best candidates to be used as active electrodes
432 N. Padma

Fig. 10.37 a Device structure of BPQD HTM-based perovskite solar cell, b corresponding energy
level diagram and c J–V characteristics of this device (“Reprinted (adapted) with permission from
(J. Phys. Chem. Lett., 2017, 8, 591). Copyright (2018) American Chemical Society”)

in supercapacitors. Discovery of graphene, fulfilling these basic requirements, has

turned the global interest to replace carbon-based electrode materials with graphene.
The advantage offered by the 2D nature of graphene is that the electrolyte can seep
into the gap between the layers due to the weak van der Waals forces, thereby coming
into contact with the entire surface area of each layer. This results in enormous EDLC,
thereby improving the performance of the devices. A number of studies are reported
in this direction with good success [154–156].
Yang et al. have demonstrated a graphene-based supercapacitor with specific
capacitance of around 300 F/g and 100 F/g using pure ionic liquid 1-ethyl-3-
methylimidazolium tetrafluoroborate (EMIMBF4 ) and 1.0 M LiPF6 electrolytes,
respectively, at current densities of around 1A/g [154]. Maiti et al. have prepared
holey graphene aerogel, which is shown in Fig. 10.38b and developed two elec-
trode symmetric supercapacitors using these aerogels as electrodes [155]. They
have reported an area capacity of about 35 mF/cm2 at a discharging current rate of
10 mA/cm2 . Though specific capacitance for supercapacitors is generally provided
as a gravimetric capacitance (measure of Farads per unit gram (F/g)), Maiti et al.
have used the parameter F/cm2 to represent the areal capacitance, as thin sheets are
10 Exfoliation Routes to the Production of Nanoflakes … 433

Fig. 10.38 a Supercapacitor device assembly, b graphene gel (Maiti, U. N.; Lim, J.; Lee, K. E.;
Lee, W. J. and Kim, S. O. Three-Dimensional Shape Engineered, Interfacial Gelation of Reduced
Graphene Oxide for High Rate, Large Capacity Supercapacitors. Adv. Mater. 2014. 26. 615.
Copyright Wiley–VCH Verlag GmBH & Co. KGaA. Reproduced with permission), c CV curves,
d charge–discharge cycles, e specific capacitance as a function of discharging current and f capac-
itance retention curve of graphene-based supercapacitor. c–f (“Reprinted (adapted) with permis-
sion from (ACS Appl. Mater. Interfaces, 2017, 9, 22,588). Copyright (2018) American Chemical
Society”)

being used. Recently, Zhao et al. have reported a RGO-based supercapacitor with
improved gravimetric specific capacitance of around 450 F/g [156]. Here they have
prepared a mixture of an aqueous dispersion of liquid crystalline GO (LC-GO) with
salt and urea and coated the mixture on Au-coated plastic substrates (current collec-
tors) by doctor blade method. After drying, the solidified GO sheets, mediated by
NaCl and urea are hydrothermally reduced forming nanoporous and rumpling N-
doped RGO sheets. They have reported a high volumetric specific capacitance of
693 F/cm3 at 1A/g in 1 M H2 SO4 in a symmetric cell configuration. The typical CV,
434 N. Padma

charge/discharge cycles, specific capacitance as a function of current density and the

retention cycles are shown in Fig. 10.38c–f.
Re-aggregation of the graphene nanosheets has been observed to be a serious
bottleneck affecting the performance of the supercapcitors, resulting in a lesser
specific capacitance than that is predicted theoretically. Attempts to functionalise
graphene sheets to widen the interlayer gap and minimise re-aggregation have also
resulted in conductivity loss. There are many other layered materials being attempted
as the electrode materials. These materials are either used individually or in combi-
nation with graphene and/or other 2D materials like MoS2 , VS2 etc. and many
conducting polymers [157, 158]. MXenes are now considered as better replace-
ments for graphene due to their high conductivity, in-spite of having functional
groups attached to them during their synthesis. Recently, Yang et al. have attempted
a composite of MXene with RGO and have reported an improved areal capacitance
of around 800 F/cm2 at a scan rate of 10 mV/s [159].
Apart from these applications, 2D materials are proving to be potential candidates
for batteries, piezogenerators, thermoelectric devices, gas sensing, etc.[160–163].
Rao group and others have demonstrated their significant contributions in water
splitting devices [164–167].

10.6 Conclusions

The production of nanolayers of some of the graphene analogous materials through

different routes has been discussed. Though mechanical exfoliation is a simple
process requiring simply a scotch tape, it suffers from limitations in reproducibility
and scalability. Liquid phase exfoliation (LPE) has been shown to be a better alter-
native, which can result in yields as high as 1–40 mg/mL depending on the bulk
material. Various solvents with high boiling points have been found to result in good
yield. The green routes for the production of nanolayers, by using a simple mixture
of water and alcohol or by using supercritical CO2 have been an attractive alternative
as it is environment friendly and cost-effective. Lithium intercalation or other alkali
metal intercalations have been found to result in high yield but they suffer from the
change in the phase of the flakes and the restacking of the same. Surfactant interca-
lation has been shown to offer stable dispersion of nanoflakes, preventing restacking
of the same. Optical microscopy, AFM and vibrational techniques like Raman spec-
troscopy have been demonstrated to be useful tools for identifying layer thickness
and change in electronic properties. Though LPE method results in scalable produc-
tion, they generally suffer from some of the disadvantages, leading to defective layers
and limitations in their size. They also result in large size distributions, which can
be solved to some extent by carrying our size selected exfoliation with centrifuga-
tion at different steps. The layer thickness-dependent electronic properties demand
strong control over the thickness for practical applications of the nanolayers. This is
a difficult task to achieve in both mechanical as well as liquid exfoliation methods.
Therefore, further improvements are being attempted to improve LPE to increase
10 Exfoliation Routes to the Production of Nanoflakes … 435

the yield in order to produce to industrial scale (typically in the kilograms range)
in a cost-effective and environment friendly manner. The method also needs to be
extended to a wider range of layered materials. The resultant nanoflakes should be
adaptable to the usage in device applications.
Liquid exfoliation could prove useful for chemical functionalisation of various
materials that could enhance its applications in gas sensing, targeted drug delivery
etc. Their other diverse range of properties makes them well suited for applications in
electronics, photonics, energy harvesting and storage applications like thermoelec-
tric, piezoelectric and photovoltaic devices, batteries, supercapacitors, etc. They can
be envisaged as strong candidates to take over the nanotechnology world completely
in future. The fascinating behaviour and the rich physics offered by these 2D mate-
rials as well as the relatively simpler methods of production motivate the research
community to look for further new and interesting layered materials.

Acknowledgements The authors wish to thank Dr. Rekha Rao from Solid State Physics Division
(SSPD), Bhabha Atomic Research Centre (BARC), Mumbai, for constant discussion and experi-
ments/investigations on 2D materials. The authors would also like to thank Dr. Uday Narain Maity,
Asst. Prof, IIT Guwahati, for valuable information on MXenes and supercapacitors. The authors
would like to thank Mr. Ram Ashish Yadav, Homi Bhabha National Institute (HBNI) and SSPD,
BARC, for helping in making figures and the references list.

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Chapter 11
Drying of Tiny Colloidal Droplets:
A Novel Synthesis Strategy
for Nano-structured Micro-granules

Debasis Sen, Jitendra Bahadur, and Avik Das

Abstract Colloids are ubiquitous, and they form an interesting branch of soft-matter
science owing to the nature of interactions among the constituent phases. The stability
of a colloidal dispersion is governed by various intriguing competitive forces, such as
electrostatic, entropic, van der Waals interactions, etc., among its dispersed phases.
If continuous medium of colloidal dispersion starts disappearing, e.g. evaporation
of water from aqueous colloids, the interaction among the constituent particles gets
significantly altered. In fact, the phenomenon of quick evaporation of suspension
droplets, known as spray drying, is widely used in several industries including
food and pharmaceutical industries. Since last decade, this novel technique has
re-embellished itself in nano-science and nano-technology promising ample scope
for synthesis of advanced materials. Fast-evaporating tiny colloidal droplets exhibit
spectacular behaviour due to sudden transition from liquid to powder state associ-
ated with evaporation-induced assembly of the nanostructures. Using such evapo-
rative technique, various hierarchically structured micro/meso/macroporous gran-
ules can be synthesized. The quick evaporation of the solvent owing to large avail-
able surface area of the atomized droplets, makes the process one-step and energy-
efficient. The morphology of the synthesized nano-structured micro-granules can be
tuned from spherical to non-spherical, such as doughnut, multi-faceted doughnut,
etc. The reason behind such morphological transition is primarily associated with
buckling of elastic shell that forms during evaporative assembly. These granules,
owing to their characteristic structure and porosity, promise for potential technolog-
ical applications too. Understanding the mesoscopic structure and correlation among
the constituent nanostructures in a granule is indeed crucial. In this regard, small-
angle neutron/X-ray scattering and scanning electron microscopy have been found
to be effective tools in probing such correlated nano-structured granules. In this
chapter, the synthesis strategy of such novel nano-structured micro-granules, their
mesoscopic characterization will be elaborated.

D. Sen (B) · J. Bahadur · A. Das

Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
Homi Bhabha National Institute, Anushaktinagar, Mumbai 400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 445
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_11
446 D. Sen et al.

Keywords Evaporation-induced assembly · Colloids · Spray drying · Porous ·

Micro-granules · SAXS · SANS

11.1 Introduction

Granular materials are ubiquitous in our daily life. Sand is a common example
of such naturally occurring material. In general, granular material is defined as a
conglomeration of discrete solid particles. They behave in a significantly different
way than conventional solids, liquids or gases, which has inspired many to charac-
terize such materials as a new form of matter. Apart from various scientific inter-
ests owing to their complex flow properties, these materials play an important role
in many industries, such as mining, agriculture, civil engineering, pharmaceutical
manufacturing, etc. Often the granular materials that we are regularly habituated are
of macroscopic length scale. Since the last couple of decades, much attention has
been paid to synthesize granular materials having smaller dimension, e.g. micro-
metric or sub-micrometric length scale. Of course, one extreme of this field is popu-
lated by fascinating field of nanoparticles. Thus, bottom-up approach happens to
be more effective compared to top-down approach to realize such micro-granules
with nanoparticles as building blocks. It is easily understandable that such nano-
structured micro-granules possess several inherent interesting structural features.
Due to the presence of constituent nanoparticles, the granules are expected to have
large available surface area. Further, the granules are inherently micro/meso porous
in nature owing to the formation of the nanoparticle interstices. Such pores facilitate
a percolation path for fluid transport through these granules.
Various strategies have been made to realize such nano-structured micro-granules
including various low temperature chemical routes [1–4]. However, in many cases,
such methods suffer from various issues including up-scalability for laboratory to
commercial production, energy efficiency and total time duration of synthesis. Most
of these shortcomings regarding the synthesis of such micro-granules could be over-
come by following idea from an age-old industrial technique which is known as
‘spray drying’. This technique is well known, particularly in food and pharmaceu-
tical industries, since long time. In this process, powder particles are obtained from
drying of atomized droplets of liquid solution. Milk and coffee powder are common
examples of spray-dried materials used in everyday life. Since the last decade, this
technique has re-embellished itself in the field of nano-science and technology by
producing various novel nano-structured micro-granules [5, 6]. The main principle
behind this novel one-step technique is based on interlocking of colloidal particles
in drying micrometric droplets through evaporation-induced assembly (EIA) owing
to the dynamic interplay between several competitive forces arising due to the modi-
fication of potential landscape as solvent evaporates. At this juncture, it is worth
mentioning that such assembly process is also often seen around us, as in the case
of formation of ring when a drop of coffee gets dried [7] in a cup. Unlike drying
11 Drying of Tiny Colloidal Droplets … 447

of bulk suspension, evaporation of solvent in spray drying becomes more energy-

efficient owing to availability of large surface area of the atomized droplets. However,
simultaneous involvement of several dynamic physicochemical parameters, such as
volume fraction [8], interparticle interaction [9, 10], diffusion of the particles [11,
12] in the drying droplet, hydrodynamic effects, etc., impose a challenge to decipher
the exact role of individual parameter in order to tune the granule morphology and
interparticle correlation in the granules.

11.2 Synthesis of Micro-granules by Spray Drying

In a practical situation, such evaporation-induced assembly is achieved through usage

of a spray dryer. ‘Spray’ and ‘Drying’, these two words together simply define the
one-step facile process involving a phase separation of colloidal suspension from
its solvent and interlocking of the dispersed phase through drying of sprayed liquid
droplets into a hot chamber associated with air suction. Figure 11.1 depicts the
schematic diagram of the different components of a typical spray dryer. A liquid
stream of colloidal suspension is fed by peristaltic/syringe pump to an atomizer,
which atomizes the feed solution into tiny droplets. The transformation of bulk

Fig. 11.1 Schematic diagram of a typical spray dryer for realizing micro-granules from colloidal
dispersion
448 D. Sen et al.

liquid into tiny droplets (typically 10–200 μm sizes) increases surface-to-volume

ratio significantly, which enables more heat transfer in shorter duration of time.
Controlling the atomization process, i.e. the fission of bulk liquid into large number
of droplets is extremely crucial for a spray dryer as this particular process plays an
important role in deciding the size distribution of the synthesized powder granules.
The atomization process is familiar in everyday life which include shower heads,
perfume sprays, etc. In spray drying process, normally such atomization process
involves air-compressed nozzles. In air spray atomization, fluid emerging from a
nozzle at low speed is surrounded by a high-speed stream of air. Friction between the
liquid and air accelerates and disrupts the fluid stream and causes atomization. The
energy source for air atomization is air pressure. Figure 11.2 illustrates how a stream
of feed solution gets atomized while passing through an orifice. The atomized droplet
size is a function of the type of atomizer nozzle and spray parameters including the
feed flow rate, feed pressure, specific gravity of the feed, surface tension and viscosity
of the feed [13]. However, the effective droplet size (D) can be approximated by

D = C P −n M 1 ηw σss ρ −t (11.1)

where ‘P’ is the atomization pressure, ‘M’ is the liquid feed rate, ‘η’ is the viscosity
of the liquid, ‘σ s ’ is the surface tension, ‘ρ’ is the density of liquid and ‘C’, ‘n’,
‘l’, ‘w’, ‘s’, ‘t’ being positive constants. Apart from air-compressed nebulizer, other
types of atomizer also exist, such as electrostatic atomizer or ultrasonic atomizer.

Fig. 11.2 Illustrates the

atomization process of fluid
by compressed air at the
orifice of the nozzle
11 Drying of Tiny Colloidal Droplets … 449

Electrostatic atomization exposes a fluid to a high electric field between the atom-
izer and the ground. The charge transfers to the fluid, and repulsive forces between
the atomizer and the fluid tear the droplets from the atomizer. Ultrasonic atomiza-
tion relies on an electromechanical device that vibrates at a very high frequency
(20 kHz–10 MHz). Fluid passes over the vibrating surface, and the vibration causes
the fluid to break into droplets. Ultrasonic atomizers have advantage of producing
narrow size distribution of droplets as compared to polydisperse droplets produced
by air-compressed atomizers. An electromechanical device made of two piezoelec-
tric crystals that vibrate at a very high frequency governs the ultrasonic atomizer.
However, ultrasonic atomization technology is primarily effective for low-viscosity
Newtonian fluids. In subsequent stage of atomization, the droplets are brought into
contact of hot gas in the spraying chamber. The evaporative assembly of the dispersed
particles occurs in this part. The drying chamber is kept evacuated to ensure efficient
evaporation and heat transfer from the hot gas to the droplets. The efficient drying
at lower temperature makes the process economic. The solvent vaporizes in contact
with hot gas leaving behind the micro-granules. The drying time should be less than
the value of L/v, where ‘L’ denotes the length of the chamber and ‘v’ being the
aspiration speed. The micro-granules are generally collected in cyclone separator by
drawing the gas stream containing the evaporated moisture. It is worthy to mention
that the rate of evaporation of the solvent molecules has a significant role to play
which defines the morphology of the resultant powder and will be discussed later.

11.3 Colloidal Self-assembly During Spray Drying

It should be noted that for synthesis of the nano-structured micro-granules through

spray drying, the starting ingredient is primarily a stable colloidal dispersion or sol,
which is made up of dispersed phase and dispersion liquid. However, onset of evap-
oration during this one-step process suddenly starts altering the stability landscape
owing to the continuous removal of solvent from the droplets. Thus, in order to
understand the consequence of the spray drying process, it is required to discuss in
brief about the stability of a colloidal dispersion where tiny dispersed particles have
a typical dimension between 1 and 100 nm. The stability of a colloidal dispersion
is defined by the particles remaining suspended in dispersion medium. To maintain
the stability, it is required to prevent the aggregation of the colloidal particles which
collide with each other through Brownian motion. For a charge stabilized system, this
is generally achieved by increasing the surface charge associated with the particles.
The stability of such a colloidal system is thus governed by the force balance between
attractive van der Waals force and the repulsive electrostatic force. The DLVO theory
(after Boris Derjaguin and Lev Landau, Evert Verwey and Theodoor Overbeek) tries
to explain such stability by combining the effects of attractive and repulsive compo-
nents. The typical variation of potential energy profile with interparticle distance
is shown in Fig. 11.3. The combination of short-range attractive van der Waals and
long-range repulsive screen Coulomb forces results in a deep attractive well, which is
450 D. Sen et al.

Fig. 11.3 Typical DLVO

potential energy profile
between two colloidal
particles as function of
interparticle separation (r)

referred as the primary minimum. At larger distances, the colloidal particles remain
stable in secondary minimum in balance with attractive and repulsive forces. When
the colloids come closer to each other, repulsive force shoots up resulting in energy
profile maxima, called potential barrier. This barrier prevents the aggregation of
colloids in the dispersed liquid phase. However, any external force can help them to
overcome the potential hill to jump into the deep attractive well vis-à-vis primary
energy minimum configuration. This is where the evaporation of liquid phase of the
tiny droplets has significant role to play. As soon as the droplets come in contact
with hot gas, the evaporation of solvent molecules commences creating a capillary
pool among the dispersed particles. The attractive capillary force serves as the neces-
sary external drive to overcome the potential barrier, and subsequently, the particles
get interlocked into a deep potential well. Thus, the drying of the colloidal droplets
inside the spray drying chamber induces self-assembly of nanoparticles resulting into
nano-structured micro-granules. At larger distances, the energy profile goes through
a maximum, and subsequently, passes through a barrier and then a shallow minimum,
which is referred to as the secondary minimum. It should be noted that during the
evaporation of solvent from a tiny colloidal droplet, the distance between particles
starts to decrease due to capillary force. If the capillary forces are strong enough,
attractive force can overcome the barrier leading to interlocking of particle into a deep
potential well. This suggests that such induced assembly during the evaporation of
solvent from tiny colloidal droplets can be a great way to realize nano-structured
granules constituting interlocked nanostructures.
Let us discuss about physicochemical parameters that influence the drying rate of
a droplet. The first factor which affects the drying is the phase change from liquid
to vapour, i.e. the rate at which molecules escape the liquid–air interface [14]. The
11 Drying of Tiny Colloidal Droplets … 451

second factor is the transport of the vapour molecules away from the droplet surface
in the surrounding air. This transport can be purely diffusive [15], or a combination
of diffusive and convective transport. The third rate-limiting factor is the evaporative
cooling and heat transfer to the liquid–air interface [16]. The drying of droplets under
atmospheric condition is mostly governed by the diffusive transport of vapour. The
shrinkage of the isolated spherical droplet during drying under atmospheric condition
is governed by the following equation [17]:

2DV m V
R0 2 − R 2 (t) = (Ps − P∞ )t (11.2)
ρkT

where ‘R0 ’, ‘R(t)’ is radius of droplet at t = 0 and t, respectively; ‘Dv ’ and ‘mv ’
are diffusion coefficient and molecular mass of water vapour, respectively. ‘ρ’ is
the mass density of water. ‘Ps ’ is the saturation vapour pressure at the surface of
the droplet, and ‘P∞ ’ is the vapour pressure at a distance very far from the droplet,
‘k’ is Boltzmann constant and ‘T ’ is absolute temperature. The shrinkage rate of
the droplet deviates from Eq. (11.2) when it contains disperse or dissolved phase.
Equation (11.2) suggests that typical drying time of an isolated water droplet of
micrometer size in vacuum (P∞ ~ 0) is extremely small and is typically less than
millisecond order. However, in reality in a spray dryer, there are plenty of droplets
instead of a single droplet. These droplets make ‘P∞ ’ significant, and drying time is
relatively more than that for a drying of a single droplet in vacuum.
It is important to discuss how the self-assembly of colloids takes place during
drying of contact-free spray droplets. Here, only two dominant processes are consid-
ered that play crucial role in the assembly of colloids during drying. The first process
is shrinkage of droplet which depends on rate of drying that depends on the temper-
ature, aspiration rate, etc. The second process is the diffusion of colloids inside the
droplet. These two phenomena are competing in nature as far as the assembly nature
of the particles is concerned. The shrinkage of the droplet results into the accumu-
lation of the colloids near droplet surface, whereas diffusion of colloids makes the
concentration of the colloids uniform throughout droplet. A dimensionless parameter,
known as Peclet number (Pe ) is defined as follows:

τmix R2
Pe = = (11.3)
τdry Dτdry

where ‘τdry ’ is the drying time of the droplet and ‘τmix ’ is the mixing time, i.e.
diffusion time of the colloidal particles from the droplet surface to its centre. ‘R’ is
the radius of the droplet. ‘D’ is the diffusion coefficient of colloidal particles (radius r)
in the droplet. The diffusion coefficient for Newtonian fluids can be expressed using
Einstein-Stokes, as D = 6πηr kT
. The case when Pe << 1 implies that the diffusion
of colloids is faster than the shrinkage rate of droplet. In this case, concentration of
the colloids remains uniform across the droplet, and the droplet shrinks isotropically
throughout the drying process resulting into spherical granule [10, 18, 19]. This
452 D. Sen et al.

scenario is considered as slow drying, and no buckling of the drying colloidal droplet
is expected in contrast to the fast-drying regime. Under the slow-drying regime using
mass balance during drying, one can derive a relation between the droplet radius and
volume fraction of colloids.

R 3 (t)φ(t) = R0 3 φ0 (11.4)

where ‘R0 ’ and ‘φ 0 ’ are the radius of the droplet and volume fraction of the colloids
before drying, respectively. ‘R(t)’ and ‘φ(t)’ are instantaneous radius and volume
fraction of colloids at time ‘t’, respectively.
Peclet number Pe >> 1 implies that diffusion of colloids is slower compared to
the shrinkage rate of the droplet leading to preferential accumulation of colloids
at air–water interface of the droplet. A visco-elastic shell of the colloids is formed
during drying followed by a visco-elastic to elastic transition that takes place due
to the interlocking of the colloidal particles. The mechanical response of the elastic
shell, under further compression of the droplet, may cause buckling of the shell
resulting into complex morphology of the granules [20, 21], such as doughnut-shaped
granules. The buckling of the shell indeed depends on its elastic properties and relative
thickness [21]. Such drying scenario for Pe >> 1 is regarded as fast-drying regime.
A scenario of slow and fast-drying processes is shown schematically in Fig. 11.4. It
should be noted that if the initial droplets are polydisperse in nature, the Eq. (11.4)
suggests that an isotropic drying will make the size distribution of the granules
much narrower (Fig. 11.5) compared to the size distribution of the initial droplets.
Further, the size distribution of the granules obtained by anisotropic drying will
be broader compared to that obtained by isotropic drying (Fig. 11.5). So, accurate
measurements of droplet size distribution and the granular size distribution (either

Fig. 11.4 Schematic

representation of isotropic
assembly at slow drying and
anisotropic assembly at
fast-drying scenario
11 Drying of Tiny Colloidal Droplets … 453

Fig. 11.5 Schematic representation of initial droplet size distribution and final granular size
distribution under isotropic and anisotropic assembly scenario

by electron microscopy or by scattering techniques) can hint, in principle, about the

nature of drying, isotropic or anisotropic. The jamming of colloids gives rise to the
formation of mesopores owing to the presence of interstices between the jammed
colloids. The pore size and specific surface area depend on the size of colloids and
nature of jamming [22]. The spray drying technique can also be used to obtain
pores with tunable size and porosity. The soft template such as polymer, surfactant
and bacteria with hard colloids, such as silica, can be used to obtain the composite
granules. The removal of the softer component results into templated pores [23] in
the self-assembled granules. Figure 11.6 illustrates the template mechanism during
drying of droplet under slow-drying regime.

Removal of
Spray drying template

Fig. 11.6 Schematic representation of template mechanism during spray drying

454 D. Sen et al.

11.4 Characterization Techniques

Often use of multiple characterization techniques become indispensable to gain

insight into hierarchical structure of the assembled granules. The direct techniques
like electron microscopy provide topological information of granules such as its
shape and size. Electron microscopy, in particular, scanning electron microscopy
(SEM) is the most suitable tool for investigating granules of micron size and below.
However, internal structure of the granules such as packing fraction of colloids and
nature of jamming cannot be probed using SEM. Further, standard transmission
electron microscopy (TEM) is also not a very effective tool for getting internal struc-
ture of the granules due to limited penetration of electrons through the micron size
granules. Moreover, real-time measurements during assembly of colloids are not
feasible using microscopy techniques. Small-angle scattering (SAS) [24–26] using
neutron and X-rays is an ideal technique to probe self-assembled granules having
hierarchical structure [27]. Basic principle of microscopy and small-angle scattering
technique is compared in Fig. 11.7. Microscopy techniques give information about
object in real space whereas the scattering experiment provides information in recip-
rocal space. The microscopy and SAS methods are complementary techniques to
probe the hierarchical nanostructures. We will describe SAS technique in a more
detailed manner.

Incident beam

Image

Sample Focusing Op cs
Microscopy: Magnified Image

θ
Incident beam
Detector

Sample
SAS: Interference Pa ern

Fig. 11.7 Comparison of basic principle of the microscopy and small-angle scattering techniques
11 Drying of Tiny Colloidal Droplets … 455

SAS provides structural information on inhomogeneities of mesoscopic dimen-

sion (1–1000 nm); structural features include size, shape, dimensionality and inter-
particle spatial correlation. The radiations such as X-rays, neutron and electrons
interact with matter differently. Electrons being a charged particle interacts with
matter strongly, hence, penetration of electron in the matter is less. This makes elec-
trons as a local probe of the matter. Neutron is a neutral particle and hence it interacts
with matter weakly. The penetration power of the neutron is quite high that makes it
bulk probe of the matter. The X-ray interacts with matter via electromagnetic forces,
the penetration power of X-rays falls in between that of electron and neutron.
X-rays and neutrons can be used as probe for SAS depending on the contrast it
offers between the object and matrix where the objects are embedded. The strength
of scattering of X-rays and neutron by an atom is quantified as scattering length.
For X-ray, scattering length for each element scatters proportionally to its number
of electrons. This indicates that scattering profile measured in an X-ray experiment
will be primarily defined by the scattering from heavy Z elements. Neutron scattering
lengths are determined by the quantum mechanics of the neutron–nucleus interaction
and they vary irregularly across the periodic table. The basic differences between
X-rays and neutrons as a probe for material are tabulated in Table 11.1.
In a SAS experiment, neutron/X-ray is incident on the sample with wave vector
‘K i ’ and is scattered into the state with wave vector ‘K f ’. The intensity of scattered
neutron/X-rays is thus measured as a function of momentum transfer (see Fig. 11.8):
q = (K f − K i ) where q is known as the wave vector transfer. The magnitude of a wave
vector is defined as its wave number: |K | = K = 2π/λ, where λ is the wavelength.
For elastic scattering process |K f | = |K i | = K and the magnitude of wave vector
transfer ‘q’ is given by |q| = q = 4π λ
sinθ , where ‘2θ ’ is the scattering angle. The
detailed theory of small-angle scattering and its analysis procedure can be found in
literatures [24–26, 28]. The scattering intensity from a two-phase particulate system
can be expressed as,

Table 11.1 Comparison of the various scattering parameters for Neutron and X-ray
Parameter Neutron X-ray
Intensity Low High
Hydrogen-sensitivity High None
Isotope-sensitivity Strong None
Heavy elements Low High
Spin-sensitivity Strong Average
Penetration depth High Low
Sample size/amount Large Small
Measurement time Long Short
Interaction Nuclear (No systematic variation with Z), Electron (varies as Z2 )
Magnetic
Radiation damage Negligible High
456 D. Sen et al.

Fig. 11.8 The scattering law for elastic scattering scenario

I(q) = NVp2 ( ρ)2 P(q)S(q) (11.5)

where ‘N’ is the number density of scattering objects, ‘V p ’ is the particle volume and
‘( ρ)2 ’ is the contrast factor. The term ‘P(q)’ is a dimensionless function known
as form factor that describes scattering from a single particle and is dependent on
both its shape and size. Analytical expressions for ‘P(q)’ have been available in the
literatures for most common shapes [25, 28]. Form factors of sphere of radius R
 2
can be written as P(q, R) = 9 sin(q R)−(q R)cos(q R)
(q R) 3 . The form factors of sphere of
radius 20 nm, disk of radius 20 nm and cylinder of cross-section radius 20 nm and
length 500 nm are shown in Fig. 11.9a. It is clear from this figure that functionality
of the scattering profile significantly depends on the shape of scattering object. The
slope of the scattering profile (log–log scale), in a particular q-range, shows ~q−1
and q−2 scattering behaviour for cylindrical and disk-shaped objects, respectively.

Fig. 11.9 a Form factor corresponding to different shapes of the particles is shown. Radius of
sphere R = 20 nm, disc radius R = 20 nm, length L and radius of cylinder are 20 nm and 500 nm,
respectively. b Effect of polydispersity on the scattering profiles
11 Drying of Tiny Colloidal Droplets … 457

The scattering from spherical objects shows ~q−4 Porod scattering behaviour at
high-q. The scattering intensity for a dilute system, where the distance between
particles is much higher than their sizes, depends only on the form factor. In such a
situation, interference between scattering from different particles may be neglected,
and the measured signal carries information on the shape and size of individual
particle. As the concentration of particle increases, the interference effects between
scattering particles in the sample becomes important and is described by another
dimensionless function ‘S(q)’ that is called structure factor. ‘S(q)’ depends on the
spatial arrangements of the scattering objects, i.e. the correlations in their position
and interactions. Its formula is given by:
  
sin(qr )
S(q) = 1 + 4N π (g(r ) − 1)r 2 dr (11.6)
qr

where ‘g(r )’ is the particle pair distribution function which describes the spatial
distribution of the particles as a function of the average separation distance, ‘r’.
Analytical expressions for the structure factors have been derived for hard sphere
interaction [29], sticky hard spheres between particles [28, 30, 31]. Similarly, for
charged particle, structure factor has been derived using screen Coulomb interaction.
Please note that Eq. 11.5 is valid for monodisperse particles only. For an ensemble of
polydisperse particles, under local monodisperse approximation [32], the expression
of the scattering intensity can be written as,

I(q) = N( ρ)2 Vp 2 (R)P(q, R)D(R)S(q, R)dR (11.7)

where, ‘D(R)’ is the size distribution of the particles.

The structure factor S(q) ~ 1 for dilute ensemble of polydisperse particles and the
Eq. 11.7, in this case, can be written as:

I(q) = N( ρ)2 Vp 2 (R)P(q, R)D(R)dR (11.8)

The effect of the polydispersity on the scattering profiles from an ensemble of

spheres possessing lognormal size distribution
   2
1 − ln R μ
D(R) = √ exp (11.9)
2π σ 2 r 2 2σ 2

is shown in Fig. 11.3b. μ is the median of the size distribution and σ is called
polydispersity index that varies between 0 and 1. It is evident that sharp oscillations in
the scattering profiles get smeared as the polydispersity index increases (Fig. 11.9b).
Figure 11.10a depicts both the form factor and structure factor as a function of q;
the intensity obtained by multiplication of these two factors using Eq. 11.5 is also
458 D. Sen et al.

Fig. 11.10 a Scattering intensity is shown as multiplication of form factor and structure factor.
b Effect of concentration of particle on the scattering profiles is depicted. Structure factor corre-
sponding to the hard sphere interaction [29] under local monodisperse approximation [32] is used
for modelling the data

shown. Polydisperse sphere with μ = 20 nm and σ = 0.2 is assumed for calculation

of ‘P(q)’. Hard sphere type interparticle interaction was considered for the simulation
of the structure factor ‘S(q)’. It is observed from Fig. 11.5a that low-q intensity is
governed by structure factor whereas the high-q scattering is dominated by the form
factor. Figure 11.10b shows the scattering profiles as a function of volume fraction
of the particle. The scattering intensity at low-q decreases with increasing volume
fraction, a correlation peak starts building up at higher volume fraction φ ~ 0.3 and
it becomes sharp and shifts to high-q as φ increases to 0.5. The average distance
between particles ‘d p ’ in a concentrated system is approximately related to peak
position qpeak as d p ~ 2π/qpeak .
In general, the granules obtained by spray drying process possess hierarchical
structure of the jammed colloid. SAS profile in a wide-q-range can provide infor-
mation about such the granule and the jamming nature of colloids. It should be
mentioned that accessing scattering data over such a wide-q-range always remains
a challenge due to limited q window of a particular instrument. In general, usage
of conventional pin-hole small-angle scattering instrument [33] as well as double
crystal-based ultra-small-angle scattering instrument [34] becomes necessary for
investigating such granules. A simplistic model has been shown below to describe
the scattering intensity from such assembled granule [35, 36]:

I (q) = C g I g (q) + C jc I jc (q) (11.10)

where ‘I g (q)’ is the scattering contribution due to overall assembled granules and
‘I jc (q)’ is scattering contribution due to jammed colloids. ‘C g ’ and ‘C jc ’ are scale
factor for granule and jammed colloid scattering contributions, respectively. It is to
be noted that above equation is valid only if size of granules is quite large (order of
the magnitude) compared to the size of individual colloidal particles.
11 Drying of Tiny Colloidal Droplets … 459

Fig. 11.11 Simulated small-angle scattering profile for assembled silica granules obtained by spray
drying a I(q) versus q. b I(q) × q4 versus q, i.e. in Porod representation

The first term in Eq. 11.10 gives information regarding the shape and size of
the assembled granules, whereas second term in Eq. 11.10 provides information
about the individual colloids such as its shape, size and nature of jamming. An
ensemble of polydisperse spherical granules with μ = 500 nm and σ = 0.2 has been
taken as model for granule scattering I g (q). Randomly jammed colloids interacting
via hard sphere interaction with a volume fraction φ ~ 0.54 is taken as model to
express I jc (q). Figure 11.11a shows simulated scattering profiles I g (q) and I jc (q)
corresponding to scattering from over all granule and correlated colloids, respec-
tively. The combined scattering intensity, i.e. sum of these scattering contributions
is also shown in Fig. 11.11a in double logarithmic scale. The two-level structure
is evident in Fig. 11.11b where data is plotted in Porod representation, i.e. I(q) ×
q4 versus q. Two constant levels in Porod plot indicate the presence of two-level
structure in well-separated length scales. The Porod level at high-q is due to the
scattering from individual colloid, whereas the Porod level at low-q is attributed to
the scattering from overall granules.

11.5 A Few Illustrative Examples

11.5.1 Nano-structured Silica Micro-granules with Spherical

and Doughnut Morphology

Silica micro-spheres as inorganic supports have become increasingly important for

a variety of applications, including isolation of nucleic acids, cell separation and
immuno- and DNA-based assays. They offer combined advantage of a broad platform
and unique properties of a silica substrate. Silica micro-granules can be synthesized
by spray drying technique with silica nano-suspension as starting material. The shape
460 D. Sen et al.

Fig. 11.12 FESEM micrographs showing: a spherical and b doughnut-shaped nano-structured

silica granules. Reproduced with permission from Ref. No. 40 (Adapted with permission from
(Biswas et al. Langmuir 2016. 32(10): p. 2464–2473) Copyright (2016) American Chemical Society)

of the granules can be tuned by controlling the physicochemical conditions during

spray drying [37]. Figure 11.12a, b shows spherical and doughnut-shaped granules,
respectively. The formation of doughnut-shaped granules may be explained due to
buckling of the shell formed during the rapid anisotropic drying as mentioned earlier
[13, 20, 37–39].
It may be recalled from the earlier section that the Peclet number (Pe ), signi-
fying the nature of assembly, is given by Pe = ττmix
2

dry
= DτRdry , where the diffusion
coefficient of the nanoparticles in the droplet is ‘D’. An increase in drying rate
decreases ‘τdry ’. This in turn increases ‘Pe ’. It has been observed experimentally
that gradual increase in drying rate results in increase in hollowness and subsequent
bucking into doughnut shape [40]. The quantitative information on silica-silica corre-
lation in the granules may be obtained from detail analysis of small-angle scattering
profiles (Fig. 11.13). The correlation peak ~0.2 nm−1 in SAS profiles appears due to
interparticle interference among the jammed silica particles in the granules.
These nanoporous silica granules have been found potential sorbents for cationic
dyes such as methylene blue [41]. It needs to be mentioned that after sorption, the
granules settle faster (Fig. 11.14), and thus allows easy decantation of the solvent
in contrast to the situation with bare nanoparticles. It has been found [22, 42] that
incorporation of such granules in ultra-filtration polysulphone membrane enhances
11 Drying of Tiny Colloidal Droplets … 461

Fig. 11.13 Combined SAXS (Zone-I) and medium resolution SANS (Zone-II) data for nano-
structured silica micro-granules. Reproduced with permission from Ref. No. 40 (Adapted with
permission from (Langmuir 2016. 32(10): p. 2464–2473) Copyright (2016) American Chemical
Society)

t=0 T=24 hr

Fig. 11.14 The sorption of methylene blue dye by the granules from aqueous solution. The micro-
granules, being heavier than bare nanoparticles, settle fast allowing easy decantation of the solvent
after sorption. [41] Reproduced with permission from Ref. (Adapted with permission from Colloids
and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 279–288)

the pure water permeability quite significantly without affecting its rejection char-
acteristics. This is probably because of the fact that the incorporated granules can
offer suitable porous channels across membrane surface which were otherwise not
accessible because of the tapering of the pore channels in casted membranes.
462 D. Sen et al.

11.5.2 Macro/Meso Porous Silica Micro-spheres Using

Template Mechanism

It is discussed earlier that spray drying is an effective technique to achieve

macro/meso porous materials using template mechanism. Herein, an example of
fabrication of macroporous silica granules has been shown which was obtained using
E. coli bacteria as a template. E. coli are one of the primary bacterial contamina-
tions in drinking water in most of the underdeveloped/developing countries including
India. A unique approach is adopted to obtain silica-based macroporous micrometric
granules for potential application of filtration of E. coli bacteria from drinking water
using spray drying technique.
Initial silica dispersion (Visa Chemicals, Mumbai, India) was diluted in pure water
(Milli-Q, Millipore). 2wt % silica dispersion and varying E. coli (0, 2, 4 and 6% in
weight), soft component, were taken for spray drying. The inlet temperature was
kept at 170 °C and the aspiration rate was kept at ~47m3 /h. The dried powders were
collected from the cyclone separators. Removal of the imprinted materials was done
by incineration in muffle furnace at 300 °C for 10 h. The powders, with 0, 2, 4 and
6% of E. coli, are designated as S0, S2, S4 and S6, respectively.
The SEM micrographs of samples S0–S6 are shown in Fig. 11.15a–c. It is evident
that spray drying of the only silica colloids results into doughnut type granules as
explained in previous section. The imprinting of E. coli in silica granule is also
evident from the figure. The macroporosity of the spray-dried granules increases
with increasing concentration of the E. coli in the initial dispersion used for spray
drying. Interestingly, deformation of the assembled granules is increased at higher
concentration of E. coli. It has been observed from Zeta potential measurements
[9] that both silica and E. coli possess negative charge, and thus forms a repulsive
system. During drying process of mixed colloids, the bigger size component diffusion
is slow, and hence it remains primarily on the surface of the droplet during drying.
Thus, the shell formed during drying consists of silica as well as E. coli leading
to inhomogeneous shell. Subsequent compression of the droplet leads to the multi-
faceted doughnut-shaped granule through buckling of elastic shell. The buckling gets
enhanced with increase in softer component on the shell [39].
The arrest of buckling of the droplet containing mixed colloids requires preven-
tion of shell formation or increase in elastic strength of the formed shell. In order
to tune this aspect, E. coli cells were treated to impart a cationic charge on the
cell surface using polyethylenimine (PEI) (Average MW ~ 7.5 × 105 ). E. coli cells
were treated with PEI 0.2, 1 and 2%, respectively. The Zeta potential measure-
ments show that charge on E. coli becomes positive due to PEI coating and magni-
tude of charge increases with increasing coating thickness [9]. The spray drying
of the 2wt% silica and PEI-treated E. coli have been performed with identical
drying parameters used previously. The dried granules obtained for 0.2, 1.0 and
2.0 wt% PEI-treated E. coli have been designated as ST1, ST2 and ST3, respec-
tively. Figure 11.15d–f show the micrographs of spray-dried granules obtained for
11 Drying of Tiny Colloidal Droplets … 463

Fig. 11.15 SEM micrographs of a 2wt% silica, b 2wt% silica + 2wt% E. coli, c 2wt% silica
+ 6wt% E. coli. Reproduced with permission from Ref. No. 20 (From D. Sen et al., Buckling-
driven morphological transformation of droplets of a mixed colloidal suspension during evaporation-
induced self-assembly by spray drying. EPJ-E, 2010. 31(4): p. 393–402 with kind permission of
The European Physical Journal (EPJ)) d 2wt% silica + 6wt% E. coli coated with 0.2% PEI, e 2wt%
silica + 6wt% E. coli coated with 1.0% PEI and f 2wt% silica + 6wt% E. coli coated with 2.0%
PEI. Reproduced with permission from Ref. No. 9 (Reproduced from Ref. 9 with permission from
the Royal Society of Chemistry)

mixed colloids containing PEI-treated E. coli. It is evident from the figure that defor-
mation of the granules significantly reduces with increasing PEI coating. The silica
nanoparticles coat the surface modified E. coli bacteria due to the attractive force
between them. Thus, the formed shell, exposed to the air-water interface, primarily
contains silica coated reinforced E. coli and that results in its improved elastic proper-
ties. The increase in the elastic strength of the shell causes arrest of buckling of drying
droplet resulting in spherical granules. A schematic of the assembly mechanism is
shown in Fig. 11.16.
In order to get the quantitative information about the macroporous assembled
granules, SANS measurements have been carried out in a wide-q-range (Fig. 11.17).
The data were analysed using three length scale model. First contribution originates
from the jammed silica in the granules, while the second contribution arises due
to scattering from the E. coli templated pores. The third contribution is due to the
scattering from the overall granular shape. Table 11.2 shows the important fitting
parameters as obtained from analysis.
464 D. Sen et al.

Fig. 11.16 Schematic representation of the assembly process of silica and E. coli. a Both silica
and E. coli have negative surface charges and the system is repulsive. The assembled grains are
deformed. b Silica is negative as in earlier case, but the E. coli surface is coated with PEI to
impart positive charge on the E. coli surface. The assembled grains are spherical in this case and
no buckling has occurred. [9] Reproduced with permission from Ref. No. 9 (Reproduced from Ref.
with permission from the Royal Society of Chemistry)

Fig. 11.17 SANS profiles 101

(Porod representation) of the
E. coli template macroporous 10-1
I(q) x q 4 (arb. unit)

granules over a wide-q-range

10-3
([9] Reproduced from Ref.
with permission from the 10-5
Royal Society of Chemistry)
10-7
S0
10-9 S6
ST1
10-11 ST2
10-13 ST3
Fit
10-15
10-4 10-3 10-2 10-1 100
-1
q (nm )

11.5.3 TiO2 /SiO2 Nano-composites Via Spray Drying

of Mixed Colloids

Spray drying technique has unique advantage because of its ability to mix colloids
of similar size uniformly during the drying process. An example of fabrication of
TiO2 /SiO2 composite micro-spheres has been discussed below. TiO2 -based materials
11 Drying of Tiny Colloidal Droplets … 465

Table 11.2 Structural parameters obtained from SANS analysis. [9] Reproduced with permission
from Ref. No. 9 (Reproduced from Ref. with permission from the Royal Society of Chemistry)
Sample Assembled granule size Templated cylindrical macro pore
distribution
Rgrain R por e
Mean radius Rgrain Length (L pore ) (nm) Average radius R por e
(Rgranule ) (nm) (Rpore ) (nm)
S0 200 0.099 – –
S6 2394 0.658 2000 102 0.205
ST1 2266 0.533 2050 115 0.209
ST2 2266 0.533 2600 167 0.305
ST3 2159 0.531 2600 167 0.305

are quite important due to their photocatalytic properties [43]. It is known that TiO2
has three allotropes, namely, Anatase, Brookite and Rutile [44]. It is well established
that anatase phase of TiO2 is a more efficient photocatalyst as compared to its other
allotropes [45]. However, the thermodynamic stability depends on particle size [46].
For particle size below ~14 nm, anatase phase is more stable than rutile phase. If
TiO2 nano-crystals are heated, crystal growth leads to alteration of phase stabilities
and, ultimately, conversion of anatase phase to rutile phase takes place. Such phase
transformation of anatase to rutile is considered to be one of the drawbacks for photo-
catalytic applications. Moreover, photocatalytic application of the TiO2 requires a
good dispersion of TiO2 nanoparticles, as its efficiency increases because of avail-
ability of more surface area for reaction. Here, spray drying technique has been used
to fabricate a TiO2 /SiO2 composite that is stable against the anatase to rutile phase
transformation. The incorporation of TiO2 nanoparticles in the silica matrix leads to
higher active surface area for the catalytic reaction.
A stable dispersion of the TiO2 and SiO2 has been mixed in the weight ratio of
2:1 for spray drying. The atomization pressure for the droplet generation was kept at
2.0 kg/cm2 and inlet temperature during drying was fixed at 170 °C. Solution feed
rate was kept as 2 ml/min and aspiration rate was fixed at 50 m3 /h. The spray drying
has also been carried out on the individual dispersions of SiO2 and TiO2 . The average
size of the silica and titania colloids was determined using SAXS measurements [24,
25]. The average size of silica colloid was found to be ~16 nm, whereas the TiO2
colloids possess biomodal size distribution with average size of 6 and 17 nm [47].
Figure 11.18 shows the SEM micrographs of the composite micro-spheres in low and
high magnification. Nice spherical-shaped granules of micrometer size is achieved
which is similar to the morphology of the TiO2 and SiO2 granules [47]. The energy
dispersive X-ray (EDX) analysis was also carried out on the composite sphere which
confirms the formation of TiO2 /SiO2 composite (Fig. 11.18c).
Combined SANS profiles of the SiO2 , TiO2 and TiO2 /SiO2 micro-spheres have
been depicted in Fig. 11.19a. Scattering profiles are also shown in Porod representa-
tion (I(q)q4 versus q) as depicted in Fig. 11.19b. It is evident from the figure that the
assembled granules possess hierarchical length scale structure, and existence of two
466 D. Sen et al.

(a) (b)

4 μm 1 μm

(c)

KeV

Fig. 11.18 TiO2 /SiO2 micro-spheres: a in low and b high magnification (Adapted with permission
from [47] Reproduced with permission from Ref. (Langmuir, 2012. 28(31): p. 11, 343–11, 353)
Copyright (2012) American Chemical Society). The EDX spectrum of the composite is shown in
(c)

Fig. 11.19 SANS profiles of TiO2 , SiO2 and TiO2 /SiO2 composite micro-sphere is shown in two
representations. a I(q) versus q and b I(q) × q4 versus q. [47] Reproduced with permission from
Ref. (Adapted with permission from (Langmuir, 2012. 28(31): p. 11,343–11,353) Copyright (2012)
American Chemical Society)
11 Drying of Tiny Colloidal Droplets … 467

Fig. 11.20 XRD patterns of

2500 A(101)
the TiO2 , SiO2 and the
composite micro-spheres.
2000

Intensity (arb. unit)

[47] Reproduced with
permission from Ref. R(110) TiO2/SiO2
(Reprinted with permission 1500
from (Langmuir, 2012.
28(31): p. 11, 343–11, 353) A(101)
Copyright (2012) American 1000
Chemical Society)
500 R(110) TiO2

SiO2
0
20 30 40 50 60 70 80
2θ (°)

Porod levels is evident. The SANS profile of silica micro-spheres shows a distinct
correlation peak at q ~ 0.45 nm−1 corresponding to jammed silica nanoparticles,
the oscillations in the scattering profiles is due to low polydispersity in the size of
colloids. A relatively broader hump is observed in the SANS profile of TiO2 micro-
spheres because of relatively larger polydispersity in the size of TiO2 colloids. SANS
profile of the composite shows a silica correlation peak which is broader than that
for SiO2 granules. The X-ray diffraction (XRD) profiles have been recorded for all
the samples and it is shown in Fig. 11.20. A broad hump is observed for the silica
micro-sphere indicating the amorphous nature of the silica nanoparticles.
The TiO2 micro-sphere shows the diffraction peaks indicating its crystalline
nature. The phase identification reveals that both anatase and rutile phase exist in
85:15 weight ratio [47]. The position of (101) and (110) planes corresponding to
anatase and rutile phase, respectively, is marked in the figure. The XRD measure-
ments were performed on TiO2 and composite that were heat-treated at different
temperatures. The evolution of (101) and (110) planes of the anatase and rutile phase
as a function of temperature is shown in Fig. 11.21. It is evident that anatase to rutile
phase transformation occurs beyond 600 °C for TiO2 micro-sphere. However, no
phase transformation takes place in case of composite micro-sphere. This suggests
that composite granules are thermally stable against anatase to rutile phase transfor-
mation. The growth of TiO2 nano-crystal is hindered in the composite granules as it
is surrounded by SiO2 nanoparticles; this leads to arrest of phase transformation at
higher annealing temperature. Thus, spray drying technique using binary colloidal
systems is a one-step method to fabricate composite granules with improved proper-
ties. The structure and dispersion properties can be tuned by ratios of size of colloids
and its concentration.
468 D. Sen et al.

Fig. 11.21 XRD pattern of the TiO2 and TiO2 /SiO2 composite as a function of temperature. [47]
Reproduced with permission from Ref. (Adapted with permission from (Langmuir, 2012. 28(31):
p. 11,343–11,353) Copyright (2012) American Chemical Society)

11.5.4 Formation of Nano-composite Micro-spheres

with Core–Shell Spatial Distribution

Spatial distribution of the building blocks during assembly may be controlled, and
granules in the form of Janus [48] or Core–Shell [49] morphology can be synthe-
sized in one-step process. Here, an example of core–shell micro-granules has been
discussed, where contrasting interfacial interaction of two types of nanoparticles
with solvent has been exploited during evaporation-induced self-assembly by spray
drying. A mixed colloidal solutions of carbon black (from M/s. Hi-Tech Carbon of
grade N-330) and silica (LUDOX® SM30 from M/s. Sigma Aldrich) nanoparticles
are taken as feed to spray drying. The reason behind choosing carbon and silica is
that they possess opposite polarity of water-affinity. Carbon being hydrophobic hates
water molecules, whereas silica is hydrophilic in nature. The colloidal particles in
mixed suspension remain dispersed in spatially random manner in water. However,
after the colloidal suspension is sprayed inside the drying chamber, the fluid starts
evaporating out of the droplet in radially outward direction. The movement of water
molecules builds up a competition between hydrophilic and hydrophobic compo-
nents. The water-loving component moves in radially outward direction along with
water molecules, but water-repelling component tries to propel against the motion
of water molecules and occupy water-depleted region. Thus, the contrasting interfa-
cial interaction with solvent molecules creates a spatial distribution of hydrophilic
and hydrophobic components in the drying droplet. The hydrophobic particles, i.e.
11 Drying of Tiny Colloidal Droplets … 469

Fig. 11.22 Schematic representation of nano-composite core–shell micro-granules of carbon and

silica. FESEM micrographs show silica-wrapped core–shell micro-granules and the carbon core
after leaching. [42, 43] Reproduced with permission from Ref. (Reproduced from Ref. with
permission from the Royal Society of Chemistry)

carbon nanoparticles assemble near the core, while hydrophilic particles, i.e. silica
nanoparticles occupy the peripheral region of the droplet. In the course of drying,
nano-structured carbon gets encapsulated by porous nano-structured shell of silica
[42]. The schematic in Fig. 11.22 depicts how the contrasting interfacial interac-
tion of nanoparticles with solvent has been utilized during evaporation-induced self-
assembly to encapsulate nano-structured porous carbon core inside nano-structured
porous silica shell.
SANS and SAXS measurements have been carried out to characterize the hier-
archical mesoscopic structure of the spray-dried micro-granules. Combining SANS
and SAXS (Fig. 11.23), a wide wave vector transfer range of three decades (0.003–
2.5 nm−1 ) has been accessed to map the positional correlation and particle form factor
in mesoscopic length scale domain. In complementary to scattering investigations,
field emission scanning electron microscopy (FESEM) has also been used to directly
image the micro-granules in order to corroborate the results inferred from scattering.
The granules show unique features as far as application in water filtration is
concerned. The hydrophilic shell of highly correlated nano-silica offers a wetting
surface for convenient incorporation in polymeric ultra-filtration membrane. In addi-
tion to this, water transport occurs through the interstitial nano-pores towards the
meso porous carbon core. It is to be noted that for decades, activated carbon is being
used as water purification filter, because of its high specific surface area enabling
adsorption of various organic compounds. Carbon is widely used in every household
water filter for its high efficiency in maintaining the taste and odour of drinking
water. In modern method of household drinking water purification, polymeric semi-
permeable ultra-filtration membranes are also being exploited in separating colloidal
470 D. Sen et al.

Fig. 11.23 Combined

SANS and SAXS profile of
the silica–carbon composite
spray-dried granules. The
inset shows the electron
micrographs of the
silica-wrapped spray-dried
granules. [42, 43]
Reproduced with permission
from Ref. (Reproduced from
Ref. with permission from
the Royal Society of
Chemistry)

and suspended matters from water [50, 51]. The carbon–silica nano-composite micro-
granule, because of its core–shell morphology, is easy to incorporate into ultra-
filtration membrane, and thus allow us to combine two separate filtration unit into
a single one. The incorporation of these granules into a polymeric membrane has
been accomplished and the performance is tested [42, 51]. Results reveal signifi-
cant enhancement of water permeability (up to ~18%) through the micro-granules-
incorporated membranes, and the rejection of PEO-100 K from water is almost
100% which has a huge impact as far as membrane separation characteristics are
concerned. This is due to available interstitial pore channels and large specific surface
of mesopores present in the micro-granules. The synthesized composite membrane,
in comparison to standard polymeric membrane, can be utilized to gain the benefits of
superior adsorption properties of mesoporous carbon combining with its own ultra-
filtration separation characteristics with enhanced flux. Use of such silica–carbon
composite membrane will make a household water filter substantially compact as the
need for separate charcoal column, used in a standard filter, will become redundant.

11.6 Future Outlook

The representative studies discussed in this chapter show that the evaporation-induced
assembly through spray drying technique is indeed a novel route to realize nano-
structured micro-granules with interesting shape and pore structure. At this juncture,
it is relevant to discuss the future prospects and associated challenges of this novel
bottom-up technique. There are several aspects in this field which needs to be brought
into closer scrutiny in order to understand this complex assembly procedure which
crucially depends on several physicochemical parameters. Understanding the nature
11 Drying of Tiny Colloidal Droplets … 471

of assembly of anisotropic colloids is highly desirable. Such assembly may ulti-

mately result into a facile route in realizing porous granules with aligned ordered pore
channels in the granules. Further, evaporative assembly of the anisotropic colloids
can also be coupled with electric or magnetic field in realizing tunable architecture
of granules. Apart from synthesis, the challenge remains in establishing an appro-
priate methodology in analysing small-angle scattering data from such granules with
complex internal structure. Here, it is interesting to mention that random jamming
of anisotropic particles is an interesting problem in general, and the established
theory about the interparticle correlation in such concentrated system of anisotropic
particles may be verified. Creation of Janus and core–shell granules by controlling
the interparticle interaction during assembly still remains a challenge. Atomization,
using three-fluid nozzle, of mixture of two colloids with contrasting hydrophilic
and hydrophobic characteristics and proper tuning of interparticle interactions may
result in such interesting morphology of the granules and thus needs attention. The
inherent procedure of spray drying technique often involves hydrodynamic parame-
ters apart from the thermodynamic parameters. Thus, it indeed remains a challenge
to differentiate the individual role of these parameters in tuning the shape of the
granules as well as the internal correlation of the nanoparticles. It is discernible from
the above sections that such porous granules have several potentials for technolog-
ical use including filtration and remediation depending on their shape and internal
structure. Thus, challenge remains to optimize the synthesis parameters to tune the
shape of the granules in addition to realizing extremely narrow distribution of their
size. It is worthy to mention that in standard spray drying process, the coalescence
of the droplets in the chamber at high feed rate remains an issue. Thus, experiments
on levitated single drying colloidal droplets in an ultrasonic levitator may be useful
in this regard while deciphering the role of various competitive physicochemical
parameters. Further, it is worth mentioning that the effects of confinement on various
chemical reaction equilibrium in nanoporous materials is an emerging field, and thus
these porous granules may be used as host materials for such chemical reaction.
In short, evaporation-induced assembly of the colloidal particles in contact-free
droplets can be realized through spray drying in order to obtain nano-structured
micro-granules. The granular shape, internal correlation, porosity, etc., can be tuned
by proper control of the governing parameters, including drying rate, viscosity,
surface tension, size of colloids, interparticle interaction, etc. Such porous granules
promise several technological applications.

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Chapter 12
Amphiphilic Self-Assembly
in the Synthesis and Processing
of Nanomaterials

Bijaideep Dutta, K. C. Barick, Gunjan Verma, Sipra Choudhury,

R. Ganguly, and P. A. Hassan

Abstract In recent years, the self-assembly of amphiphiles has been exploited to

create nanostructures with controlled architecture and morphology. Maneuvering the
intermolecular interactions between organic molecules offers attractive routes to tune
the morphology of self-assembled structures. These structures can act as templates
or nanoreactors for the creation of different inorganic materials. Amphiphiles have
a significant role in regulating the nucleation and growth process of nanomate-
rials during liquid-phase synthesis. Dynamic equilibrium structures of micelles are
employed in fine-tuning the colloidal stability, size distribution, and morphology of
a variety of inorganic materials, polymers, etc. The synthesis of inorganic mate-
rials in the presence of organic additives offers nanostructured composites with
superior properties. Microemulsions are employed as nanoreactors for the synthesis
of size-controlled nanoparticles of lipids, polymers, metals, etc. The application
of block copolymers in the production and ordering of nanomaterials is gaining
increasing attention. Molecular self-assembly has become a key tool in the fabrica-
tion of a variety of materials with potential applications in biomaterials development,
as carriers for drug delivery and templates for ordered nanostructures. Thus, this
chapter focuses on the principles of the self-assembly process, its role in control-
ling the structure of materials and its applications in the emerging areas of materials
development.

Keywords Self-assembly · Amphiphiles · Surfactants · Nanomaterials ·

Composite · Thin film

B. Dutta · K. C. Barick · G. Verma · S. Choudhury · R. Ganguly · P. A. Hassan (B)

Chemistry Division, Bhabha Atomic Research Centre, Mumbai, India
e-mail: [email protected]
Homi Bhabha National Institute, Mumbai 40094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 475
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_12
476 B. Dutta et al.

12.1 Introduction

Amphiphiles undergo spontaneous association into longer and meticulous arrange-

ments. In this process, molecular building blocks organize into a well-ordered struc-
ture, by virtue of specific mutual interactions [1, 2]. Self-assembly processes, related
to amphiphilic molecules, offer a unique platform for developing new nanoma-
terials for advanced scientific applications [3]. Nature created the maturation of
biomolecules from the primordial by self-assembly and eventually shaped a colossal
amount of complex biological systems. In biological systems, self-assembly is
omnipresent and the assembled structures have their exclusive cellular functions.
Thus, the self-assembly processes of amphiphiles have drawn significant interest
for the past few decades due to their explicit biological system mimicking compe-
tence such as assembly of proteins and lipids apace with comprehensive utilization
in biological applications. Contemporary advancements in the area of nanotech-
nology accelerated the amalgamation of elementary processes of self-association
with the progressive concept for the design of hierarchical nanostructures. Inaugu-
ration of stimuli-responsive amphiphilic assembly–disassembly mechanism grants
new methods for producing diverse bionanotechnology applications. Hence, studying
amphiphilic self-assembly is imperative to the present effort of nanotechnology as
this process caters to the direction of creating molecular building blocks [4–7].

12.2 Self-Assembly of Amphiphiles

Amphiphiles are natural or synthesized molecules that contain two distinct parts;
namely, a hydrophilic part (water-loving, polar) designated as “head” group and a
hydrophobic part (fat-loving, ‘tail” group), which are able to aggregate into various
nanostructures [8]. In conventional amphiphiles, the fat-loving tail often consists
of a long hydrocarbon chain (either saturated or unsaturated), whereas the water-
loving head can be ionic (cationic/anionic) or nonionic in nature. Typical hydrophilic
head groups of the nonionic surfactants are polyhydroxyl or polyether units. Unlike
ionic surfactants, these surfactants do not dissociate upon dissolving in an aqueous
medium and possess a wide range of properties based on the ratio of hydrophilic-
lipophilic balance (HLB). The most common nonionic surfactants are polyglycerol
alkyl ethers, ester-linked molecules, Spans (sorbitan esters), Brij and Tweens, etc.
Cationic surfactants are composed of a positively charged headgroup and a halide
counterpart. Cetyltrimethylammonium bromide (CTAB) and dodecyltrimethylam-
monium bromide (DTAB) are widely used cationic amphiphiles. Anionic surfactants
generally consist of negatively charged headgroups (carboxylate, sulfate, sulfonate
and phosphate) and positively charged counterparts (Na+ , K+ or NH4 + ions). Sodium
bis(2-ethylhexyl) sulfosuccinate, with the trade name Aerosol-OT (AOT) and sodium
dodecyl sulfate (SDS) are common examples of anionic surfactant. In zwitterionic
amphiphiles such as phospholipid phosphatidylcholine, the headgroups have both
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 477

Fig. 12.1 Structures of a few common surfactants under different categories

positive and negative charge moieties. The chemical structures of some surfactants
are shown in Fig. 12.1.
When dissolved in water, the polar head group of the surfactant interacts with the
water, whereas the nonpolar tail migrates toward the interface (either toward air or
nonpolar liquid). Thus, the interruption of cohesive energy at the interface helps the
formation of micelles, vesicles, lamellae, etc. Micelles are equilibrium assemblies of
amphiphile/ surfactant molecules dispersed in a liquid medium. Micelles are formed
when the concentration of amphiphile reaches above a threshold value known as
the critical micelle concentration (CMC). In a normal micelle, polar or ionic heads
create an outer shell in association with water, whereas nonpolar hydrophobic tails are
seized in the interior. The amphiphilic molecules can also form micelles in nonpolar
organic mediums. These micelle aggregates are termed as inverse or reverse micelles.
In inverse (reverse) micelles, the polar head groups are situated at the core, while the
tails extend outwards to the solvent medium. In addition to micelles, amphiphiles help
in the formation of microemulsions which are clear and thermodynamically stable
liquid dispersions containing water, oil and surfactant. Often, in microemulsions, the
aggregates are much larger in size. There are mainly three varieties of microemul-
sions such as direct (oil dispersed in water, o/w), reversed (water dispersed in oil,
w/o), and bicontinuous. They have large liquid cores surrounded by a surfactant
monolayer which stabilizes the dispersion. The microemulsion domains are typi-
cally studied by making ternary-phase diagrams mainly consisting of two immiscible
liquids and a surfactant. Most of the microemulsions use water and oil as two immis-
cible liquids. The shape of micelles is mainly spherical. However, other shapes like
bilayers, ellipsoids, and cylinders also exist. In a few cases, micelles can grow very
long and entangle like long-chain polymer. The amphiphiles do not always associate
with micelles and in some cases, they associate into extended flat lamellae without
forming a closed structure (so-called lamellar structure). Closed bilayer structures are
known as vesicles which encircle an aqueous pool and are surrounded by an aqueous
solution. It composes of a bilayer of amphipathic molecules, in which the hydrophilic
heads of the outer layer are exposed to the outer side, whereas the hydrophilic heads
478 B. Dutta et al.

Fig. 12.2 Schematic representation of different structures formed by amphiphiles

of the inner layer make the inner hydrophilic core. The hydrophobic tails are situ-
ated in between the bilayers of two concentric circles. The schematic representation
of micelles, vesicles, and lamellae is shown in Fig. 12.2. The formation of these
self-assembled structures based on critical packing parameters is discussed in the
following section.

12.2.1 Morphological Control of Self-Assembled Structures

12.2.1.1 Surfactant Assemblies

The self-association of amphiphilic molecules results in a large variety of struc-

tures such as spherical micelles, anisotropic micelles, bilayers, vesicles, liposomes,
microemulsions, liquid crystalline dispersions, etc. The morphology of these aggre-
gates is governed by the interaction of hydrophilic and hydrophobic forces respon-
sible for the self-assembly process [9, 10]. The hydrophobic effect due to the hydro-
carbon tails favors the self-assembly process. On the other hand, the solvation of the
hydrophilic head group restricts the packing of amphiphilic molecules and hence
opposes the self-assembly. The electrostatic repulsion between the head groups
of ionic surfactants also contributes toward limiting the growth of self-assembled
structure. In general, the stability of association structures in solution depends on
the hydration of the polar head groups and insertion of the nonpolar tail in the
solvent. The amphiphile self-assemble into various supramolecular structures mainly
due to the combined effect of various noncovalent interactions such as solvation,
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 479

hydrogen bonding, hydrophobic effect, etc. The other important interparticle inter-
action involved in amphiphile self-assembly, specifically with ionic amphiphiles
self-assembly is denoted by the Derjaguin, Landau, Vervey, and Overbeek (DLVO)
theory [11]. This theory is the key foundation to rationalize the interfacial forces
acted among charged amphiphiles and explain their agglomeration behavior in solu-
tion [12]. Further, the geometry (size and shape) of self-assembled structures depends
on various additional factors like surfactant concentration, nature of surfactant, ionic
strength of the medium, nature of the counterion, temperature, pH and nature of
the additives, etc. The prediction of the geometry of a self-assembled structure
in a surfactant-water system was a subject of major interest in the past. Conse-
quently, some models have been proposed, which are helpful in predicting the shape
of self-assembled structures in the surfactant-water system. The morphology of self-
assemblies is satisfactorily explained by the geometric packing models [13, 14].
According to this model, the three main factors that dictate the geometry of a surfac-
tant aggregate are length (l) and the volume (v) of the hydrophobic chain and the
effective interfacial (head group) area (ao ) of the surfactant molecule. For a hydro-
carbon chain, the length (l) and volume (v) of the surfactant tail can be found by the
Tanford formulae using the following equations:

v = 27.4 + 26.9n (Å)3 (12.1)

1 = 1.5 + 1.265n (Å) (12.2)

“n” represents is the number of carbon atoms in the linear alkyl chain.
The head group area of the surfactant molecule can be obtained from surface
tension (γ) data using Gibbs adsorption isotherm. Surfactants are amphiphilic in
nature and in their presence, the surface tension of water decreases due to the adsorp-
tion of molecules at the surface. A steady reduction in γ followed by a linear decrease
can be seen in the plot of γ versus log C (concentration of surfactant). Once CMC
is attained, no change in γ occurs. From the slope of the linear portion of γ versus
-logC plot, the surface excess concentration  (number of moles of surfactants per
unit area (m2 ) at the interface) can be determined using Gibb’s equation.
According to the Gibbs relationship, at constant temperature, the surface
tension γ and the surface excess () for a single surfactant component can be simply
expressed as follows:

dγ d log C = −2.303RT (12.3)

where C, R, and T represent the surfactant concentration, gas constant, and absolute
temperature, respectively.
The area per molecule can be obtained from , by using the relation,
  
Area per molecules (ao ) = 1 NA m2 (12.4)
480 B. Dutta et al.

  
or 1018 NA nm2 (12.5)

where NA is Avogadro’s number. For ionic surfactants having carboxylate, sulfate,

headgroups, etc., the area per surfactant is usually in the range of 0.4 nm2 , while
for nonionic surfactants it is much higher (1–2 nm2 ). Israelachivili and coworkers
[14] suggested that the geometry of aggregated structures formed in the solution
is a resultant of the optimum packing of molecules into aggregates. The optimum
packing of surfactants into a surfactant assembly can be defined by a dimensionless
parameter known as the critical packing parameter. The critical packing parameter
(N) depends on the length (l) and volume (v) of the hydrophobic part, and the effective
head group area (ao ) of the surfactant molecule.

N = v ao 1 (12.6)

The packing parameter for different geometries of aggregates is different as

per simple geometric calculations. For instance, the volume and surface area of
a spherical micelle of radius, R and aggregation number, N can be expressed as

4 3π R3 = Nv (12.7)

4π R2 = Nao (12.8)

Here v and ao are the volume and headgroup area of the single surfactant molecule.
Since the maximum radius of a spherical micelle can be the length of the
hydrocarbon part, l. by rearranging the Eqs. 12.5 and 12.6, we get

R = 3v ao ≤ 1 (12.9)

or in in the form of packing parameter, we can write it as

 
v ao 1 ≤ 1 3 (12.10)

Therefore, if the value of N is less than 1/3, the aggregates will preferably result
in spherical geometry. In a similar manner, if the packing parameter is calculated
for cylindrical geometry, N will be between 1/3 and 1/2, while for curved bilayer or
vesicles, it is 1/2. For flat bilayers, the packing parameter approaches 1, whereas, for
reverse micelles, the value of N is > 1.
In the case of vesicles, bilayers etc., there is another factor known as curvature
energy, which is very crucial in controlling the geometry of the aggregates. As per
the model of Helfrich [15], the free energy (F) per unit area (A) of a bilayer is related
to the bilayer curvature by the equation
 
F A = 1 2κs (c1 + c2 − cs )2 (12.11)
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 481

where c1 and c2 represent two principal curvatures of the bilayer and cs represents
spontaneous curvature. The rigidity of the bilayer is related to κs , the bending modulus
which is of the order of kβT, where kβ is Boltzmann constant. The different aggregate
structure which can be anticipated from the packing parameter is shown in Fig. 12.3.
It is worth mentioning that the packing considerations of the surfactant molecule
are built in the spontaneous curvature of the bilayers. For instance, if the interac-
tion between the polar head groups of the surfactant results in a smaller packing
area as compared to the hydrophobic tail interactions, the surfactant monolayer will
tend to curve in such a way that the polar headgroups are on the inner side of the
monolayer. On the other hand, if the interaction between the headgroups leads to
the larger packing in comparison to the tail–tail interaction, the polar headgroups
arrange themselves on the outer side of the monolayer.

Fig. 12.3 Different aggregate structures which can be predicted from critical packing factor
482 B. Dutta et al.

12.2.1.2 Block Copolymer

The concept of amphiphile can be extended to macromolecular polymer-based

amphiphiles by linking hydrophilic/hydrophobic polymer blocks. Block copolymers
are mainly macromolecular compounds having two or more chemically dissim-
ilar blocks conjugated to each other by covalent bonds. These materials exhibit
amphiphilic character when the two blocks show different polarities [16]. The inves-
tigation of self-assembly characteristics of these compounds is an interesting research
area to explore due to their rich structural polymorphism and different applications
such as lithography for microelectronics, photovoltaics, drug delivery, nanostructure
formation, etc. [16–19]. Further, block copolymer self-assembly can produce well-
ordered structures of different morphologies such as spheres, cylinders, lamellae,
vesicles, bicontinuous structures, and many other complexes or hierarchical assem-
blies [20]. Depending on the absolute and relative block lengths, the nature and
architecture of the blocks, these copolymers form a diverse set of nanostructures
that range from discrete micelles to vesicles to even gel-forming continuous network
structures [16]. Recent progress in the synthesis route facilitate the preparation of
block copolymers with desired molecular weights, compositions and architectures
[16]. Like conventional surfactants, the self-assembly of these compounds in an
aqueous medium is entropy driven arising out of gain in entropy due to destruction
of water structures around the hydrophobic blocks [16].
Figure 12.4 shows a typical phase diagram of a block copolymer–water two-
component system. At low and very high block copolymer concentrations normal and
reverse micelles are formed. Liquid crystalline structures with different microstruc-
tures are formed at copolymer concentrations in between these two extremes [21].
Micelles formed are usually core–shell types with the core comprising hydrophobic
blocks and the corona comprising the hydrophilic blocks.
Self-assembly behavior of many of these block copolymers is strongly dependent
on temperature because of the differential solubility of the different blocks [22].
The solubility of the blocks in general decreases with an increase in temperature
and they show phase separation at characteristic temperatures called cloud points

Multiphase
Temperature

Cloud Point
L2: Reverse
Micelles
L1 I1 H1
I1: Cubic phase
Lα
L2
0 Copolymer Concentration 100
L1: Micellar solution H1: Hexagonal phase Lα: Lamellar phase

Fig. 12.4 Typical phase diagram of a block copolymer–water two-component system

12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 483

[22]. Besides, micellar structural changes from spherical to rod-like or to disk-like

shapes or to layered vesicle-like structures are also observed on approaching the
phase separation temperatures [23]. These are attributed to changing critical packing
parameters of the self-assembled structures as a function of temperature. Some of
the block copolymers also exhibit critical behavior because of the onset of micellar
attractive interaction and resulting micellar cluster formation on the verge of phase
separation [24].
Self-assembly characteristics of block copolymers in water are also sensitive to the
presence of additives that modulate the solubility characteristics of the blocks. Water
structure making salts, hydrophobic solvents and solvents like glycerol increases
the hydrophobicity of the copolymers and promotes the formation of aggregates
[25]. Water structure breaking salts and solvents like ethanol, on the other hand,
have disrupting influence on the self-assembled structure formation [25]. Triblock
copolymers like Pluronics form a rich set of self-assembled structures in water-block
copolymer–oil three-component systems [21].

12.2.2 Kinetics of Micellization of Amphiphiles

The primary requirement for the formation of self-assembly of amphiphile is the

lowest free energy state at equilibrium. Generally, the self-assembly of the struc-
ture of amphiphile has lower entropy than the individual counterparts. Thus, the
self-assembly of amphiphilic molecules is governed by the interfacial energy of the
micellar core with solvent and the conformational distortion energy of the soluble
chains and the favorable increase in entropy of the solvent molecules. Micelles
are generally considered as spherically aggregated inert structures of amphiphile
molecules. However, they are in dynamic equilibrium with individual amphiphile
which is continuously replaced among bulk and micelles. Further, the micelles
themselves undergo dissolution and reforming. Therefore, there are two relaxation
processes occurred in micelle solutions [26]. The fast relaxation process of relaxation
time, τ1 (order of microseconds) is related to the exchange of amphiphile monomers
among micelles and the surrounding bulk phase through the collision process. The
second slow relaxation time, τ2 (in the order of milliseconds to minutes) is asso-
ciated with the process of complete disruption of micelles. The micellar relaxation
kinetics are dependent on the concentration of micelle, temperature, and pressure of
the micellar solution. A schematic illustration of the two relaxation times, τ1 and τ2
related to micelle formation is shown in Fig. 12.5.
Hadgiivanova et al. [27] demonstrated a new free-energy-based theoretical
approximation to the kinetics of amphiphile micellization, where the different stages
of aggregation are considered as constrained path ways on a single free energy land-
scape. They have identified three stages of micelle formation such as nucleation,
growth, and relaxation steps of well-separated time. The first stage is involved with
homogeneous nucleation of micelles, which are dependent on the concentration of
surfactant, rate of nucleation, and critical size of nuclei. The first stage is much longer
484 B. Dutta et al.

Fig. 12.5 Schematic illustration of the two relaxation times, τ1 and τ2 for an amphiphile solution
above CMC (reproduced with permission A. Patist et al., Colloids Surf. A: Physicochem. Eng.
Asp. 176 (2001) 3–16, Copyright © 2001 Elsevier Science B. V. [26]

than the other two as it is an activated process. The growth stage is diffusion limited
for the concentration of surfactant slightly higher than CMC and it is either diffusion
limited or kinetically limited for higher concentrations. Depending on the surfactant
concentration, the micelle size may be either bigger or smaller than its equilibrium
size at the end of the growth stage. In the relaxation stage, micelles relax to the
equilibrium size by fission (a decrease in aggregate size) or fusion (an enhancement
in aggregate concentration) process.
Kinetics of formation of block copolymer self-assembled aggregates is slower
by a few orders of magnitude than that of ionic surfactants owing to their higher
molecular mass [28]. Many of the aqueous block copolymer systems thus exhibit
time-dependent micellar structural changes and even leads to the formation of kineti-
cally arrested metastable systems [29, 30]. Quite expectedly such tendencies increase
with an increase in hydrophobicity and molecular weight of the copolymers making
their kinetics of aggregate formation increasingly sluggish.

12.3 Principle of Nanomaterials Synthesis

The nanostructured materials deal with the property-decisive phenomenon that

happens in typically the size range of 1–100 nm. The most important part to be
focused on is to what the accord between their structures and compositions is, and
how their interface supervises the property of the material as a whole [31]. Mainly
two different types of methods are often used for producing nanostructures. The first
one is the bottom-up method where the material is manufactured from atomic or
molecular species through chemical reactions, which enables the particles to grow
in size to produce nano-sized structures. These nanostructures can sometimes form
in parallel and be nearly identical, with no long-range order. [32, 33]. An opposite
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 485

approach is to break a bulk material into smaller pieces using chemical, mechanical
or other forms of energy, called the top-down method [34]. In this, lithographic tech-
niques are used to design materials. Materials science desires a handy policy to link
these two approaches and to permit the production of materials with a satisfactory
resolution [35, 36]. There are many instances of self-assembly connecting top-down
and bottom-up constructions [37]. However, bottom-up self-assembly is surprisingly
beneficial because it grants the accumulation of structures too small to be manipulated
independently into the ordered arrangements or patterns. Researchers have developed
varieties of soft-chemical approaches based on bottom-up self-assembly to formu-
late nanoparticles of well-defined composition, shape, and size. These soft-chemical
approaches for the preparation of nanomaterials include the coprecipitation method,
sol–gel process, hydrothermal synthesis, high-temperature reactions, microwave
irradiation synthesis and polyol method, sonochemical synthesis, microemulsion,
etc. [38–40]. In all these synthesis methodologies, the formation of nanoparticles
undergoes two important processes, namely nucleation and growth.

12.3.1 Nucleation

In soft-chemical approaches, the nucleation process kicks off the evolution of a

new phase from a solution. The atoms or molecules of the reactants reshuffle into a
cluster of products, which has the ability to grow irreversibly to a macroscopically
bigger size. The cluster or group is entitled as a nucleus or critical nuclei [41].
When nucleation occurs without the presence of foreign particles or crystals in the
solution, it is termed as homogeneous nucleation. On the other hand, if the nucleation
is induced by the existence of any foreign particles in the solution, it is termed as
heterogeneous nucleation. These two together are termed as primary nucleation. In
contrary to primary nucleation, secondary nucleation comes into the picture when
crystals of the same substance induce nucleation.
The main driving force behind nucleation and subsequent growth of a crystal is
supersaturation. This depends on the chemical potential of a molecule in solution
(μs ) and that in the bulk of the crystal phase (μc ) as follows:

μ = μs − μc (12.12)

Thus, using thermodynamics we can write from Eq. (12.12):

μ = kβ T ln S (12.13)

where T is the absolute temperature, k is the Boltzmann constant and S is the super-
saturation ratio [42]. The solution is termed as supersaturated, when μ > 0, thereby
confirming the possibility of nucleation and/or growth, whereas μ < 0 suggests
486 B. Dutta et al.

that the solution is under saturated and dissolution will take place. Now, this super-
saturation ratio can have different forms based on the system under consideration.
The mathematical expression for the degree of supersaturation is given below:

aini
S= ni (12.14)
ai,e

where ni is the number of ith ions in the molecule of the crystal, and ai and ai,e are
the activities of the ith species in supersaturated solution and in equilibrium state,
respectively.
Now, let us look at the thermodynamics of homogeneous nuclei formation.
Figure 12.6 shows the (a) free energy diagram for nucleation explaining the exis-
tence of a “critical nucleus” and (b) a representative plot of nucleation rate, J as a
function of supersaturation, S showing critical supersaturation. The total free energy
of nanoparticles is the summation of the bulk free energy (Gv ) and surface free
energy (GS ), as shown in Fig. 12.6a [43]. Thus, for a spherical particle with surface
energy γ , radius r, and the free energy of the bulk crystal Gv , the total free energy
G is given by Eq. 12.5. The bulk free energy (Gv ) depends on the degree of
supersaturation and is given by Eq. 12.16, where k β is Boltzmann’s constant, S is the
supersaturation ratio and V is its molar volume.

4
G = 4πr 2 γ + πr 3 G v (12.15)
3
−kβ T ln(S)
G v = (12.16)
V
The surface free energy and crystal free energy are always positive and negative,
respectively. Thus, a maximum free energy can be found which a nucleus will surpass
to produce a stable nucleus. This critical value of radius can be obtained by equating
the first derivative of G with respect to r equal to zero. The critical radius which
indicates the minimum size at which a particle can form in the solution without getting
dissolved is given in Eq. 12.18. It is evident from the equation that the possibility of
nucleation in a given system increases with the increase in supersaturation as critical
radius decrease [44].

4
G crit = γ πrcrit
2
= G homo
crit (12.17)
3
2γ 2γ V
rcrit = − = (12.18)
G v kβ T ln S

The rate of nucleation, J which is defined as the number of nuclei formed per unit
time per unit volume is expressed by an Arrhenius-type equation (Eq. 12.19) with
the activation barrier equal to Gcrit :
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 487

Fig. 12.6 a Schematic representation of the free energy diagram for nucleation explaining the
existence of a “critical nucleus” and b a representative plot of nucleation rate, J as a function of
supersaturation, S showing critical supersaturation

J = Ae−G crit /kβ T (12.19)

From a representative plot of J as a function of S (Fig. 12.6b), we can clearly see

that up to a certain value of supersaturation, nucleation rate is essentially zero and
then it starts increasing exponentially from there. This critical supersaturation (Δμc )
point describes the allegedly metastable zone showing crystal growth can advance
without having collateral nucleation.
Equation 12.17 and 12.18 have shown us that the G crit and rcrit both are highly
dependent on the surface free energy parameter, i.e., γ . Thus, any change in this
parameter will have a certain effect on the nucleation process. Presence of foreign
substances decreases the value of G crit and rcrit at constant supersaturation and
making nucleation more favorable [45]. Decrease in γ also declines the value of crit-
ical supersaturation, thus making the heterogeneous nucleation much more feasible
than homogeneous nucleation at low supersaturated states. Now, this reduction in
surface free energy is maximum when the foreign substance and the crystallizing
substance are identical which leads to secondary nucleation.

12.3.2 Growth

Crystal growth is another intricate process where an atom or molecule is deposited

over the surface of the crystal, which leads to the increase of size. This growth
process can either be reaction limited or diffusion limited. Most of the cases have
shown to be diffusion controlled only where temperature and concentration gradient
has played a major role in defining the rate of growth as the new material is added to
the surface of the particle [46]. There are various theories of nucleation and growth
488 B. Dutta et al.

of nanoparticles available in the literature. We will be discussing a few here to get

an overall idea about the same.
(a) LaMer mechanism
The inaugural idea of nucleation and growth was given by LaMer [47] where
he separated the nucleation and growth into two different stages (Fig. 12.7). He
investigated the preparation of sulfur sols from the decomposition of sodium
thiosulphate and proposed two distinct steps where nucleation is the formation
of free sulfur from thiosulphate and growth is the formation of sulfur sols. The
full process is further fractioned into three parts. (A) at first, the concentration
of the free monomer is raised in solution, (B) the second part is the “burst
nucleation” that reduces the free monomer concentration and at this point,
nucleation is almost arrested due to very low monomer concentration, (C)
the third portion is diffusion mediated growth in the solution. Changes in the
reactant concentration during all three stages are depicted in Fig. 12.7 [48, 49].
(b) Ostwald ripening
In 1900 another theory was published to describe the growth phenomenon of
crystal in solution which was termed as Ostwald ripening [50]. In his theory,
he described the crystal growth where smaller particles are being consumed by
larger particles and the main cause behind this is the solubility of nanoparticles
in size-dependent manner. Greater solubility and the surface energy of smaller
nanoparticles in solution enforce them to redissolve and grow larger ones even
larger. A detailed mathematical explanation of Ostwald ripening is described
by different research groups [51, 52]. Digestive ripening is basically just the

Fig. 12.7 Schematic illustration of the changes in reactant concentration as per LaMer mechanism
of nucleation and growth
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 489

opposite of Ostwald ripening where larger particles redissolve and smaller

particles grow [53].
(c) Finke–Watzky mechanism
Another mechanism was proposed for describing nucleation and growth of
nanoparticles which is called as the Finke–Watzky two-step mechanism. In
this nonclassical process, nucleation and growth both occur simultaneously
[54]. This model fits well in various systems including the synthesis of iridium,
platinum, ruthenium, and rhodium [55–57].

12.3.3 Role of Surfactants in Nanomaterials Synthesis

Irrespective of the synthesis approach, the preparation of nanomaterials always

comprises nucleation and growth processes. The separation between them is tremen-
dously difficult in the aqueous-based chemical synthesis approaches. The polydis-
persity of nanoparticles is remarkably decreased when nucleation and growth steps
are well separated, which is extremely difficult to achieve. As far as thermodynamics
is concerned, without any stabilizer the agglomeration of smaller particles in solu-
tion is inevitable. This agglomeration can take place at any stage of synthesis and
thus making it a subject of investigation. Mainly two kinds of stabilization can be
imparted to nanoparticles. First, electrostatic stabilization by means of repulsion
between charged species at the surface and secondly, steric stabilization by virtue of
surface fictionalization or capping the surface by long-chain moieties such as surfac-
tants and polymers [58]. The second one is quite common and mostly followed due
to its easy fabrication and chemical stability in a wide pH range [59].
Various surfactant molecules are used for the stabilization of nanoparticles in solu-
tion and the prevention of nanoparticles aggregation in solution by forming robust
coating around the particles during synthesis or post-synthesis process. In addition
to this, surfactant amphiphiles are also used as templates or nanoreactors for the
synthesis of different shaped controlled nanoparticles [60]. The tuning of the nucle-
ation process with the assistance of surfactant amphiphiles has a significant degree
of control over the size distribution of the synthesized nanoparticles. Therefore,
nanoparticles synthesis by surfactant self-assembly has been extensively used due to
its superior ability in controlling the structural morphology and size of nanoparticles
[61–63]. Specifically, nanoparticles–amphiphiles soft interactions are accountable
for nanoparticles functionalization, colloidal and chemical stability procedures.
490 B. Dutta et al.

12.4 Self-Assemblies as a Template for Nanomaterials

Synthesis

12.4.1 Surfactant Assisted Synthesis

Self-assembly process is ubiquitous in nature. There are several examples in

living organisms, where the self-assembly process fabricates unique structures. For
example, in bones, teeth, spines, shells, etc., the biomineralization takes place through
a self-assembly process on a protein scaffold. In these structures, the organic template
and inorganic minerals interact at molecular level and results in the structures with
remarkable properties in spite of having very soft templates and brittle minerals
as the constituting elements. The use of synthetic templates, inspired by nature is
evolving as one of the promising routes for the fabrication of novel materials with
controlled architecture inspired by nature. Recently, there is a growing interest in
the preparation of hollow inorganic nanomaterials having well-defined geometrical
features because of their characteristic properties such as controlled geometry and
pore size, low density, huge specific area, and high mechanical and thermal stability.
Owing to their fascinating properties, these hollow nanomaterials have tremendous
potential for diverse technological applications ranging from everyday materials and
processes, medical and health care, energy applications, electronics, and information
technology applications to environmental remediation. A number of materials have
been involved in pharmaceutical formulations, cosmetics, paint industry, catalysis,
as well as for dyes and ink. The geometrical parameters of nanostructures including
size, shape, composition, architecture, and surface area are some of the most impor-
tant parameters to define various important properties of inorganic nanomaterials.
Hence a lot of efforts have been made to exploit the fabrication of well-defined inor-
ganic nanostructures using various methods involving physical as well as chemical
routes. The involvement of sacrificial templates such as polymeric nanoparticles,
self-assembled structures, etc., in the fabrication of nanomaterials with controlled
size, morphology, and surface properties have also emerged as a growing field.
The self-assembly templating method has revolutionized the fabrication of smaller
well-defined hollow nanomaterials having diameters in the nanometer range. Self-
assemblies of amphiphilic molecules are one of the most promising templates to
synthesize nanomaterials having defined architecture and high surface area. As
discussed above, the self-association of amphiphilic molecules such as ionic/nonionic
surfactants results in different structures and the morphology of these self-assembled
structures is decided by a number of factors including, surfactant concentration,
temperature, and nature of surfactant molecule as well as additives, if any. Self-
assembled structures are dynamic in nature and are very receptive to the changes made
in the constituting solutions. Hence, their microstructure and properties can be tuned
easily by changing the concentration of surfactant, addition of inorganic electrolytes
or organic additives as well as by varying the pH and temperature of the medium. For
example, in the case of ionic micelles, the addition of inorganic electrolytes decreases
intermicellar repulsion as it screens the charge at the micelle surface. This changes
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 491

the packing parameter, which in turn changes the morphology of the aggregates.
Organic hydrotropes (hydrotropes are used to solubilize hydrophobic compounds
in water medium by means other than micellar solubilization) are very effective in
inducing the morphological changes in ionic aggregates by decreasing the surface
charge at the micellar surface. The swelling of the micelles also takes place due to
the solubilization of organic additives in the hydrophobic cores of the aggregates.
Similarly, the change in the temperature of the solution results in the alteration of
the head group area of the ionic and nonionic surfactants. As a consequence, the
packing parameter of the surfactant changes and results in a change in the size and
shape of the aggregates [64–69]. Hence, one of the major advantages of using self-
assemblies as templates is that the morphology and porosity of the materials can be
tuned to the desired extent by tuning the parameters affecting the microstructure of
self-assemblies. Amphiphilic block copolymers have also been broadly employed for
designing hollow nanostructures and ordered mesoporous materials. The polymeric
micelles have a core composed of a hydrophobic block of copolymers and corona
made up of the hydrophilic group of copolymers. The core of the micelles acts as a
template of the hollow nanostructures and corona acts as a reservoir of the inorganic
precursors [70].
The synthesis of inorganic materials, such as silica, titania, alumina, hydrox-
yapatite, metal oxide, metal phosphate, etc., using self-assembled structures as a
template, has been a topic of tremendous importance [71]. There are several reports
in which the employment of self-assembly during synthesis has resulted in materials
with controlled geometry, and defined porous structure and are found to be very
promising for diverse applications. MCM-41, belonging to the family of silicates
is a well-known porous material with very high surface areas of the order of 1000
m2 /g with a pore size ranging from 2 to 20 nm and ordered arrays of cylindrical
mesopores with very regular pore morphology [72]. During the synthesis of MCM-
41, the hexagonal arrays of rod-like micelles of cationic surfactant, cetyltrimethy-
lammonium bromide are employed as a template. The synthesis of material takes
place at the surface of the templates and during calcination, the organic template
is removed leaving a highly ordered porous material. Due to the large surface area
of these materials, the possibility of reactant molecules reacting with the catalyst
surface increases. These materials are widely used for catalytic applications. Since,
the discovery of mesoporous molecular sieves by Kuroda et al., known as KSW-1 [73]
and FSM-16, [74] and by Exxon Mobil, called M41S [72] a great deal of attention
has been given to the investigation of mesoporous silica materials due to their wide
range of applications. Recently, hollow silica spheres (HSS) with significant inner
spaces, high specific surface area, mesoporous structure, and amorphous shell were
synthesized using cetyltrimethylammonium bromide micelles as a soft template. The
composite membrane prepared by mixing HSS with waterborne polyurethane showed
improved water vapor permeability, water resistance, and mechanical performance
[75]. In another study, hollow silica nanospheres with a highly uniform size were
prepared using a micellar template with a core–shell-corona architecture composed of
a triblock copolymer, poly (styrene-b-2-vinyl pyridine-b-ethylene oxide). The empty
space in the hollow particle could be regulated by the size of the core regulated by
492 B. Dutta et al.

the chain length of the polystyrene block, while the shell thickness of nanospheres
could be tuned by altering the concentration of the inorganic precursors [76].
Porous hydroxyapatite has attracted increasing interest because of its biocompat-
ibility, bioactivity, osteointegration, osteoconductivity, and composition similarity
with human bones and teeth. Hydroxyapatite is an inorganic material belonging to the
apatite group, which is comprised of calcium, phosphate, and hydroxide. The chem-
ical formula of hydroxyapatite is Ca5 (PO4 )3 (OH), which is commonly written as
Ca10 (PO4 )6 (OH)2 suggesting the presence of two entities in the crystal unit cell. Bone
is a hybrid structure comprised of inorganic needle-shaped carbonated and calcium-
deficient hydroxyapatite nanocrystals and the organic part is mainly composed of the
collagen matrix. The collagen matrix controls the nanoscale structure of hydroxyap-
atite and dictates its properties. Inspired by biomineralization, a great deal of attention
has been paid by the chemists to the biomimetic synthesis of hydroxyapatite having
controlled dimensional, morphological, and architectural features by using nanos-
tructured self-assemblies as templates. The involvement of synthetic polymers and
surfactant assemblies similar to that of collagen matrix during synthesis of hydrox-
yapatite could mimic biomineralization and leads to materials with characteristic
morphology and porosity. Due to its excellent properties, synthetic hydroxyapatite
has been extensively used in a range of biomedical applications including repairing
and regeneration of damaged bones, as a filler for bone defects, and to replace ampu-
tated bones and as a bone graft. Hydroxyapatite has also been applied as a coating
material to prosthetic implants in order to provide biocompatibility and bioactivity
to implants.
The morphology and porosity of hydroxyapatite play an important role in making
it a suitable material for biomedical applications. The presence of pores in hydrox-
yapatite supports the in-growth of bone tissue and full assimilation with the bones.
Recently, porous hydroxyapatite is also being considered as a potential carrier for
various molecules such as drugs, osteogenic agents, etc., which are used in treating
bone infection, diseases, etc. There are several reports, which show the prepara-
tion of hydroxyapatite with controllable properties and porous structure using self-
assemblies as templates. Stupp and coworkers employed ordered nanofibrous self-
assemblies of peptide amphiphiles [77, 78] as nucleating centers for the mineral-
ization of hydroxyapatite. They have also synthesized apatite-based materials using
homopolymer poly(amino acids) and synthetic polyelectrolytes [79]. Self-assemblies
of surfactants, as well as block copolymers, have been found very promising in
dictating the geometry and porosity of hydroxyapatite. The usage of spherical
micelles of cationic surfactant cetrimide as a template during synthesis resulted
in spherical particles of hydroxyapatite, while in the presence of rod-like micelles
of cetyltrimethylammonium bromide, the hydroxyapatite nanoparticles formed were
rod-shaped [80–82]. Similarly, well-aligned hydroxyapatite nanorods were formed
due to the templating by hexagonal liquid crystalline phase of a nonionic surfactant,
Triton X-100, [83]. Several groups have also prepared hydroxyapatite nanostructures
using self-assemblies as a template for drug delivery applications. Calcium-deficient
hydroxyapatite hollow nanorods having mesopores on their surface were prepared
using P123 and tween-60 as templates. The nanorods showed enhanced protein load
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 493

and sustained release behavior with a cumulative release of 84.2% over a period of
72 h [84]. In another study, hydroxyapatite hollow nanoparticles (HA HNPs) prepared
using core–shell micelles composed of pluronic P123 and Tween-60 showed much
higher drug loading for vancomycin drug as compared to nanoparticles prepared
in the absence of micelles. In the presence of citric acid used as a cosurfactant,
the morphology of the HA HNPs changed from nanospheres to nanotubes and the
drug loading efficiency improved further due to the presence of a layer of citrate
molecules on the hydroxyapatite surface [85]. An anticancer drug paclitaxel loaded
in hydroxyapatite-collagen composites showed enhanced toxicity toward highly
metastatic MDA-MB-231 cells in comparison to that of poorly metastatic MCF-
7 cells through in-vitro studies. However, the collagen-containing free paclitaxel in
the absence of hydroxyapatite was nontoxic toward both the cancer cells suggesting
that hydroxyapatite-collagen composite could be employed as a promising drug
carrier for paclitaxel [86]. The textural properties of hollow mesoporous carbonated
HAp microsphere (CHAM) fabricated using sodium dodecyl sulfate (SDS) mediated
precipitation can be controlled by changing the concentration of SDS. The CHAMs
showed excellent biodegradability, high loading efficiency for cis-diammineplatinum
(II) dichloride and a pH-dependent sustained release of drug. In vitro studies showed
that drug-loaded CHAMs have high toxicity toward human squamous cell carcinoma
[87].
Mesoporous “transition metal oxides” in particular, titania (TiO2 ) have also drawn
the attention due to the their intrinsic optical and electronic properties. The meso-
porous titania shows extraordinary performance in applications such as photocatal-
ysis and optical devices, which has made it to play a substantial role in solar-energy-
based photovoltaic devices. Similarly, the high surface area, larger pore volume,
and ordered pore structure of mesoporous TiO2 make them desirable for various
applications. For example, mesoporous TiO2 (anatase phase) is highly desirable in
photovoltaic applications as the photoanodes as high surface area mesoporous TiO2
maximizes the dye-loading capacity and results in high photovoltaic efficiency [87].
There are several reports presenting the surfactant template-assisted synthesis of
mesoporous TiO2 [88]. Several liquid-crystalline phases of ionic/nonionic surfac-
tants are being employed as a template during the synthesis of mesoporous TiO2
[89].

12.4.2 Block Copolymer Mediated Nanomaterial Synthesis

Numerous nano-sized self-assembled structures that are formed by block copolymers

are good templating agents for generating nanostructured materials with desired and
tunable structural properties. Various types of nanostructures formed by using these
materials as templates are discussed here. Of late, block copolymer micellar systems
are the preferred choice over those of classical surfactants for use as nanocontainers
to form metal nanoparticles because of their better kinetic stability and a more robust
core-corona structure, which provide better stability to the nano particles against
494 B. Dutta et al.

Ostwald ripening [16, 90, 91]. By incorporating coordination properties in the consti-
tuting blocks, we can also induce selectivity in nano particle formation [16, 90, 91].
When physically adsorbed on metal nanoparticles, these block copolymers can stabi-
lize them and in addition, can facilitate their integration into different systems where
hydrophobic surface poses a problem [92]. Some block copolymers act as reductants
thus avoiding the use of environmentally hazardous reagents and the material proper-
ties can be tuned by simply changing the composition of the block copolymers [93].
The presence of block copolymers like Pluronic F127 helps in promoting the forma-
tion of nanonetwork and dendritic metal structures with tunable surface properties
[94]. In these cases, the copolymer used at a concentration below its CMC indicating
that the formation and growth of metal nanostructure occurred along the unaggregated
free copolymer chains. Finally, metal nanoparticles formed and dispersed in block
copolymer three-dimensional liquid crystalline structures can make nanocomposite
materials with suitable mechanical, optical, and electrical properties [95, 96].
According to IUPAC notation, a mesoporous material consists of pores with diam-
eters in the range of 2–50 nm. Apart from silica, which is the most commonly used
material for this, other materials like alumina, carbon niobium, tantalum, titanium,
zirconium, cerium, and tin too reported to form mesoporous structure [97, 98]. Meso-
porous materials have tremendous applications in drug delivery, catalysis, biosensing,
ion exchange, optics, and photovoltaics. Block copolymers are widely used to form
mesoporous oxides because of their nontoxic and biodegradable nature.
Traditionally, top-down lithographic techniques were used to form structural
patterns at nanoscale. These methods are expensive and are inherently slow in pattern
writing. Bottom-up self-assembly processes involving block copolymers are thus
being considered as a suitable alternative to these traditional methods. Selective
etching of one block from the self-assembled structures formed in block copolymer
films can be used to form templates for making nanopatterns of magnetic and metal
nanoparticles for application in photovoltaics, biosensing, etc. [99].

12.5 Microemulsions as Nanoreactors for Synthesis

of Nanomaterials

Schulman et al. proposed the word microemulsion in 1959 [100]. It is a special

case of reverse micelles. Reverse micelles are formed when surfactant molecules are
dispersed in organic solvents [101]. These spherical aggregates having polar head
groups pointed toward the core can also be formed in presence of water molecules.
However, larger aggregates are generally appeared in presence of water molecules.
If the water to surfactant ratio is greater than 15 (W° > 15), then aggregates formed
contain a large amount of water molecules, which are termed as microemulsions
[102]. Microemulsions are easily differentiated from emulsions through their trans-
parency, low viscosity, and thermodynamic stability. Microemulsions consist of two
immiscible liquid (oil and water) phases, where one phase is dispersed in the other
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 495

by an interfacial film of surfactant molecules. In microemulsions, both immiscible

phases are brought into a macroscopically homogeneous and thermodynamically
stable single phase with the help of interfacial surfactants film accumulated at the
oil–water interface. Microemulsion contains at minimum three components, such
as water (a polar phase), oil (a nonpolar phase), and a surfactant. In many cases, a
cosurfactant or cosolvent is added to form a microemulsion. Based on the content of
these components and hydrophilic-lipophilic balance (HLB) value, the microdroplets
exist in the form of oil-swollen micelles dispersed in water as oil-in-water (O/W)
microemulsion (Fig. 12.8a) or water-swollen micelles dispersed in oil as for water-
in-oil (W/O) microemulsion, also known as reverse microemulsion (Fig. 12.8b). It is
well established that the W/O microemulsions are formed when surfactants with low
HLB values (3–6) are used, whereas the formation of O/W microemulsions occurred
with surfactants with high HLBs (8–18). On the other hand, microdomains of oil
and water are interdispersed within the system in case of bicontinuous microemul-
sion (Fig. 12.8c). Among these, nano-sized water droplets dispersed in an oil phase
have been extensively studied as nanoreactors for aqueous reactions wherein particle
formation takes place and size of the droplets decide the size of nanoparticles as
well as their polydispersity [103–106]. Other factors such as surface-active agent,
the concentration of aqueous reactants, and temperature played important role in
controlling of particles size.
The formation of microemulsion in a three-component system of water, oil, and
surfactant can be depicted as shown in Fig. 12.9. Water-in-oil microemulsion can
be prepared by dispersing water in a hydrocarbon-based continuous phase and posi-
tioned to the oil apex of the triangular phase diagram of water/oil/surfactant. In
this region, thermodynamically guided surfactant molecules self-assembled to form
reverse micelles. However, these micelles are in dynamic equilibrium with indi-
vidual amphiphiles. They frequently collide through Brownian motion and merge to
produce dimers, which may exchange contents and then separated. Thus, the inor-
ganic/organic precursor loaded inside the micelles mixed thoroughly. This exchange
process is central to the synthesis of nanoparticles in the core of reverse micelles.

Fig. 12.8 a Schematic illustration of water-in-oil (W/O) microemulsion, b oil-in-water (O/W)

microemulsion, and c bicontinuous microemulsion
496 B. Dutta et al.

Fig. 12.9 A hypothetical

phase diagram of a
microemulsion system
comprising of oil (O), water
(W), and surfactant +
cosurfactant (S)

Thus, the reverse micelles mainly act as “nanoreactors” and offer the desired condi-
tion for controlled nucleation and growth of particles [107]. In the latter stages of
growth, the surfactant layer forms a robust coating on the surface of nanoparticles;
thereby reduce the nanoparticle aggregation through steric stabilization [108].
The first step of nanoparticle synthesis in a microemulsion is the reaction between
the reactant and the precipitating agent or the two reactants trapped in the core of the
microemulsion. There are mainly two approaches for the synthesis of nanoparticles
using microemulsion; “Single microemulsion method” and “Double microemulsion
method” [109]. Nanoparticle production in a single microemulsion method can be
either “energy triggering” or “one micro emulsion plus reactant” method. In the
energy triggering method, the reaction is started by applying a triggering agent into
the single microemulsion having a precursor. For instance, Kurihara et al. used pulse
radiolysis and laser photolysis to trigger the synthesis of gold nanoparticles in water-
in-oil microemulsions [110]. In the second approach, the reaction is started directly by
introducing one reactant into the microemulsion containing another reactant, i.e., in
one microemulsion plus reactant method. In the double microemulsion methods, two
reactants that are dissolved in the aqueous nanodroplets of two different microemul-
sions are permitted to mix through the fusion–fission events. Thus, this method
mainly depends on the fusion–fission events between the nanodroplet as shown in
(Fig. 12.10).
In general, reactants exchange and mixing occur through the collision of water
droplets in microemulsion. The reactants exchange takes place very fast and precipita-
tion reaction occurs in the nanodroplets, followed by subsequent nucleation, growth,
and coagulation process to form final nanoparticles. Rauscher et al. [111] demon-
strated a typical time-dependent study of the precipitation reaction of CaCO3 in the
microemulsion system.
Various metal, magnetic, and semiconductor nanoparticles were successfully
prepared by using microemulsion methods. Among the metallic nanoparticles, plat-
inum, palladium, iridium, and rhodium nanoparticles were successfully synthesized
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 497

Fig. 12.10 Fusion and

fission processes in
microemulsion-mediated A B
nanoparticles synthesis

AB

from the microemulsions method [112]. For example, Pal et al. [113] synthesized
Pt nanoparticles (<5 nm) by reducing H2 PtCl6 using NaBH4 in w/o microemul-
sions of water/TritonX-100/cyclohexene/1-hexanol. Martı́nez-Rodrı́guez et al. [114]
prepared of shape-controlled Pt nanoparticles using a water-in-oil microemulsion
method. They have reported that the shape/surface morphology of Pt nanoparti-
cles is dependent on the concentration of HCl in the water phase of microemul-
sion. Chen et al. [115] synthesized palladium nanoparticles by reducing Pd salt
in aerosol-OT (AOT)/isooctane microemulsion using hydrazine. Kurihara et al.
[110] prepared Au nanoparticles by reducing chloroauric acid in w/o microemul-
sions and reported many advantages of nanoparticles synthesis in the microemul-
sion method than those in homogeneous solutions. Mihaly et al. synthesized
bare and thiol-coated Au nanoparticles through microemulsion assisted photore-
duction method using ternary water/Brij 30/n-heptane system [116]. Barnickel
and Wokaum [116] successfully prepared Ag and Au colloidal nanoparticles
by reduction of AgNO3 and HAuCl4 in a dodecyl heptaethyleneglycolether and
hexane microemulsions. Qiu et al. [117] reported the preparation of spherical Cu
nanoparticles in SDS/isopentanol/cyclohexane/water microemulsions with NaBH4 .
Bimetallic alloy nanoparticles of Cu-Pt and Pd-Au were also prepared in water-in-
oil (w/o) microemulsions of water/CTAB/isooctane/n-butanol through the simulta-
neous reduction of H2 PtCl6 and CuCl2 using hydrazine at room temperature [118,
119]. Metallic magnetic nanoparticles were also prepared by using microemulsion
methods. For instance, Duxin et al. [120] obtained body-centered cubic α-Fe using
498 B. Dutta et al.

anionic surfactants (AOT), whereas Wilcoxon and Provencio [121] prepared face-
centered cubic α-Fe using nonionic surfactant (nonylphenol polyethoxylate). Tanori
et al. [122] developed magnetic mixed metals (alloys) by using mixed metal precur-
sors in the microemulsion method. Xia et al. [123] discussed the formation of Ag–
Ni core–shell nanoparticles by reducing AgNO3 and of Ni(NO3 )2 using NaBH4
in water/polyoxyethylene (4) nonylphenol and polyoxyethylene (7) nonylphenol/n-
heptane W/O microemulsions. Highly monodispersed ultra-small magnetic oxide
nanoparticles were also prepared microemulsions method [124–127]. For instance,
Inouye et al. prepared magnetic iron oxide nanoparticles by oxidation of Fe2+
salts in an AOT/isooctane system. Lu et al. developed a water-in-oil microemul-
sion route for synthesizing of Fe3 O4 nanoparticles using different kinds of surfac-
tant, n-heptane, and n-hexanol [126]. Liu et al. prepared CoFe2 O4 nanoparticles using
sodium dodecylbenzenesulfonate microemulsions in presence of hydrazine [127].
Other magnetic oxides such as MnFe2 O4 , (Mn,Zn)Fe2 O4 , (Ni, Zn)Fe2 O4 , ZnFe2 O4 ,
Ca0.5 Sr0.5 MnO3, and BaFe12 O19 were also prepared by various research groups using
microemulsion methods [125, 128–131]. In addition, different non-magnetic metal
oxide nanoparticles such as Fe2 O3 , SiO2 , ZrO2 , TiO2, and GeO2 were also devel-
oped using this method [132–141]. For instance, Esquena et al. [133] prepared SiO2
nanoparticles by addition of Si(OC2 H4 )4 to the solubilized aqueous ammonia solu-
tion in AOT and ployoxyethylated nonulphenyl ether W/O microemulsions. Li et al.
[140] prepared TiO2 nanoparticles by microemulsion-mediated hydration method
having well-controlled structure and high photoactivity. Geng et al. [135] prepared
zirconia nanoparticles in water-in-oil microemulsions of water/cyclohexane/Triton
X-100/hexyl alcohol. Han et al. [137] developed size-controlled NiO nanoparticles
in W/O microemulsion of Triton X-100/n-hexanol/cyclohexane/water. The reverse
microemulsion process is also used for the preparation of core–shell nanoparticles. In
this synthesis process, the thickness of the shell is usually tuned by different reaction
conditions such as time, temperature, concentration of precursor, etc. [142, 143].
A large variety of semiconductor nanoparticles including CdS, ZnS, PbS, CuS,
Cu2 S, and CdSe [144–150] were successfully prepared through the microemulsion
route. For instance, Agostiano et al. [144] prepared CdS nanoparticles by mixing two
microemulsions formed by cetyltrimethylammonium bromide (CTAB), pentanol,
n-hexane, and water having Cd(NO3 )2 and Na2 S. Petit et al. [145] prepared CdS
nanoparticles in AOT and triton reverse micelles having cadmium lauryl sulfate
and cadmium AOT surfactants. Manyar et al. [149] fabricated ZnS nanoparticles
using four-component “water in oil” microemulsions containing CTAB, cosurfactant
(pentanol or butanol), n-hexane, and water. Ethayaraja et al. [151] synthesized CdS-
ZnS core–shell semiconductor nanoparticles using different water-in-oil microemul-
sions and demonstrated a two-stage mechanism for the preparation of core–shell
nanoparticle.
Organic nanoparticles such as whey protein and polymer nanoparticles were
synthesized by the microemulsion method. Zhang and Zhong [152] synthesized
whey protein nanoparticles with higher heating stability by using microemulsions as
nanoreactors. Guo et al. [153] investigated polymerization of styrene in microemul-
sion of SDS/pentanol/water adding water soluble (potassium peroxodisulfate) as
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 499

well as oil soluble (2,2 -azoisobutyronitrile) initiators. Palani et al. [154] explored
the polymerization of methyl methacrylate (MMA) through MMA/ethylene glycol
dimethacrylate/water microemulsion using acylamide as amphiphile. Microemul-
sion systems were also employed to synthesize organic nanoparticles of choles-
terol, Rhovanil, retinol, Rhodiarome etc. [155, 156]. In an interesting review,
Margulis-Goshen and Magdassi [157] discussed various approaches used to prepare
organic nanoparticles from microemulsions. Microemulsion not only served as
nanoreactors for particle formation but also prevent the agglomeration of nanopar-
ticles as surfactants form a robust coating on particle surface when the particle size
reaches that of the water pool.
Microemulsions served as good candidates for drug delivery. Microemulsions are
found to improve the therapeutic efficacy of drug molecules and minimize the toxic
side effects. It offers several other benefits such as increased absorption, long shelf
life, improved clinical potency, decreased toxicity, and ease of preparation and admin-
istration. Specifically, the administration of drug molecules through microemulsions
is easier for children and adults who have difficulty in swallowing powder or tablet
forms of drugs. Thus, microemulsions have been widely used as carriers for the
delivery of drug molecules through the oral route. Further, microemulsions have a
low viscosity which makes their administration by an intravenous route much easier.
Microemulsions are also used for transdermal drug delivery because of their higher
solubilization capacity for both hydrophobic and hydrophilic drugs. For example,
antifungal hydrophobic agents such as miconazole, ketoconazole, and itraconazole
have been delivered via microemulsions-based formulation [158].

12.6 Langmuir–Blodgett Approach for Mesostructured

Composites and Thin Films

In today’s material science and electronic industries, suitable organic materials in

their structured and organized states are of prime importance, as downsizing inor-
ganic material beyond a certain point changes their properties completely. In this
respect, Langmuir–Blodgett (LB) technique provides the desired control on the order
at the molecular level. Hence, it is a potential technique for the construction of
future organic as well as inorganic materials (from organic precursors) for various
applications as the molecular orientation and packing can be highly controlled by
using various organic amphiphilic molecules with suitably designed architecture and
functionality.
Irving Langmuir [159] developed experimental and theoretical concepts which
form the basis for the modern understanding of sizes and shapes of molecules
in monolayers and their orientation at the interface. He has demonstrated that
amphiphilic molecules (having hydrophilic and hydrophobic groups) accumulate on
the water surface and form a monolayer where the hydrophilic group (e.g., -COOH,
-NH2 , -OH) immersed in the water surface and hydrophobic group (long-chain
500 B. Dutta et al.

hydrocarbon) remains above the surface. His early work concentrated on floating
monomolecular layer (Langmuir films) at the air–water interface. Later in 1919
under his guidance, Katherine Blodgett [160] had been able to develop, a technique
to transfer the monomolecular film from a water surface onto a solid substrate. This
is universally known as Langmuir–Blodgett technique. Around 1965 Hans Kuhn
[161] and his colleagues began work on the organization of monolayers and their
spectroscopic and other physical properties.
The most common technique for studying Langmuir monolayer has been to
measure pressure-area isotherm, which is the change in surface pressure as a func-
tion of surface area per molecule at a constant temperature. When a long amphiphilic
molecule such as fatty acid dissolved in a volatile solvent is spread onto the water
surface, the solvent evaporates and molecules remain dispersed as a layer at the air–
water interface. By the addition of the surface-active reagent (fatty acid or amine)
the surface tension of the water is lowered. The monomolecular layer of the surface-
active reagent on the surface of the water exerts a film pressure (π), depending on
the surface concentration, such that π = γ0 − γ where, γ0 = surface tension of the
pure water and γ = surface tension of the monolayer covered water.
The pressure area (π − A) isotherm of the monolayer of amphiphilic molecule
(fatty organic compound) at the air–water interface (Langmuir films) frequently show
features suggesting phase transition [162]. Figure 12.11 shows the (a) schematic of
surface pressure-area isotherm of a long-chain fatty acid (e.g., stearic acid) with
their various phases, (b) different packing of the molecules in monolayer at various
phases, and (c) multilayer structure of the molecules after the collapse at the air–
water interface. If a solution of stearic acid is spread on the water surface, surface
pressure area isotherm shows various phases, i.e., gas, liquid and solid which has an
analogy with the pressure–volume isotherms in three dimensions. In the gas phase
(at very low surface pressures), the molecules are almost flat on the water surface.
The steepest part of the π − A isotherm is associated with a solid and closed-packed
region. The intermediate pressure region has been identified as the liquid phase with
the hydrophobic hydrocarbon chains start to interact with each other and being lifted
away from the water surface. Beyond the closed packed region for a smaller area
per molecule, there is collapse and molecules may be forced out of the monolayers.
The value of the collapse pressure for a simple fatty acid can be in excess of 50
mN/m which would be equivalent to about 200 atm [163] when extrapolated to three
dimensions.
Figure 12.12 shows (a) schematic of LB trough and (b) surface pressure area
isotherm of arachidic acid measured using the LB method. When the monolayer
on the water surface is compressed with the barrier, the monolayer can be either
expanded, partly expanded, or close-packed state at the air–water interface depending
on the surface pressure. The structure of the monolayers depends on the nature of
the subphase especially for films of fatty acids (or amines) under ionizing conditions
when the ionized head group is complexed to its counter cation (or anion). This factor
is important in understanding the nature of multilayer LB films as the dissociation
of the fatty acid carboxylic group or fatty amine group in presence of different
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 501

(a)

(b) (c)

Collapse of monolayer

Fig. 12.11 a Schematic of surface pressure area isotherm of a long-chain fatty acid (e.g., stearic
acid) with their various phases, b different packing of the molecules in monolayer at various phases
and c multilayer structure of the molecules after the collapse at the air–water interface

Fig. 12.12 a Schematic of LB trough and b surface pressure area isotherm of arachidic acid
measured using LB trough
502 B. Dutta et al.

multivalent cation or anionic complexes in the subphase depends on the pH of the

solution.
R-COOH + H2 O → R-COO− , R-NH3 + H2 O → R-NH4 + (where R is the long
hydrocarbon chain).
In order to form LB multilayer films (Fig. 12.13), a suitable substrate is passed
through a compressed monolayer, at a controlled speed to deposit layer by layer
on the substrate from the air–water interface. The nature of subsequently deposited
layers depends on the surface quality and composition of the substrate. The surface
pressure is kept constant during the deposition. The first monolayer is deposited onto
a hydrophilic substrate when the substrate rises up through the air–water interface.
From the subsequent dipping, two more monolayers are deposited on the first mono-
layer. The deposition made in a head-to-head and tail-to-tail configuration is referred
to as Y-type. There are two more deposition modes X and Z, where deposition occurs
as the substrate is being inserted into the subphase or only as the substrate is being
removed through air–water interface, respectively. The deposition process can be
quantified through transfer ratio (TR) which is given by

Area of the monolayer removed from the surface at constant pressure

TR =
Area of substrate immeresed in water
To investigate the orientation of the molecules and structure of LB films, various
analytical techniques such as X-ray diffraction, Fourier transform infrared spec-
troscopy, X-ray photoelectron spectroscopy, and atomic force microscopy have been
used.
It is vital to understand the nature of the stacking of the monolayers in the multi-
layer LB films in order to obtain the physical–chemical basis for the structure.

Fig. 12.13 a Deposition of multilayers by Langmuir Blodgett technique b various type of deposition
mode
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 503

Fig. 12.14 X-ray diffraction pattern of 29 monolayers LB film of cadmium arachidate (C20 fatty
acid) indicating 00 l reflections obtained with Cu Kα radiation (λ = 1.5405 Å). The film was
deposited at a constant surface pressure of 30 mN/m using CdCl2 solution (20–4 M, pH = 6.5)

Evidence for the multilayer structure may be obtained directly from X-ray diffraction
studies of these films. Figure 12.14 represents the diffraction pattern of a multilayer
Cd-arachidonate film showing the characteristic odd–even intensity oscillations of
the 00 l reflections. The d value obtained from the 00 l lines using Bragg’s law
equation is 55.6 Å, which is close to the value of bilayer thickness with hydrocarbon
chains and the metal ions. The unit-cell c-parameter of LB films of metal salts of fatty
acid changes by ~5.0 Å if the carbon atoms in the fatty acid are doubled [164]. The
projected C–C distance along the c-axis is 1.25 Å obtained for all trans configurations
assuming a perpendicular orientation of the chains, a tetrahedral angle between the
carbon atoms and a C–C distance of 1.54 Å.
Initially, Langmuir–Blodgett technique was used for depositing organic
amphiphilic molecules. Pure organic multilayer LB film was made by charge transfer
complexes such as molecular electron donor, tetrathiafulvalene and acceptor, tetra-
cyanoquinodimethane derivatives. These films are conducting in nature. Conducting
polymers based on polycarbazole, polyaniline, polypyrrole, and polythiophene were
organized by LB technique. Metal ion incorporation in the LB film is known for stabi-
lizing of Langmuir monolayer in presence of divalent metal ions such as Cd, Pb, Mn,
etc. Organometallic compounds like ferrocene, metal porphyrin, and metal phthalo-
cyanine have been organized by the LB technique [165]. The inorganic–organic
hybrid materials such as polyoxometallates incorporated in dimethyldioctadecylam-
monium can be prepared in a layered structure by the LB technique. These hybrid
materials have a great impact in areas of catalysis, medicine, etc.
Langmuir monolayers, due to their simple two-dimensional nature, have been
employed as templates that facilitates the crystallization of organic and inorganic
materials [166–168]. Functional groups of amphiphilic molecules of Langmuir
monolayer act as nucleation or/and growth centers, which control the morphology
and orientation of crystal-axis of the crystals grown. Using Langmuir monolayer as
a template, the oriented crystals of various inorganic salts such as NaCl, CaCO3 ,
504 B. Dutta et al.

BaSO4 , SrSO4 , ice, CdS, PbS, and silver propionate have been successfully grown
at the air–water interface. Crystals of Prussian blue analogues are difficult to grow
in bulk. However oriented crystals of magnetic Prussian blue analogues have also
been deposited at the air–water interface using octadecyl amine (ODA) monolayer
as the template. Protonated amine head groups of ODA monolayer acted as the sites
for the growth of oriented crystalline film of Prussian blue analogues.
Figure 12.15 shows schematically the growth of oriented crystallization of nickel
(II) hexacyanoferrate (III) (NiHCF) in an LB trough at the air–water interface under
the ODA monolayer. Initially, when ODA is spread on a (1.5 × 10–4 ) M NiCl2
solution, a stable monolayer is formed. A few drops of concentrated K3 Fe(CN)6
solution were put through a micro syringe to the NiCl2 forming greenish-yellow
crystalline film of NiHCF after sixteen hours at the water interface. This crystalline
film is transferred to a solid substrate by LB technique and from the X-ray diffraction
studies, parallel alignment of the {100} crystal plane of Ni-hexacyanoferrate to the
ODA surface has been observed [166]. Similar to NiHCF crystallization, growth of
cobalt (II) hexacyanoferrate (III) (CoHCF) single crystals and other transition metal
hexacyanochromates was observed under the Langmuir monolayer [167, 168]. Other
crystals of the Prussian blue family which are generally difficult to grow in the bulk,
can be grown at the air–water interface using the ODA monolayer as the template.
Langmuir–Blodgett (LB) technique has been used for preparing ultrathin metal
oxides recently [169–175] as an alternative method for metal oxide thin film forma-
tion. Usually, by LB technique, a uniform and ordered thin films of various organic
materials based on amphiphilic molecules are prepared. To make metal oxide thin

Fig. 12.15 Schematic illustration of oriented crystallization of Prussian blue analogue, nickel (II)
hexacyanoferrate (III) under Langmuir monolayer
12 Amphiphilic Self-Assembly in the Synthesis and Processing of Nanomaterials 505

Fig. 12.16 Schematic of metal oxide thin film preparation by using LB technique

films, initially uniform and ordered multilayer LB films of metal salts of amphiphilic
molecules are deposited on substrates and then decomposed by heating in the pres-
ence of oxygen. Metal ions form thin oxides on the substrate after the dissociation of
the salts, decomposition/desorption of long hydrocarbon chain while heating. Thin
films of metal oxides such as SnO2 , TiO2 , WO3, and PdO [169–175] have been
prepared by deposition of multilayer films of their corresponding anionic salt and
ODA complex, from the air–water interface and subsequent decomposition of multi-
layer LB films (Fig. 12.16). These metal oxide films prepared from LB precursors
have been used for gas sensing, photosensitization, and electrochromism [171–175].

12.7 Conclusions and Future Perspectives

Amphiphiles molecules have a strong affinity to self-assemble in selective solvents

into various structures including lamellae, micelles, and vesicles. Diverse morpholo-
gies with an internal feature in the nanometer-length scale can be produced by the
assembly of small molecules. Such association is occurred by various noncovalent
interactions and hence can be modified by varying the environmental conditions
such as solvent dielectric constant, pH, temperature, ionic strength, etc. This offers
an attractive strategy to develop nanomaterials with tailored properties. The prin-
ciple of self-assembly process and guiding rules to control the morphology of the
assemblies is provided in this chapter. Various of liquid-phase synthesis methodolo-
gies of nanomaterials, and the role of amphiphiles in controlling the nucleation and
growth process of nanoparticles has also been addressed in detail. The dynamics
of these equilibrium structures and their influence on material synthesis are also
presented. Applications of a variety of amphiphilic assemblies such as micelles,
506 B. Dutta et al.

microemulsions, block copolymers, etc. in modulating the microstructure of nanopar-

ticles are discussed. The role of amphiphiles in developing thin-film materials with
controlled thickness and internal structure using Langmuir–Blodgett approach is
being discussed. In summary, self-assembly has been recognized as a novel route for
the development of nanomaterials. The future of nanotechnology lies in the large-
scale production of materials with controlled structure and order over multiple length
scales, and self-assembly could play a promising role in realizing this goal.

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Chapter 13
Synthesis of Functionalized Noble Metal
Nanoparticles

Abhishek Das and Nandita Maiti

Abstract Noble metals, for instance, silver and gold, have been extensively mined
and utilized by mankind since time immemorial. Newer noble metals such as plat-
inum group metals, namely platinum and palladium, became available for application
with the advancement of metallurgy. The inert chemical nature and corrosion resis-
tivity of the noble metals was the major attraction for their deployment in diverse tech-
nological avenues. With the advent of nanotechnology, further interest was created
among researchers for the investigation of interesting structural, photophysical and
catalytic properties. In this chapter, the advancement in the field of synthesis and
application of surface-functionalized noble metals have been discussed. The different
methods of nanoparticles synthesis such as chemical, radiolytic and photochem-
ical have been discussed with few examples to draw out the advantages as well as
disadvantages of one method in comparison to another. The importance and utility
of the characterization techniques, which are usually used by researchers such as
optical absorption, electron microscopy, etc., have been discussed. The observation
of surface plasmon in noble metal nanoparticles and its role in quantitative analysis,
as well as probing surface reactions, by surface-enhanced Raman scattering, have
been explained by way of illustrations and examples. The interaction of plasmonic
nanoparticles resulting in the variation in colour of the colloidal particles has been
illustrated with examples of colorimetric sensing of analytes. The role of noble metal
nanoparticles in heterogenous catalysis has also been discussed in this chapter.

Keywords Noble metal nanoparticles · Synthesis · Functionalization ·

Applications · Surface Plasmons · Surface-enhanced Raman scattering (SERS) ·
Colorimetric detection · Surface catalysis

A. Das · N. Maiti (B)

Radiation & Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
A. Das
e-mail: [email protected]
N. Maiti
Homi Bhabha National Institute, Mumbai 400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 515
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_13
516 A. Das and N. Maiti

13.1 Introduction

The word “noble” imparts a sense of detachment from the masses yet instils exquisite-
ness. Noble metals (NM) like gold (Au) and silver (Ag) are different from other
metals in terms of reactivity. In fact, these metals tend to retain their intrinsic shine
for a longer time. The inert nature of noble metal arises from its high standard
reduction potential. These noble metals, viz., gold and silver exist in nature mostly
in their elemental form [1, 2] as pure metal or alloy. Purification of ore metal to
pure metal involves cyanidation followed by electrolytic extraction [3]. Extraction
of noble metal in pure elemental form is an age-old process. In 1959, renowned
physicist Richard Feynman presented a talk entitled, “There’s Plenty of Room at the
Bottom: An Invitation to Enter a New Field of Physics” [4], in which a number of
interesting ramifications of manipulating matter on an atomic scale were discussed.
With the discovery of sophisticated imaging techniques [5], for example, transmis-
sion electron microscopy (TEM), atomic force microscopy (AFM) and scanning
electron microscopy (SEM), the synthesis of noble metal nanoparticles (NPs) gained
popularity among scientists owing to their interesting surface chemistry as well as
unique optical properties. In this chapter, efforts have been made to bring out various
popular and rare synthetic approaches along with some noteworthy applications of
functionalized noble metal NPs. With the aim to recognize and also appreciate the
properties of noble metal NPs, it is essential to be informed about the bulk properties
of the noble metals.
Gold is one of the first discovered metals. Throughout the history of mankind, gold
has been considered a precious metal in many cultures across the world. This may
be due to the fact that gold resists atmospheric oxidation due to its high standard
reduction potential of 1.5 V [6]. Bulk gold metal is characterized by its lustrous
yellow glow, high malleability [7], high ductility and high reflectivity. The yellow
colour of gold metal has its origin in the interband transition which takes place in the
visible region of the electromagnetic spectrum owing to the relativistic effects [8].
Apart from the above physical properties, gold exists in the oxidation states ranging
from −1 to + 6 [9–11], with + 1 and + 3 being the more dominant states [12].
Silver, unlike gold, is less abundant in nature in pure elemental form as it is more
reactive than gold, with the standard reduction potential of 0.80 V [6]. Hydrogen
sulphide readily available in the environment, from decomposed organic matter,
tarnishes the shine of silver and blackens it with a layer of silver sulphide. The black
layer of silver sulphide can be removed by chemical reduction [13]. Interestingly,
silver occurs in the elemental form mostly along with gold in a natural alloy known as
electrum, with a silver content of 8–10% [14], which makes electrum less dense than
pure gold. Earlier in Egypt, gold was separated from silver in electrum by heating the
alloy with sea salt[15]. Later, the salt of silver was reduced to obtain pure elemental
silver. Unlike gold and copper (Cu), silver metal has the brightest white shine which
makes it useful for the fabrication of a perfect mirror. Roman first devised the method
to deposit silver on glass, which was later revived in the nineteenth century by Justus
von Liebig [16]. This reaction is a variation of Tollen’s reaction for testing aldehyde
13 Synthesis of Functionalized Noble Metal Nanoparticles 517

[17]. Apart from virtual image formation in mirrors, silver is also associated with
the development of photography [18]. Ag NPs are readily formed upon exposure of
silver bromide to light. These negatives on polymer films are developed to produce
a photograph, which is again another form of an image. Silver is known to exist in 0
to + 3 oxidation states with +1 being the most common [19]. Silver also contributes
to the health aspect of human life. Silver-coated utensils are found to show antibiotic
activity [20]. The anti-microbial activity of silver is not clearly understood, yet there
are some proposed theories explaining the mechanism. Silver ions undergo oxidation
at the surface of the cell membrane, which may form complexes due to their “soft”
or more polarizable nature and disrupt the normal physiological functioning of the
cell [21].
Platinum group metals (PGM), for instance, platinum (Pt), palladium (Pd),
osmium (Os), etc., are also considered noble metals owing to their elevated chem-
ical inertness and high oxidation resistance [22, 23]. Unlike gold and silver that is
found naturally in elemental form, PGMs occur in nature in the form of arsenide
or sulphide, viz., (Pt,Pd,Ni)S, (Pt,Pd)S, Pt(AsS)2 , PtS, PtAs2 , etc., which are gener-
ally extracted by hydrometallurgical methods [24]. Ores are generally concentrated
by froth floatation followed by oxidation of the concentrate by smelting and reduc-
tion of the oxides in the converter. The PGM concentrate is then processed in a
base metal refinery by pressure oxidation leach or dissolution–precipitation, molec-
ular recognition technology and solvent extraction and ion exchange, where PGMs
are separated from the base metals. The main challenge in PGMs extraction is the
escalating content of chrome in the feed and the premature collapse of the refrac-
tory lining in the smelter. This is overcome by the Kell method of extraction [25].
PGMs are often used for applications in automotive, jewellery, electronics, catalysts,
etc. [26]. The most noted application of platinum includes catalytic converters of
automobiles where inert platinum surface coating facilitates heterogeneous catalytic
oxidation of carbon monoxide [27]. Palladium metal is well known for its application
in hydrogenation reactions [28].
In this chapter, the various methods of synthesis of noble metal NPs along with
their physical, chemical properties as well as their applications have been discussed.

13.2 Synthetic Strategies

Noble metal NPs show interesting physico-chemical properties that depend on the
shape and size of the particles [29–38]. The most important activity in the area of
nanoscience involves the NPs synthesis and its functionalization. Researchers are
involved in the development of various synthetic protocols for the preparation of
functionalized metal NPs that can be used as molecular markers [39–42] and are
also applicable in the areas of catalysis [43–45], sensors [46–49], etc. The synthesis
of anisotropic NPs is also being investigated due to their unusual electronic, optical,
catalytic and sensing properties [50–53]. The simplest approach towards the synthesis
of colloidal metal NPs is achieved by the following methods: the “top-down method”
518 A. Das and N. Maiti

as well as the “bottom-up method” [54]. The top-down process involves the breaking
down of the bulk metal by mechanical means, viz., nanolithography, micromachining,
ion implantation, inert gas condensation, laser pyrolysis, high energy ball milling,
melt mixing, pulse vapour deposition, flash spray pyrolysis, electrospraying, etc. [55,
56]. The resulting metal NPs are then stabilized by various protecting agents. This
method, however, has a few drawbacks, namely the difficulty in obtaining a narrow
distribution of particles size. The bottom-up methods, on the other hand, involve the
wet chemical route of the NP preparation. In this approach, the NPs are prepared either
by chemically reducing the metal salts or using electrochemical reduction and/or
the controlled decomposition of metastable organometallic compounds in solution.
Precise control over the growth of the primarily formed NPs is usually achieved with
various stabilizers, viz., donor ligands, polymers, surfactants, etc. The mechanism
behind the bottom-up approach involves a stepwise formation of NPs that consists
of nucleation, growth and agglomeration [57–60] and is shown in Scheme 13.1. In
this chapter, the bottom-up approach for preparing the noble metal NPs is discussed.
The metal ion reduction followed by the NP formation can be achieved in numerous
ways of which a few are listed as follows:
(a) Chemical reduction method
(b) Radiolytic reduction method
(c) Photochemical reduction method

Scheme 13.1. Mechanism showing the bottom-up approach involving the stepwise formation of
NPs consisting of nucleation, growth and agglomeration
13 Synthesis of Functionalized Noble Metal Nanoparticles 519

Methods of Characterization of Synthesized Nanoparticles

Synthesized NPs are generally characterized by optical spectroscopy, microscopy,
diffraction, electrophoresis and light scattering techniques.
In UV–visible (UV–vis) absorption spectroscopy, the noble metal or plasmonic
NPs are characterized by the appearance of the surface plasmon resonance (SPR)
band. The origin of the colour in noble metal NPs is fundamentally different from
that in bulk metal. Noble metals are the only group among the transition elements
in the periodic table that show colour in their elemental form [61]. The selection
rule for the electronic transition is l = ± 1, S = 0, where l is the azimuthal
quantum number of subshells involved in the transition and S is the total spin of all
the electrons [62]. In transition metal complexes, a strong colour is observed due to
the d–d transition, where the selection rule is relaxed as the orbital character of the
d-orbitals is lost due to mixing with ligand orbitals. But in pure elements such kind of
mixing is not possible, resulting in mostly colourless transition metals, an exception
being gold and copper. The origin of colour in noble metal lies in their electronic
arrangement [61, 63]. The origin of colour in NPs of gold and silver is completely
different from the above-mentioned discussion. Plasma is known as a state of matter
where charged and uncharged matter co-exist, with overall electro neutrality [64].
Free electrons exist in the background of positive ionic cores in metals, which is also
plasma. When electromagnetic radiation, i.e., photons, interacts with the metallic
surface, it polarizes the electron cloud on the surface giving rise to “lossy” particles
called polaritons [65]. Absorption of some of these polaritons leads to the intraband
transition as discussed above, giving rise to the colour response of the metal. The
rest of the polaritons are scattered back as photons.
In 1908, Gustav Mie proposed the Mie theory of light scattering by a homogenous
sphere [66]. As a special case, light interacting with a particle comparatively much
smaller than the incident electromagnetic radiation wavelength was discussed. It was
proposed that under such a condition, the particle experiences a uniform electric field.
For example, a metal NP of ~10 nm in size when excited with electromagnetic radi-
ation of wavelength 520 nm experiences a uniform electric field. A gold NP of size
~10 nm contains about 30,000 atoms, out of which only ~40% constitute the surface.
The electrons of the metal NP undergo polarization under such an electric field. The
polarization of this electron gas forms a polariton that oscillates and scatters light,
synchronously with electromagnetic radiation. The natural oscillation frequency of
plasma, known as plasma frequency, is an intrinsic property of a metal. Under reso-
nance conditions when the incident electromagnetic radiation frequency matches the
metal plasma frequency, a built-up of electrons occurs and maximum damping of
oscillation is observed. This phenomenon is known as SPR [67], wherein the surface
electrons oscillate collectively as shown by a schematic illustration in Fig. 13.1. At
this frequency of light, the metal NPs absorb light to give colour. Gold and silver in
the nanometric domain show the SPR band in the visible region. The electron density
of both gold and silver is very close, despite having different atomic numbers. As a
result, their plasma frequency is expected to lie close to each other. On the contrary,
their SPR frequencies are quite different. The SPR peak of Ag NPs emerges at about
520 A. Das and N. Maiti

Fig. 13.1 Schematic diagram showing the collective and coherent oscillation of quasi-free electrons
present in a metal NP exposed to the uniform electric field of incident radiation

400 nm whereas that of Au NPs appears around 520 nm. This is because the intraband
transition of gold, which lies in the visible region, perturbs the SPR band of gold
and shifts it from 400 to 520 nm. The SPR band of Ag NPs remains unaffected as its
intraband transition lies in the UV region. Like gold, Cu NPs also show an SPR band
at around 650 nm. The SPR band of Pd and Pt NPs does not appear in the visible
region. For sizes of NPs from 2 to 20 nm, dipolar oscillations constitute the SPR band
whereas upon increasing the size of the NPs multi-polar modes start contributing to
the SPR band, due to the non-uniformity of the electric field as experienced by the
particle. Thus, upon increasing the size of the NPs, the SPR band gets broader and
red-shifted.
The presence of the SPR band in metal NPs explains the colour of Au, Ag and
Cu NPs. Au NPs of size roughly ~5–10 nm show intense red colour. As the size
of the particles increase, the colour changes from red, purple and blue. Similarly,
Ag NPs show yellow colour for small particles, which turns grey with increasing
size. Although this SPR phenomenon was understood recently, due to scientific
advancement and technological progress, Au NPs were found to be used since the
Roman age. Lycurgus cup [68, 69] shows red colour in transmitted light owing to
the presence of Au NPs of size ~70 nm, trapped in the glass matrix. Interestingly,
this was discovered by accidental contamination of minutely ground gold dust.
UV–vis (optical) absorption spectroscopy is used to identify the approximate
size of the sphere-shaped NPs [70]. In the case of anisotropic NPs, two SPR bands
are observed, transverse and longitudinal. The transverse mode corresponds to the
plasmon across the minor axis and appears at a lower wavelength, whereas the longi-
tudinal mode corresponds to the plasmon across the major axis and appears at a
higher wavelength. Mulvaney et al. [71] have shown that for Au nanorods (NRs),
variation in the aspect ratio leads to the shift of the SPR bands corresponding to the
longitudinal and transverse modes.
TEM is used to record the morphology of the particles, i.e., the size and shape of
the NPs [72]. Even though TEM is considered a non-invasive technique, an electron
13 Synthesis of Functionalized Noble Metal Nanoparticles 521

beam is often found to locally heat the particles, leading to their fusion with time
[73]. Different materials in a TEM image can be distinguished from the contrast of
the image that depends on the material electron density [74]. The lattice spacing
of materials can also be visualized by TEM in the form of lattice fringes [72]. In
order to record a TEM image of noble metal NPs, a drop of solution is placed
on the copper mesh grids, which is then air-dried. SEM technique is also used for
studying the morphology of NPs at a lower magnification than TEM. It is often used
to establish the particles size distribution [75]. Apart from TEM and SEM, AFM is
another microscopic technique that uses the change in deflection of laser light, which
is incident on the cantilever of the AFM tip, as a function of force between the AFM
tip and the sample [76]. AFM can be used to measure the depth of the NPs (deposited
on silicon or mica wafer) along the Z-axis. The size of the NPs in the XY plane is
not the real size of the particles as it is influenced by the tip features.
X-ray diffraction (XRD) method is used to validate the formation of noble metal
NPs [77–79]. Sometimes silver oxide [80] or silver chloride [81] formation can be
confirmed using XRD. The XRD technique also provides information concerning
the crystallite size of the particles from the observed lattice contraction[82]. But in
the case of NPs, the Scherrer formula [82] has limited use in effectively calculating
the particle size because of inadequate crystallinity and overlapping XRD peaks.
Surface charge [83] is another parameter useful for knowing the stability of the
synthesized NPs. Zeta potential [84] is the measure of effective surface charge on any
NP and is measured by electrophoresis along with laser Doppler velocimetry [85–
87]. Zeta potential essentially provides an estimate of the electrical double-layer
thickness, which is the determining parameter for the stability of NPs in solution
[88].
Dynamic light scattering (DLS) is also an important technique that gives infor-
mation about the hydrodynamic radius of NPs in solution [89]. The principle of DLS
is based on time-dependent fluctuation of Rayleigh scattering which is a function
of the hydrodynamic size-dependent diffusion behaviour of a NP. The size obtained
from TEM may vary with that obtained from the DLS technique as the size obtained
from DLS is the average ensemble size which is insensitive to deviation from the
spherical shape of NPs. Depolarized Fabry–Perot interferometry (FPI) [90] is a less
commonly used method for the size determination of anisotropic NPs.
The above-mentioned characterization techniques are often used to evaluate the
quality as well as quantity of the NPs after synthesis. In the following sections, exam-
ples of characterization of noble metal NPs are presented for a better understanding
of readers.

13.2.1 Chemical Reduction

The chemical reduction method is a rapid and simple approach for the metal NPs
synthesis in the form of colloidal dispersions that remain stable in aqueous or
organic solvents. The metal NPs with varying sizes and shapes can be prepared
522 A. Das and N. Maiti

using this approach. This process involves the initial creation of nuclei, induced
by the commonly used reducing agents like sodium borohydride (NaBH4 ) [91,
92], hydrazine [93], sodium citrate [94, 95], hydroxylamine hydrochloride [96],
ascorbic acid [97], anionic ligands [98], etc. Some solvents like formamide [99,
100], N, N -dimethylformamide (DMF) [101], formaldehyde [102], phenols [103,
104], methanol [105], ethanol [106–108], iso-propanal [109], ethylene glycol [110],
etc. can act both as solvents as well as reducing agents. Various other methods
of synthesis of composite nanomaterials are based on the dispersion of the NPs
in a polymeric matrix. This method of synthesis of composite nanomaterials is
of growing importance owing to their wide variety of applications. The frequently
used polymers for the preparation of colloidal NPs are poly(vinylpyrrolidone) (PVP)
[111, 112], poly(ethylene glycol) (PEG) [113–115], poly(methacrylic acid) (PMAA)
[116], polymethylmethacrylate (PMMA) [117], polyacrylamide [118–122], etc. The
type of reducing agent employed for the synthesis of NPs has been found to greatly
affect the size of the resultant particles. It has been observed in the case of silver
that stronger reductants such as NaBH4 lead to the formation of smaller nuclei in
the “seed” while employing weaker reductants such as citrate lead to the wider size
distribution of particles owing to a slow reduction rate [123]. During the ripening
process with strong reducing agents, the nuclei grow to produce the colloidal metal
NPs with a narrow size distribution. The creation of nuclei is followed by a growth
stage. The growth can be controlled using a stabilizer or it may result in the devel-
opment of aggregated particles in the absence of a stabilizer. The reductant may also
act as a stabilizer so as to avoid the agglomeration of the particles. A few commonly
used synthetic protocols are discussed below.

13.2.1.1 Sodium Borohydride Reduction

In this method, the Ag NPs synthesis involves chemically reducing the Ag ions by
NaBH4 [91]. Briefly, 10 mg of NaBH4 is added to 100 mL (N2 saturated) AgNO3
solution (100 μM). The solution is then shaken vigorously. The appearance of a clear
yellow coloured solution confirms the formation of Ag NPs. The solution pH is ~9
owing to the hydrolysis of the excess amount of NaBH4 . The redox reaction is as
follows:

2AgNO3 + 2NaBH4 + 6 H2 O → 2Ag + 2NaNO3 + 2H3 BO3 + 7 H2 O

(13.1)

N2 purging before the addition of NaBH4 is necessary in order to eliminate O2

and to circumvent the oxidation of Ag particles.

4Ag + O2 + 2H2 O → 4Ag+ + 4OH− (13.2)

In the beginning, zerovalent Ag NPs are produced that owing to the occurrence
of excess BH4 ¯ gets chemisorbed on the surface of particles causing deposition of
13 Synthesis of Functionalized Noble Metal Nanoparticles 523

surplus electrons on the Ag particles. In this case, the Ag NPs are ionic in nature
providing them hydrophilic character.
The alternative approach for the preparation of colloidal Ag NPs is according to
the modified Creighton’s method [92]. In brief, 10 mL of AgNO3 (1 mM) solution is
added gradually to 30 mL of 2 mM NaBH4 (ice-cold) solution with slow stirring. The
reaction is executed in an ice bath with continuous stirring. The colour of the solution
changes steadily to pale yellow. Stirring is sustained till the solution is cooled down
to room temperature (RT). The Ag NPs prepared by the modified Creighton’s method
leads to the development of monodisperse particles with a characteristic peak with
an absorption maximum at 390 nm as displayed in Fig. 13.2. These particles are
ideal for surface modification and functionalization. The alkaline pH (9) of the Ag
NPs facilitates the dissolution of adsorbate molecules even with low solubility. The
alteration in the SPR absorption band after surface modification/functionalization can
be investigated using optical absorption spectroscopy. The size and shape of the NPs
thus formed can be monitored using transmission electron microscopy (TEM), atomic
force microscopy (AFM) and scanning electron microscopy (SEM) techniques. The
representative TEM and AFM photographs of the Ag NPs formed by the modified
Creighton procedure are shown in Figs. 13.3 and 13.4, respectively. The figures
clearly display the development of spherical particles with ~15–20 nm average size.
The addition of 0.03 M HCl to borohydride stabilized NPs led to the formation
of AgCl/Ag NPs [124]. The contrast in TEM image originating from the difference
in electron density of Ag and AgCl NPs, as displayed in Fig. 13.5, along with the
(SAED) selected area electron diffraction pattern led to the identification of AgCl/Ag
hybrid particles.
Platinum (Pt) NPs can also be prepared by reducing Pt ions with NaBH4 in the
presence of a protecting agent [125–127]. Pt NPs were synthesized by reducing
chloroplatinic acid by NaBH4 in the presence of mercaptosuccinic acid as a stabilizer
[128]. The above method led to the development of well-separated Pt particles of
size ~2.5 nm, which was characterized by TEM and is shown in Fig. 13.6.

Fig. 13.2 SPR band of

borohydride stabilized Ag 1.0
NPs
Absorbance (arb. units)

0.8

0.6

0.4

0.2

200 300 400 500 600 700 800

Wavelength(nm)
524 A. Das and N. Maiti

Fig. 13.3 TEM image of borohydride stabilized Ag NPs

Fig. 13.4 AFM image of borohydride stabilized Ag NPs

Palladium (Pd) NPs stabilized by citrate can be synthesized by reducing palla-

dium chloride with sodium borohydride at room temperature [129]. The Pd particles
obtained were 6.5 nm in size. The Pd NPs were then loaded on polystyrene (PS)
microspheres to make composite materials. The main idea behind the use of PS
microsphere is to easily recover the composites after each catalytic cycle. The TEM
image and associated histogram of the Pd NPs as well as the TEM photograph of
13 Synthesis of Functionalized Noble Metal Nanoparticles 525

Fig. 13.5 TEM image of borohydride stabilized AgCl/Ag NPs

Fig. 13.6 HRTEM photograph of Pt NPs, synthesized in aqueous medium by reducing chloro-
platinic acid with NaBH4 in the presence of mercaptosuccinic acid. Inset displays the electron
diffraction pattern and size distribution of particles. Reprinted and adapted with permission from
Ref. [128] Copyright 2001 American Chemical Society
526 A. Das and N. Maiti

Fig. 13.7 TEM image of Pd NPs displaying the size (average) of a ~6.5 nm and b histogram with
size distribution; TEM photographs of Pd/PS composites with different magnification; low c and
high (d). Reprinted with permission from Ref. [129] Copyright 2015 Royal Chemical Society

Pd/PS nanocomposites is displayed in Fig. 13.7. The catalytic application of Pd NPs

is discussed later.

13.2.1.2 Sodium Citrate Reduction

A rapid and simple method of Ag NPs preparation involves reducing AgNO3 with
sodium citrate by Lee and Meisel technique [94]. In brief, 100 mL aqueous solution
of AgNO3 (1 mM) is boiled, 3 mL of sodium citrate (1% wt/v) solution is then
added dropwise with continuous stirring and the heating sustained for further 5 min
until the colour of the solution turns intense yellow. The solution is subsequently
cooled down to RT. The particles thus formed have high polydispersity and show the
characteristic SPR absorption band with a maximum of about 400 nm.
For the preparation of Ag NPs with controlled shape and size, the balance
involving nucleation and growth is of great importance. The modified Lee Meisel
method [130] for the controlled preparation of quasi-spherical Ag NPs depends on
combining the original Lee Meisel method and the seed-induced growth involving
the reduction of AgNO3 by heating with sodium citrate. Here, the citrate-capped
Ag NPs having sizes varying up to 80 nm can be obtained through a single step or
stepwise growth mechanism with the use of 4 nm Ag particles that are spherical in
shape as the starting seeds. The major problems involving the development of NRs
13 Synthesis of Functionalized Noble Metal Nanoparticles 527

and secondary nucleation through the growth process can be efficiently overcome by
adjusting the experimental conditions, viz., the amount of seed, reaction temperature
and tuning of pH. It is established that, regardless of the homogeneity of seeds, the
ratio of monomer versus seed plays a crucial part in influencing the shape and size of
the final particles. With the aim to restrain the formation of NRs and events related to
the second or further nucleation, the monomer to seed ratio needs to be kept moder-
ately low. These crucial factors, i.e. the reaction temperature, the amount of seed
and pH alteration are necessary for the fabrication of size- and shape-controlled Ag
NPs. Schematic illustration of a single step followed by the stepwise seed-induced
growth of Ag NPs is displayed in Scheme 13.2. The optical absorption spectrum of
the synthesized Ag NPs solution and the TEM photograph of the particles are given
in Fig. 13.8a. The representative SEM photographs of the Ag NPs prepared by the
Lee Meisel method and through seed-induced growth with 10, 5, 3, 1.5 and 0.75 mL
of Ag seeds, respectively, are shown in Fig. 13.9.
Synthesis of Au NPs can be carried out using the modified Turkevich method
[131]. In this method, 100 mL aqueous solution with 0.01 g of chloroauric acid is
heated at first, followed by the dropwise addition of 3 mL of 1% (w/v) solution of
sodium citrate with continuous stirring. Heating is then sustained for a further 15 min
until the solution colour turns intense red. The solution is subsequently cooled down
to RT. The Au NPs show a characteristic SPR peak with a maximum of 520 nm
as shown in Fig. 13.10 and the particles remain stable for several weeks. The size
(~20 nm) and spherical shape of the particles are clearly seen from the representative
TEM and AFM photographs in Figs. 13.11 and 13.12, respectively.
Pt NPs can also be synthesized by reducing the Pt ions with sodium citrate by
refluxing at 100 °C for 8 h, in the presence of inorganic salts as a stabilizer [132].
Different sizes of Pt NPs can be obtained by altering the ratios of Pt ion and citrate
ion as well as Pt ion and the inorganic salt used as a stabilizer. The representative
TEM photographs of the Pt NPs are displayed in Fig. 13.13.

Scheme 13.2. Schematic representation showing a single step and stepwise seed-induced growth
of Ag NPs (Lee Meisel method). Boundaries with twinning are demarcated with red lines. Reprinted
with permission from Ref. [130] Copyright 2013 Elsevier
528 A. Das and N. Maiti

Fig. 13.8 a UV–vis absorption spectrum of the synthesized Ag NPs; An inset showing the photo-
graph of the colloidal Ag NPs and its TEM image with the scale bar of 20 nm. b HRTEM photograph
of the colloidal Ag NPs displayed in panel a with a scale bar of 5 nm. Reprinted with permission
from Ref. [130] Copyright 2013 Elsevier
13 Synthesis of Functionalized Noble Metal Nanoparticles 529

Fig. 13.9 SEM photographs of a the synthesized Ag NPs. b–f The synthesized Ag NPs displaying
seed-induced growth with 0.75 to 10 mL of Ag seeds as per Ref [130]. Scale bars of 0.2 μm.
Reprinted with permission from Ref. [130] Copyright 2013 Elsevier
530 A. Das and N. Maiti

Fig. 13.10 SPR band of 1.0

citrate stabilized Au NPs

Absorbance (arb. units)

0.8

0.6

0.4

0.2
200 300 400 500 600 700 800
Wavelength(nm)

Fig. 13.11 TEM image of

Au NPs prepared using
modified Turkevich method

13.2.1.3 Functionalized Silver and Gold Nanoparticles

Amino Acids as Reducing Agent

Amino acids have been largely used for the preparation of Au NPs [133, 134] and
Ag NPs [135]. Maruyama et al. [136] have shown that out of the 20 essential amino
acids, about 9 amino acids such as alanine, asparagines, aspartic acid, glycine, histi-
dine, phenylalanine, tryptophan, tyrosine and valine can efficiently reduce as well
13 Synthesis of Functionalized Noble Metal Nanoparticles 531

Fig. 13.12 AFM image of Au NPs prepared using modified Turkevich method

as stabilize the Au NPs. The stabilization of the metal particles by amino acids is
attributed to the negative charge of the carboxylic groups [133, 134].
Tryptophan, phenylalanine and tyrosine show fluorescence, which adds another
facet to the functionality of zwitterionic amino acids. Many amino acids including
tryptophan were reported to be utilized as capping agents for functionalization of
citrate or borohydride-capped Au or Ag NPs [135]. Tryptophan (Trp) has also been
used for the preparation of Ag particles in the presence of other stabilizing agents.
The reducing power of Trp is intermediate between borohydride and citrate. This
makes Trp a suitable reductant for studying the development and growth of noble
metal NPs.
The zwitterionic property of amino acids can be imparted to Au NPs by using
Trp as a reducing agent as well as a stabilizer in a buffer medium [133]. Visual
monitoring of the colour change in the reaction mixture containing Au ions and Trp
in buffered aqueous medium at various pH revealed that the particles synthesized
at pH 6 and above were stable, as shown in Fig. 13.14. It can be seen that at pH 3
and 4, the colourless solution of Au ions and Trp at first turned reddish, and then
it turned purple as the reaction progressed and finally precipitated at the end of the
reaction. In the case of pH 5 onwards, colourless reagents first turned orange-yellow,
and finally red as the Au NPs were formed. This orange-yellow colour formation as
observed above may be due to the complex formation between Au and Trp. At lower
pH, the primary amine group of Trp due to protonation is available to a lesser extent
for complex formation. Trp-Au complex then gets reduced by decarboxylation [133,
137] which is monitored by the evolution of carbon dioxide by gas chromatography,
as shown in Fig. 13.15.
532 A. Das and N. Maiti

Fig. 13.13 TEM images of Pt NPs prepared by altering the ratio of trisodium citrate (Cyt) and Pt
ions in solution in the presence of electrolytes as per Ref. [132]. Reprinted with permission from
Ref. [132] Copyright 2014 Elsevier
13 Synthesis of Functionalized Noble Metal Nanoparticles 533

Fig. 13.14 Visual

monitoring of colour change
in the reaction mixture
containing Au ions and Trp
in buffered aqueous medium
at various pH with time.
Reprinted and adapted with
permission from Ref. [133]
Copyright 2015 Elsevier

Fig. 13.15 Gas

chromatograph of the
evolved CO2 during
synthesis of Trp
functionalized Au NPs;
a sample, b standard and
c blank. Reprinted with
permission from Ref. [133]
Copyright 2015 Elsevier
534 A. Das and N. Maiti

Chiral amino acids, viz., free cysteine and cysteine-containing peptides have been
reported to impart chirality to Au NPs, which is manifested in their circular dichroism
spectra as well as TEM image [138].
Formamide as Reducing Agent
Ag NPs synthesis in formamide [99] as stabilizing and reducing agent in the absence
of any external reductant is discussed below. The growth of the Ag NPs depends
on the Ag ions concentration. In the absence of a stabilizer, Ag films are deposited
on the walls of the glass container. However, in the presence of a stabilizer such
as poly(N-vinyl-2-pyrrolidone) (PVP) or colloidal silica (SiO2 ), a clear dispersion
is observed, which enables the formation of stable Ag NPs by complexation with
PVP or SiO2 . The time-dependent (TD) UV–vis absorption spectrophotometry, TEM
and AFM techniques are used to monitor the formation of Ag NPs. The TD optical
absorption spectrum of Ag NPs in formamide with AgNO3 (2 mM) and PVP (1%
wt/v) is displayed in Fig. 13.16a. From the figure, gradual augmentation in the SPR
band intensity at 425 nm is observed that indicates the incessant formation of NPs. In
about an hour, there is relative slowing down in particle formation and the SPR band
remains symmetric with an insignificant change in its width. This shows that the
particles size remains almost uniform. The SPR band of Ag NPs in formamide in 1%
PVP shows a maximum at 425 nm and is shifted to the red relative to the absorption
maximum of Ag NPs in water. This red shift in the SPR band is possibly due to
formamide having a higher refractive index than water. Kinetic traces displaying the
Ag particles formation in formamide for varying concentrations of Ag ions in 1%
PVP is displayed in Fig. 13.16b. From the figure, the growth rate of the particles is
observed to be enhanced with increasing concentrations of Ag ions.
The surface topography of the Ag NPs, prepared in the presence of different
stabilizers, is investigated using TEM. The TEM samples are prepared by inserting

Fig. 13.16 a TD optical absorption spectrum of Ag NPs formed by reducing AgNO3 (2 × 10–3
M) in formamide with PVP (1% wt/v). b Kinetic traces displaying the development of Ag NPs in
formamide with constant (1 wt %/v) PVP concentration and increasing concentrations of Ag ion.
Reprinted with permission from Ref. [99] Copyright 2005 American Chemical Society
13 Synthesis of Functionalized Noble Metal Nanoparticles 535

Fig. 13.17 TEM images of Ag NPs in formamide (a) for 5 × 10−3 M Ag ions concentration with
PVP (1% wt/v) [displaying twinned particles]; b typical electron diffraction pattern of a twinned
particle; and c huge flat particles having distinct geometric shapes. Reprinted with permission from
Ref. [99] Copyright 2005 American Chemical Society

a drop of colloidal Ag NPs solution on the copper grid (carbon-coated) and drying
at RT. Since formamide is extremely viscous with a high boiling point, it takes a
long time to dry these samples. A characteristic TEM photograph for a colloidal
Ag NPs solution containing PVP (1% wt/v) is displayed in Fig. 13.17. The mean
size of the particles in PVP (1%) is about 25 nm as shown in Fig. 13.17a. Twinning
of the particles is also observed at certain places as confirmed from the diffraction
pattern (Fig. 13.17b). Twinning is a phenomenon that is common for face-centred
cubic (fcc) structures. The TEM images as seen from Fig. 13.14c reveal that during
the drying process, the Ag film arrangement takes place encircling many particles
and assuming a disk type shape.
The morphology of the Ag NPs without an added stabilizer is probed by AFM.
For this purpose, glass slides are suspended in the solution for ~24 h leading to the
arrangement of Ag films on the glass surface. Once the films are formed, the slides
are taken out, washed with water and air-dried before examining the same with AFM.
Fig. 13.18 shows the AFM image of the polygonal particles with the size of 100 nm.
The glass slides, prepared by this procedure, show TD optical properties that depend
on the packing density of the Ag particles.
Polyols as Reducing Agent
Polygonal (triangular) Ag nanoprisms (NPRs) [139] can be synthesized by the reduc-
tion of silver perchlorate with formamide in the presence of polyethylene glycol
(PEG) at RT. Briefly, an aqueous solution of silver perchlorate is added to formamide
with PEG [0.1–1% (wt/v)] of varying concentrations. The solution is then uniformly
mixed and allowed to stand. The solution immediately turns grey in colour. Glass
slides are then suspended in the formamide solution with PEG. The film formation
536 A. Das and N. Maiti

Fig. 13.18 AFM photograph

of Ag NPs prepared by
reducing 5 mM Ag ions in
neat formamide. Reprinted
with permission from Ref.
[99] Copyright 2005
American Chemical Society

was found to take place on the glass slides with time. The slides are dipped in the solu-
tion for about 17 h and then these slides are removed, washed with water and dried at
RT. These slides are protected from light; both during and after the film formation.
The reduction of Ag ions by formamide results in the array deposition of triangle-
shaped Ag NPs on the glass walls of the container. AFM images are recorded to study
the morphology of the Ag films. The representative image as shown in Fig. 13.19
indicates the arrangement of triangular-shaped particles. It is observed that PEG
results in the formation of triangle-shaped particles with distinct orientations. The
structures displayed in the figure are representative of the entire film. The presence of
particles with spherical or ellipsoidal/polygonal shape at random places contributes
to less than a few percent of the surface. In addition, a three-dimensional AFM
image is also shown in the figure, which reveals the film thickness. For the Ag films,
since the reduction and aggregation processes are simultaneous, it is not possible to
characterize the films with UV–vis (optical) absorption spectroscopy. Therefore, in
order to record the optical absorption of Ag NPs, a different methodology is usually
adopted. PVP, a polymer accomplished of stabilizing and complexing the Ag NPs, is
added to the reaction mixture of Ag in formamide that contains PEG. It is observed
that PVP inhibits the Ag particles aggregation resulting in a stable clear dispersion
of Ag NPs. Thus, the Ag particles are prepared in formamide containing 1:1 ratio
of PVP and PEG. In Fig. 13.20, the optical absorption spectrum of colloidal Ag
NPs in formamide in the presence of both PEG and PVP is shown. It is seen from
Fig. 13.20a, b that with increasing concentrations of Ag+ , the SPR band gets red-
shifted with time. At first, only a single band is observed at 420 nm that corresponds
13 Synthesis of Functionalized Noble Metal Nanoparticles 537

Fig. 13.19 a AFM photograph (5 × 5 μm) displaying the Ag NPRs array obtained by reducing Ag
ions (10 mM) in formamide [1% PEG (wt/v)]. b 3D AFM photograph. Reprinted with permission
from Ref. [139] Copyright 2005 Elsevier

to the out-of-plane (oop) dipole resonance of Ag (NSPs) nanospheres. This band

steadily shifts towards a higher wavelength with the progress of the reaction and
ultimately shows a peak with a maximum of 510 nm. Thus, in the presence of (1:1)
PEG and PVP, the formation of both Ag NSPs and Ag NPRs is observed.
538 A. Das and N. Maiti

Fig. 13.20 Time-dependent

(TD) optical absorption
spectrum displaying the
development of NSPs and
NPRs obtained from a 2 mM
AgNO3 in formamide with
1% (wt/v) of PEG and PVP);
b 4 mM AgNO3 in
formamide with 1% (wt/v) of
PEG and PVP. Reprinted
with permission from Ref.
[139] Copyright 2005
Elsevier

Pt, Pt/Ag, Pd and Pd/Ag NPs can be synthesized from the metal precursors in
ethylene glycol and glycerol in the presence of PVP using the microwave technique
[140]. The formation of Pt, Pt/Ag, Pd and Pd/Ag NPs using microwave irradiation was
monitored by UV–vis absorption spectroscopy, XRD and dynamic light scattering.
X-ray diffraction (XRD) confirmed the formation of Pt, Pt/Ag, Pd and Pd/Ag NPs.
It is observed that the mixed metal Pt/Ag and Pd/Ag NPs can be synthesized either
by the amalgamation of the individual colloidal solutions or by co-reduction of the
precursor metal salts.
13 Synthesis of Functionalized Noble Metal Nanoparticles 539

Fig. 13.21 TEM images displaying the development of Ag nanoprisms obtained by reducing high
Ag+ concentration (2 × 10–2 M) in DMF in the presence of PVP, at various time intervals: a 5,
b 15 and c 60 min. Reprinted with permission from Ref. [141] Copyright 2002 American Chemical
Society

N,N-Dimethyl Formamide as Solvent and Reducing Agent

Ag NPRs with polygonal shape (triangular) were prepared by heating AgNO3 in
N,N-dimethyl formamide (DMF) in the presence of poly(vinylpyrrolidone) [PVP]
[141]. Here, DMF acts as a strong reductant. The proposed reaction is as follows:

HCONMe2 + 2Ag+ + H2 O → 2Ag0 + Me2 NCOOH + 2H+ (13.3)

The reaction involves the formation of Ag NPs in addition to carbamic acid and an
acidic environment. During this synthesis, a combination of NPRs and nanospheres
are formed. The nanospheres can be separated through repeated centrifugation. The
TEM images that show the growth of Ag NPRs as a function of time are displayed
in Fig. 13.21. These images indicate that at first small spheres are produced, which
then accumulate leading to the formation of particles with prism-like shapes. The
formed NPRs then are converted into larger particles with time, and a broader range
of shapes are observed (Fig. 13.21).
The UV−visible absorption spectrum of colloidal Ag NPs in DMF during the
formation of NPRs is shown in Fig. 13.22. Initially, a single band centred at 410 nm
is observed in the absorption spectrum that corresponds to the dipolar resonance
of Ag NSPs. As the reaction progresses, this band is red-shifted, along with the
appearance of other peaks. After 20 min of heating the reaction mixture, four peaks
are seen, which are comparable to the ones predicted by Jin et al. [142], apart from an
intense peak at 460 nm that is attributed to the existence of spherical particles (seen
from TEM). Since the NSPs present in the colloidal dispersion are evidently smaller
than the NPRs, they can be effortlessly removed by centrifugation. This method has
the benefit that PVP prevents the aggregation of the particles all through the reaction.
A one-pot approach to synthesize triangular Ag NPRs was developed by Zhang
et al. [143]. The size of the triangular Ag NPRs from 30 to 100 nm was adjusted by
altering the amount of n-pentanol solution and sodium hydroxide in the ternary
system containing water/PVP/n-pentanol. The n-pentanol solution and sodium
540 A. Das and N. Maiti

Fig. 13.22 Time evolution

of the optical absorption
spectrum showing the
development of Ag
nanoprisms in DMF
medium. Reprinted with
permission from Ref. [141]
Copyright 2002 American
Chemical Society

hydroxide led to the modification of the original pH of the ternary system. This
resulted in the extremely reproducible synthesis of triangular NPRs. In order to have
well-defined shapes of the NPs, formamide and N,N-dimethyl formamide (DMF)
were both utilized to manage the system pH. The extinction spectrum of the trian-
gular Ag NPRs was observed to be relatively narrow that made them suitable for
different biological and chemical applications. The photographs of the Ag NPRs in
ethanol dispersions of varying edge lengths (average) are displayed in Fig. 13.23a.
These dispersions as seen from the figure differ in colour owing to their LSPR prop-
erty ranging from pink, purple and blue. The dipole (in-plane) plasmon resonance
peak of Ag NPRs gets shifted to the red with an enhancement in the (average) edge
length of the NPRs. Fig. 13.23b shows the extinction spectrum of Ag NPRs with
different (mean) edge lengths dispersed in ethanol. Each spectrum displays three
distinct peaks; first strong peak at longer wavelength; second weak and broad band
and third sharp weak peak at shorter wavelength. The three bands are attributed
to in-plane (ip) dipole, (ip) quadrupole and out-of-plane (oop) quadrupole plasmon
resonance bands [144]. It is observed from Fig. 13.23b, the dipole (ip) plasmon-
resonance band gets blue shifted to a shorter wavelength with increasing amounts
of the sodium hydroxide-pentanol solution. In Ag NPRs, the 111 reflection plane
is prominent and appears at 2θ = 38.2° and is shown in Fig. 13.23c. The figure
displays that the preferred orientation of the Ag NPRs is the 111 plane. The surface
morphology of the triangular Ag NPRs is also monitored using SEM. The SEM
images as shown in Fig. 13.24a reveal that the Ag NPRs prepared using DMF have
a definite shape with pointed corners but their sizes remain uneven. The use of
formamide as displayed in Fig. 13.24b improves the shape (triangular) of the Ag
NPRs, but the range of distribution in size gets expanded leading to broad extinction
bands.
Chelating Agents as Reducing Agents
Au and Ag NPs can be synthesized using chelating agents [145, 146] such as
ethylenediaminetetraacetic acid (EDTA). It is found that EDTA forms a complex
13 Synthesis of Functionalized Noble Metal Nanoparticles 541

Figure 13.23. a Photographs and b extinction spectrum for the Ag NPRs in ethanol dispersions
of varying edge lengths (average) of (1) 30, (2) 35, (3) 45, (4) 50, (5) 60, (6) 70, (7) 80 and (8)
100 nm. c XRD spectrum of the Ag NPRs. Reprinted with permission from Ref. [143] Copyright
2019 Royal Society of Chemistry
542 A. Das and N. Maiti

with metal ions [145] which helps in the controlled release of the metal ions for
reduction. This phenomenon leads to the ligand concentration-dependent size control
in noble metal NPs. The effect of different chelating agents such as nitrilotriacetic
acid (NTA), triethylenetetramine-N,N,N’,N”,N”’-hexaacetic acid (TTHA), EDTA,
N-(2-hydroxyethyl)ethylenediaminetri-acetic acid (HEDTA) and iminodiacetic acid
(IDA) on the surface activity of Ag NPs synthesized using the above ligands is inves-
tigated [98]. The denticity of the above ligands increases in the following order:
IDA (3) < NTA (4) < HEDTA (5) < EDTA (6) < TTHA (10) where the maximum
achievable denticity is given in parenthesis. In Fig. 13.25, the TEM image and the
associated histogram of the chelating agent reduced Ag NPs is shown. It can be seen
that the ligand with the smallest denticity (NTA) has the largest particle size. The
NPs size was found to reduce with an increase in denticity. This observation indicates
that after the initial formation of the NPs, the ligands get adsorbed on the surface of
the particles, thereby controlling the growth of the particles size. Amongst NTA and
HEDTA, it can be seen that although for both the ligands, the synthesized Ag NPs

Fig. 13.24 SEM images of the Ag NPRs made from 0.6 g PVP and 3 mL of a DMF and b formamide.
Reprinted with permission from Ref. [143] Copyright 2019 Royal Society of Chemistry
13 Synthesis of Functionalized Noble Metal Nanoparticles 543

are fairly monodispersed, the NTA-capped Ag NPs are larger in size when compared
to that of HEDTA-capped Ag NPs. This observation indicates that under similar
conditions, ligands with lower denticity have poor control over the size of particles.
HEDTA-capped Ag NPs are also found to show definite geometry, indicating strong
adherence of the ligand to a selective crystal plane. In the case of TTHA, very high
denticity results in the loss of size control and thus, Ag NPs with broad size distribu-
tion are formed. TTHA-capped Ag NPs are found to coalesce, which indicates poor
stabilization by the ligand.

Fig. 13.25 TEM images and histogram of HEDTA, TTHA and NTA capped Ag NPs. Reprinted
and adapted with permission from Ref. [98] Copyright 2014 Elsevier
544 A. Das and N. Maiti

Sugars as Reducing Agent

Ag and Au NPs functionalized with α-, β- and γ-cyclodextrin (CD) are prepared by
the successive addition of AgNO3 (1 mM) and HAuCl4 ·H2 O (1 mM) and NaOH to
the aqueous solution of α-, β- and γ-CD (10 mM). In this method of preparation of
functionalized Ag and Au NPs, α-, β- and γ-CD are used both as reductant as well
as a stabilizer. The pH of the solution is maintained at ≥ 10. The solution initially
appears colourless showing no development of Ag and Au NPs. The reaction mixture
is then refluxed at ~60 °C for 10 min. During reflux, the colour of the solution
starts to change and finally turns greenish-yellow and bright red demonstrating the
development of Ag and Au NPs. The particles are then cooled to RT and used for
additional characterization. The optical absorption spectrum of the synthesized Ag
and Au NPs is shown in Fig. 13.26. The figure shows peaks with a maximum at 404
and 515 nm that correspond to the characteristic SPR bands of the Ag and Au NPs.
The shape as well as the size of the NPs is obtained from TEM (Fig. 13.27) images
that show the development of sphere-shaped particles with a size of 25 and 15 nm
for Ag and Au NPs, respectively.
Au NPs can also be prepared using β-D-glucose as a reductant. The reaction occurs
at RT in the presence of NaOH [147]. In another method, Au3+ ions are immobilized
in Ca-Fe cross-linked alginate films and reduced using 0.05 M glucose in an aqueous
medium by heating the solution for 5 min at 60 °C in a water bath [148]. The colour of
the film varies from yellow to red after the reduction of Au3+ ions. The films showing
maximum uptake of Au3+ ions are taken up for further studies. In Fig. 13.28, the TEM
image of synthesized Au NPs shows clustering of the particles in the alginate matrix,

1.5
Ag NPs
Au NPs

1.0
Absorbance

0.5

0.0
200 300 400 500 600 700 800
Wavelength / nm

Fig. 13.26 SPR bands of γ-CD functionalized Ag and Au NPs

13 Synthesis of Functionalized Noble Metal Nanoparticles 545

Fig. 13.27 TEM photographs of γ-CD-capped a Ag and b Au NPs

Fig. 13.28 TEM image of

Au NPs loaded in Ca-Fe
cross-linked alginate film

which is largely instrumental in the SERS activity exhibited by the films which will
be discussed later.

13.2.2 Radiolytic Reduction

Radiolysis of water or any organic solvent by gamma (γ) radiation or electron

−
produces primarily free radicals such as hydrated electrons (eaq ), OH• , H• and H2 O2
− •
under N2 atmosphere. eaq and H are the primary reducing species responsible for
reducing the noble metal ions or precursors to NPs [149, 150]. The standard reduction
546 A. Das and N. Maiti

− −
potential of eaq and H• expressed as E0 (H2 O/eaq ) and E0 (H+ /H• ) are −2.87 V and −
2.3 V, respectively [151]. No external reducing agent is required in this method. In
fact, the reducing agent, i.e., the hydrated electron is generated in situ and the unre-
acted electrons are absorbed by the solvent via the recombination reaction. In contrast
to the chemical methods, the lack of excess reducing agent in radiolytic synthesis
eradicates the requirement of post-synthesis purification. The radiolytic reduction
reaction takes place homogeneously, which leads to the narrow size distribution of
particles [152].
In order to exclusively construct the environment for reducing radical-mediated
reaction, potent oxidative radical OH• must be scavenged using species such as
secondary alcohols and formate anions. Radiolytic reduction reaction occurs sponta-
−
neously at RT as eaq and H• have very high diffusivity. The rate of reaction can only
be controlled by varying the dose of the ionizing radiation. The dose rate controls the
concentration of free radical generated, which in turn react with the metal precursors.
The relation between the dose of ionizing radiation and the concentration of gener-
ated radical can be understood by a detailed study of the effects of the interaction of
ionizing radiation with matter [153].
γ radiation, specifically, 60 Co source is generally used to carry out bulk reactions.
In our laboratory, recently, Ag NPs were synthesized by reducing Ag ions by γ
radiation in the presence of PVP as a stabilizer [154]. In this study, most of the critical
controlling aspects of radiolytic synthesis have been covered. AgClO4 solution of 3.0
× 10–2 M in the presence of 2-propanol (1 M) and varying concentrations of PVP was
irradiated using 60 Co γ-radiation of dose rate 1 Gy/h. The development of Ag NPs was
investigated using optical absorption spectroscopy, which is displayed in Fig. 13.29.
It is known that perchlorate ions have lower reactivity towards the reducing radicals
in comparison to nitrate ions. Thus, silver perchlorate was taken as a metal precursor
to study other associated effects. In this study, nitrate ions did not show any shape
alteration, which was otherwise observed by Kuo et al. [155]. Upon studying the
effect of PVP as a stabilizer, it was observed that higher PVP concentration (0.1%
w/v) promotes spherical Ag NPs formation, whereas lower concentration (0.01%
w/v) leads to the development of anisotropic Ag NPs, which was characterized by
the optical absorption spectroscopy. At higher concentrations of Ag ions, anisotropic
NPs of a higher aspect ratio were obtained. At a lower concentration of Ag ions, the
anisotropic effect was not observed. The appearance of the anisotropic particles at
a higher concentration of Ag ions may be due to the higher concentration of Ag0
seeds generated at a fixed dose. It was also observed that the adsorption of OH−
ions at higher pH affected the shape of the Ag NPs. Upon administration of a higher
cumulative dose of 60 Co γ-radiation, Ag nanoplates were obtained, which is given
in Fig. 13.30.
In another interesting work, radiolysis was used for the functionalization of Au
NPs in DMF and water mixtures [156]. Thiol-functionalized polyoxometalates were
subjected to in situ disulphide formation during radiolysis. This thiol or disulphide
adsorption on the surface of Au NPs controlled the shape of the particles. Secondary
alcohol added to the reaction mixture for scavenging the oxidizing radicals played
13 Synthesis of Functionalized Noble Metal Nanoparticles 547

Fig. 13.29 Optical absorption spectrum of Ag NPs prepared with varying doses of γ radiation for
the solution having AgClO4 ( 30 mM), PVP (0.01% w/v) and 2-propanol (1 M) with a dose rate
of 1 kGy hr−1 . Cuvette path length a 1 and b 0.1 cm. Reprinted with permission from Ref. [154]
Copyright 2018 Elsevier

Fig. 13.30 TEM and SAED photographs of Ag NPs with varying doses of γ radiation (A–C) 0.5,
(D–F) 2.0 and (G–I) 4.0 kGy for aqueous solutions containing AgClO4 = 30 mM, PVP = 0.01%
(w/v) and 2-propanol = 1 M with a dose rate of 1 kGy h−1 . Reprinted with permission from Ref.
[154] Copyright 2018 Elsevier
548 A. Das and N. Maiti

a significant part in the disulphide formation [156]. The TEM images of different
shapes of Au NPs obtained under different reaction conditions is given in Fig. 13.31.
Apart from γ radiolysis, the pulse radiolysis technique is also often used to
study the synthesis of noble metal NPs by electron irradiation [157, 158]. Neither
γ-radiation nor electrons interact directly with the solute molecules in a solution.
Electrons, as well as γ-radiation, usually deposit their energy in the solvent, which
leads to the formation of short-lived radicals. These short-lived free radicals interact
with the solute molecules to generate transient species, which can be observed in
microsecond (μs) time scales. In the pulse radiolysis technique, the time-resolved
optical absorption spectrum of the transient chemical species at a fixed wavelength
is recorded, which is triggered by the incoming electron pulse [159]. It is advis-
able to keep the temporal width of the electron pulse shorter than the decay time
of the absorption spectra of the transient species at a fixed wavelength, preferably
the absorption maxima. Synthesis of zerovalent metal atoms and their clusters using
the pulse radiolytic technique is most important for fundamental research, basically
to understand the reaction mechanism. The cost of production of NPs by the linear
accelerator is very high and has limited applications.
Ag ions reduced by the hydrated electrons in ethylene glycol and glycerol medium
using pulse radiolysis were investigated [160]. Ag0 appeared both in ethylene glycol
and glycerol at around 360 nm, after 1 to 1.5 μs of bombardment with the electron
pulse. At longer times, i.e., beyond 4 μs, Ag0 species was found to decay with the
emergence of other cluster species of Ag such as Ag+ 2 , which showed absorption at
310 nm. Prolonged irradiation with the electron pulse, resulted in the reduction of
Ag ions by the hydrated electrons leading to the development of Ag NPs that showed
SPR band at 410 nm [160]. Interestingly, excited metal cluster species-mediated
reduction of metal ions can also be implemented using pulse radiolysis. The study
of electron transfer from Tl+ +
2 species to Ag is reported. Similarly, Au
3+
ions when
irradiated with hydrated electrons form Au0 species, which comproportionates in
presence of excess Au3+ to form monovalent and divalent species of Au [161]. This
makes Au0 difficult to detect by nanosecond pulse radiolysis. In Au(CN)2− systems,
where comproportionation is comparatively difficult than AuCl3− 4 , due to stronger
complexation by cyanide, Au0 species could be isolated at absorption maxima of
410 nm [162].

13.2.3 Photochemical Synthesis

Photochemical synthesis of noble metals is generally implemented by irradiating

metal ions in the presence of a light-sensitive electron-donating agent [163]. Ag ions
have a high tendency of forming Ag NPs when exposed to visible light [164]. This
resulted in AgBr being an active ingredient of camera films. It is also reported that
the seeds of Ag NPs autocatalyzes the formation of particles [165]. Au NPs can
also be synthesized photochemically by using a photosensitizer that would generate
13 Synthesis of Functionalized Noble Metal Nanoparticles 549

Fig. 13.31 TEM photographs of [POM(SH2 )]4− functionalized Au NPs acquired at different
DMF/water ratios by γ-radiolysis a 3:1 b 2:1 and c 1:1 and by chemical reduction d 4:1 and
e 1:1. f Electron diffraction patterns of the particles displayed in a-d. Reprinted with permission
from Ref. [156] Copyright 2013 Elsevier
550 A. Das and N. Maiti

reducing radicals upon exposure to visible light [166]. Photochemical synthesis of

Pt NPs is also known under UV irradiation [167].
Photochemical reduction of silver chloride in the presence of a dye is being
pursued worldwide. AgCl NPs were partially reduced [168] by illumination under Xe
Lamp, which led to the formation of Ag NPs decorated AgCl NPs. These Ag/AgCl
NPs showed an excellent photocatalytic property. In another work, it was shown that
blue-violet illumination of AgCl NPs led to the formation of Ag/AgCl NPs along
with oxidative degradation of rhodamine 6G (R6G) [169]. There are other possible
chemical methods [124, 170, 171] of synthesis of Ag/AgCl NPs apart from the above-
mentioned photochemical methods [168]. Along with AgCl, TiO2 has also been
employed for the photoreduction of Ag+ ions to Ag/AgCl@TiO2 nanocomposite
[172]. Ag NPs were found to be decorated on AgCl@TiO2 support, as shown in
Fig. 13.32. Ag NPs could be differentiated from AgCl by the interplanar distance of
111 plane of Ag as shown in Fig. 13.32.
Synthesis of Au NPs in the presence of ethylene glycol and PVP by photoreduction
is also reported. A mechanism was suggested to describe the photoreduction, which
claimed that light assisted in the excitation of Au3+ and reduction of Au+ species
[173]. The formation of Au NPs was monitored by the amplification in absorbance
of the SPR band, which is shown in Fig. 13.33. Benzoquinone is a light-sensitive
material that undergoes oxidation upon illumination by visible light [174] via a
free radical mechanism. Such materials can act as photo-reduction agents for the
preparation of Au NPs [175].

Fig. 13.32 TEM photograph of the synthesized Ag/AgCl@TiO2 -20 photocatalyst. Reprinted with
permission from Ref. [172] Copyright 2012 Elsevier
13 Synthesis of Functionalized Noble Metal Nanoparticles 551

Fig. 13.33 a Optical absorption spectrum of the irradiated Au3+ solution through a xenon lamp
with band-pass filters for different times. b Absorption spectrum of the samples at various intervals
of time with interrupted irradiation. Growth of the NPs (545 nm) and Au3+ (323 nm) is observed.
Both figures are from a sample containing HAuCl4 (2.4 mM), PVP (0.01 M) and ethylene glycol
(0.59 mol fraction). Reprinted with permission from Ref. [173] Copyright 2005 American Chemical
Society
552 A. Das and N. Maiti

13.3 Applications of Functionalized Noble Metal

Nanoparticles

Role of Plasmon in Colorimetry and SERS Applications

The unique SPR phenomenon in noble metal NPs is lately being implemented in
different sensing studies. All these sensing applications are guided by inter-particle
surface plasmon (SP) coupling [176]. Metal NPs exhibiting SPR are also called
plasmonic NPs. Upon excitation of such plasmonic NPs by electromagnetic radiation
of electric field E0 , an alternating electric field is produced in the neighbourhood of
the surface of the particle, known as near field, Enf , which decays with distance r
away from the particle as 1/r3 . When two plasmonic NPs are in close proximity
to each other, each particle upon electromagnetic excitation experiences an electric
field, E, which is a sum of E0 and Enf [177]. As a result, plasmons of both particles
are coupled and a red-shifted coupled plasmon appears. This decrease in energy for
plasmonic excitation can be ascribed to the amplification of the electric field at the
junction of the particles. NPs are brought closer to each other by agglomeration
[178]. Upon agglomeration, plasmonic NPs show a change in colour either due to
plasmonic coupling [67] or due to charge transfer (CT) complex formation [179].
Colorimetric Sensing
The phenomenon of the appearance of a new plasmon band due to either agglomera-
tion or CT is harnessed for colorimetric sensing applications. DNA recognition is one
of the interesting applications of Au NPs-based colorimetric sensing [180]. Lately, a
number of biologically important molecules such as heparin [181], melamine [182],
methamphetamine [183], venlafaxine [184], etc. are detected using Au NPs as a
probe. Similarly, Ag NPs are also used for the colorimetric detection of amoxicillin
[185], hydrogen peroxide [186], etc.
Melamine is a compound that is rich in nitrogen (66%) and is often used as an adul-
terant in milk to enhance the protein content falsely in milk and dairy products [187].
Melamine is considered to be harmful if swallowed, inhaled or absorbed through the
skin. The melamine-contaminated milk powder scandal occurred in China in the year
2008, where melamine adulteration was reported in infant formula. The presence of
melamine in infant formula resulted in the formation of urinary stone in children
leading to associated renal damage and increased child mortality. The methods (Kjel-
dahl and Dumas) used for the protein assessment in food samples actually evaluate the
nitrogen content which is an indirect measure of the protein content. These methods
are thus found to be unsuitable in distinguishing between the nitrogen of protein
or non-protein source (melamine) [188, 189]. Therefore, detection of melamine in
adulterated dairy products and food items by direct methods are essential.
A colorimetric detection protocol was developed in our laboratory to study the
adulterant, melamine in real milk samples. This method of detection is inexpensive
and has a fast response with a detection limit of 2 ppm, which is considered to be the
safe limit for the adulterant. Here, firstly, colloidal Au NPs were prepared by the modi-
fied Turkevich procedure. Secondly, the adulterant, melamine was extracted from
13 Synthesis of Functionalized Noble Metal Nanoparticles 553

Fig. 13.34 Colour chart showing increasing concentrations of melamine added to Au NPs

powdered and liquid milk samples using the centrifugation method. The extracted
melamine of different concentrations could be separated in the concentrate, which
when added to colloidal Au NPs resulted in the transformation of colour from bright
red to purple and finally to blue for high concentrations of melamine as shown in
Fig. 13.34. The colour change observed in the case of Au NPs upon addition of
melamine is possibly due to agglomeration of the particles caused by sorption of
melamine on the surface of Au NPs leading to red shift in the SPR band (520 nm).
Plasmonic NPs-based colorimetric sensing can also be implemented on toxic
heavy metal ions. Au nanoflowers (Au NFs) were synthesized at RT by mixing the
requisite amount of NaOH (1 mM) with ethylene glycol. To this mixture, HAuCl4
solution (0.5 mM) in the presence of PVP as stabilizer (0.1% w/v) was added [190].
The appearance of different colours as a function of time showed the development
of stable dispersions of Au NPs. Synthesized Au NFs suspensions in ethylene glycol
were violet in colour and demonstrated an intense absorption peak with a maximum
at 570 nm (Fig. 13.35) attributed to the SPR band. Synthesized Au NFs were utilized
for the detection of heavy toxic metal ions, Hg(II) and Pb(II) in an aqueous solution
by colorimetry. The colour, as well as absorption spectrum at various time intervals,
was monitored for the colloidal solution of Au NFs with the addition of Hg(II) and
Pb(II) over a dynamic range of 1–10 μM, respectively. The Au NFs had a response
time that was dependent on the metal ions concentration.
Adding Hg(II) to the colloidal Au NFs solution did not change either the colour
or the absorption spectrum, till the optimum concentration of Hg(II) was ≥ 1 μM.
When the Hg(II) concentration was 1 μM, the Au NFs changed colour within 4 h from
violet to magenta. With an increase in the Hg(II) concentration from 5 to 10 μM, the
554 A. Das and N. Maiti

Fig. 13.35 Absorption spectrum of Au NFs with the addition of 10 μM Hg(II) ions at different
times as per Ref. [190]. Inset displays the colour variation of colloidal Au NFs (a) before and
(b) after the addition of Hg(II) ions. Reprinted with permission from Ref. [190] Copyright 2013
Elsevier

absorption spectrum gradually blue-shifted without much change in the absorbance.

The colloidal dispersion changes colour within 30 min from violet to magenta and
after 24 h to wine red (shown as an inset in Fig. 13.35). Similarly, for Pb(II) detection
in colloidal Au NFs, varying concentrations of Pb(II) was added. In the presence of
10 μM Pb(II), the absorption spectrum underwent blue shifting with a decrease in
its absorbance as shown in Fig. 13.36.
The detection procedure was also checked for other metal ions [Co(II), Cd(II),
Cu(II), Mn(II), Zn(II), Na(I), Fe(II) and Fe(III)] of environmental relevance. The
Hg(II), Pb(II) and other metal ions concentrations were fixed at 1 μM. Variation
in the SPR band of the Au NFs with the metal ions addition was studied. From
Fig. 13.37, it is observed that adding the metal ions of concentration about 10 μM
[Co(II), Cd(II), Cu(II), Mn(II), Zn(II), Na(I), Fe(II), Fe(III)] to the Au NFs has a
negligible effect on its SPR band. The feasibility of this method of detecting heavy
metal ions, Hg(II) and Pb(II), at high concentration was established in real water
samples.
SERS Applications
Electromagnetic (EM) radiation in the visible range can undergo scattering upon
interaction with materials or substances, either by losing or gaining energy. EM
radiations are transverse waves consisting of mutually perpendicular, propagating
magnetic and electric fields [191]. The electric field component of EM radiation
perturbs the electron charge cloud in a molecular or atomic orbital. An electronic
13 Synthesis of Functionalized Noble Metal Nanoparticles 555

Fig. 13.36 Variation in the absorption spectrum of Au NFs with the addition of 10 μM Pb(II)
ions at different times as per Ref. [190]. Inset displays the colour variation in the a absence and
b presence of Pb(II) ions. Reprinted with permission from Ref. [190] Copyright 2013 Elsevier

Fig. 13.37 Selectivity of the colloidal Au NFs for Pb(II) and Hg(II) ions relative to other metal
ions. Each metal ion concentration was fixed at 1 μM. The time of incubation was 2 days. The
standard deviations based on three sets of experiments are represented by the error bars. Reprinted
with permission from Ref. [190] Copyright 2013 Elsevier
556 A. Das and N. Maiti

excitation to a higher state occurs when the contour of the distorted orbital geometri-
cally matches the excited state with high energy. The above phenomenon leads to the
observation of colour that can be monitored by UV–vis spectroscopy [192]. Another
possibility is that the electric field may slightly polarize the electron charge cloud
to form a transformed or altered orbital, which does not geometrically match the
excited state orbital with higher energy. In such a scenario, no electronic transition
occurs and the above mildly polarized transformed orbital is referred to as a virtual
state that instantaneously releases the absorbed energy. This phenomenon is referred
to as “scattering”. Whenever the energy of the scattered radiation matches that of
the incident radiation, the phenomenon is referred to as “Rayleigh scattering” [193].
Raman scattering is observed when the scattered radiation is of either higher or lower
energy than the incident radiation [194]. The vibrational modes of a molecule in the
ground electronic state are shown as Raman lines (Fig. 13.38).
Raman spectroscopy and infrared absorption spectroscopy [195] are complemen-
tary to each other. The low scattering cross-section (~10–30 cm2 ) of the Raman tech-
nique [194] leads to the observation of Raman signal only in solid samples or highly
concentrated solutions(≥10–2 M). Surface plasmons (SPs) assist in the improvement
of the Raman signal of low concentrations of analyte adsorbed on plasmonic NPs by
working as a confined excitation source of adsorbed molecules [196, 197]. An SP
upon illumination behaves as an oscillating electric field similar to an electromag-
netic radiation source. As a result, any molecule present on the surface of plasmonic
NPs may get excited to a virtual state (polarized) by the SP. The radiation emitted
by the excited adsorbed molecules can be seen in the far-field as Raman signal with

Fig. 13.38 Schematic illustration showing the phenomenon of electronic excitation and Raman
scattering
13 Synthesis of Functionalized Noble Metal Nanoparticles 557

signatures of metal–molecule interaction. This phenomenon of observation of vibra-

tional bands of molecules adsorbed on plasmonic NPs is known as surface-enhanced
Raman scattering (SERS) [135, 198–219]. Using this method very low sensing limit
(≤ μM concentrations) can be attained [198, 215].
Apart from the determination of the concentration of analyte, the SERS technique
is also being used for the determination of the orientation of analyte molecule on the
metal NPs substrate [204, 211, 220]. The catalytic oxidation of 3-hydroxy anthranilic
acid (HAA) on the surface of colloidal Ag NPs was investigated using time-dependent
(TD) optical absorption (OA) spectroscopy and TDSERS [221]. In this study, the
available thermal energy at room temperature alone was sufficient for the oxidation
reaction. No external activation such as laser light source or heat was necessary
for the catalytic oxidation reaction. HAA, a tryptophan aminophenol metabolite, is
known for its anti-inflammatory and neuroprotective activity [222]. HAA is capable
of undergoing intramolecular hydrogen bonding owing to the existence of carboxylic,
hydroxyl and amino groups at ortho positions. The catalytic oxidation reaction of
HAA to its azo-derivative on the surface of colloidal Ag NPs was monitored with
time using the TDSERS and TDOA techniques.
The normal Raman spectrum of solid HAA is given in Fig. 13.39a. The calculated
Raman vibrations of HAA [221] using B3LYP functional and aug-cc-pvdz basis set
was used to assign the Raman bands of HAA solid. The Raman spectrum showed
four strong bands at 1346, 1299, 783 and 627 cm–1 (Fig. 13.39a) that are ascribed to
C-CO2 stretch (str), C-NH2 str, ring breathing and ring bending, respectively. Raman
bands of medium intensity are seen at 457, 505, 1073, 1176, 1414 and 1551 cm–1 .
These bands are ascribed to NH2 rock, ph ring bend, ph CH bend, ph OH bend, ph
C C str and NH2 scissoring (sci), respectively. Raman bands with low intensity are
also seen at 588, 821, 908, 1010, 1098, 1222, 1619 and 1652 cm–1 that are assigned
to ph OH bend, ph ring distortion, ph ring bend, ph CH twisting, ph CH bend, C–OH
str, NH2 sci and C O str, respectively. Due to the poor solubility of HAA in water,
its Raman spectrum could not be recorded in aqueous solution.
Immediately after adding HAA to Ag NPs colloidal solution, the SERS spectrum
was recorded, which is shown in Fig. 13.39a. It is to be noted from the figure that
the above SERS spectrum resembled the neat solid spectrum. The SERS spectrum
of HAA (100 μM) was recorded with 514 nm excitation. The spectrum was found
to evolve with time and is given in Fig. 13.39a. As seen from the figure, new peaks
started appearing with time at 1487, 1444 and 1392 cm–1 . The intense peak seen at
1392 cm–1 is attributed to the symmetric (sym) CO2 – str, which is known to appear
when the analyte binds to the surface of the metal NPs through the carboxylate group
[135, 203, 209]. The peaks at 1444 and 1487 cm–1 are found to grow steadily with
time as shown in Fig. 13.39a. The peak at 1618 cm–1 (NH2 sci mode) is found to
disappear with time along with the simultaneous development of the intense peaks at
1487 and 1444 cm–1 . The gradual decrease of NH2 sci vibration indicates that HAA
undergoes a structural change to form an azo-derivative, which is evident from the
emergence of two new peaks at 1487 and 1444 cm–1 , assigned to the ph C C str
in combination with N N str (trans) and N N str for the trans isomer, respectively.
Apart from the above bands, the TDSERS spectrum also showed the formation and
558 A. Das and N. Maiti

Fig. 13.39 a TDSERS spectra of HAA (100 μM) and b intensity increase of the 1444 cm−1 band
attributed to N = N str mode of the trans azo derivative as a function of time and intensity decay of
the 1444 cm−1 band relative to the 1515 cm−1 peak (cis N = N str) as a function of time (displaying
error bar of 10%) (Reprinted with permission from Ref. [221] Copyright 2014 American Chemical
Society)

development of the peaks at 1644, 1594 and 1276 cm–1 that are attributed to the ph
C C str, C O str and C–N = N bend, respectively. The gradual increase in the Raman
intensity at 592 and 1515 cm–1 assigned to the C–N = N–C torsion and N N str
vibrations is observed within a period of 15 min of initiation of the catalytic reaction
on the colloidal Ag NPs surface. These modes correspond to the cis azo derivative.
The development of the 1444 cm-1 band of the trans azo derivative followed by
its decay due to the isomerization to the cis azo derivative as a function of time is
displayed in Fig. 13.39b. It may be assumed that the initial formation of the trans
azo isomer remains bonded to the surface of colloidal Ag NPs by the carboxylate
group. Upon gradual isomerization to the cis form, the analyte remains bonded to
the Ag NPs surface via the azo (N N) group and not via carboxylate thus, resulting
in an increase in the Raman intensity at 1515 cm–1 and total diminishing of the peak
at 1392 cm–1 . The catalytic oxidation of HAA on the surface of colloidal Ag NPs is
found to be complete within a day (24 h), reaching an equilibrium between the cis
and trans azo derivatives.
The catalytic oxidation of HAA on the surface of colloidal Ag NPs is also investi-
gated by TDOA spectroscopy. The TDOA spectrum of colloidal Ag NPs (Fig. 13.40)
displays an intense peak having a maximum at 388 nm owing to the (bulk-like)
BLSPR band. Upon adding HAA (100 μM) to the Ag NPs, the absorbance of the
BLSPR band at 388 nm band is found to decrease with a concurrent manifesta-
tion of a band at 555 nm. The emergence of the red-shifted band is ascribed to
the (surface-like) [217, 223–225] SLSPR band. This peak is formed as a result of
surface sorption of the analyte molecule (HAA) on colloidal Ag NPs. The new band
appearing at 555 nm gradually gets further shifted to higher wavelengths with peaks
13 Synthesis of Functionalized Noble Metal Nanoparticles 559

at 565, 575, and 590 nm and the emergence of a broadband as well as a shoulder at
367 and 451 nm, within 10–15 min. The broad feature and the shoulder at 367 and
451 nm is credited to the π–π* and n–π* transition that corresponds to the trans azo
conformer. With an increase in time, the azo derivative (trans) gradually isomerizes
to its cis conformer. The TDOA spectrum, which is recorded after a period of 24 h
of the initiation of the catalytic oxidation reaction on the colloidal Ag NPs surface,
shows two bands having maxima at 466 and 367 nm that are ascribed to the n–π*
and π–π* transitions of the azo (cis) conformer. No further change in the absorbance
is observed. Thus, it is evident that the isomerization reaction is complete within a
day (24 h), thus attaining an equilibrium between the cis and trans azo derivatives.
Moreover, a peak that is red-shifted with a maximum at 590 nm is also observed,
which appears due to aggregated Ag NPs. The absorption spectrum of 100 μM HAA
in aqueous solution is shown as an inset in Fig. 13.40. The figure shows two peaks
having maxima at 332 and 294 nm that corresponds to the n–π* and π–π* tran-
sition of HAA. It can be concluded from the TDOA spectrum that the activation
energy for the catalytic oxidation reaction (azo formation) on the colloidal Ag NPs
surface is relatively low (<0.025 eV). This is due to the fact that the catalytic (oxida-
tion) reaction of HAA on the Ag NPs surface to the azo derivative (trans) and its
isomerization reaction occurs at RT.
The catalytic oxidation of HAA on the colloidal Ag NPs surface to its trans
azo derivative 2,2 -dihydroxy-6,6 -dicarboxylic-azobenzene (DHDCAB) and its
successive isomerization to form the cis conformer is found to robustly depend
on the prevailing external parameters, viz., pH (acidic/alkaline), temperature and

Fig. 13.40 TDOA spectrum of colloidal Ag NPs (◯) and with the addition of HAA (100 μM).
Inset displays the HAA (100 μM) absorption spectrum (Reprinted with permission from Ref. [221]
Copyright 2014 American Chemical Society)
560 A. Das and N. Maiti

the surroundings (O2 , N2 , N2 O, etc.). The surface catalyzed oxidation and the
isomerization reaction is summarized and shown in Scheme 13.3.
Selenourea (SeU) is an organoselenium diamide that is used for the production of
selenium heterocycles, which show anti-inflammatory, anti-tumor and other medic-
inal properties. The oxygen and sulphur analogues of selenourea are less studied in
comparison to their non-thiol counterparts, i.e. urea and thiourea, and relatively very
few reports are available for SeU. The surface reactions and interaction of SeU with
Ag and Au NPs are studied by the SERS technique [220]. It is observed that Au being
soft compared to Ag exhibits a higher binding affinity for the soft Se atom than the N
atom (borderline) of the amino (NH2 ) group, whereas Ag shows a higher interaction
affinity for the N atom. Raman and theoretical (DFT) results [220] indicate that SeU
exists as the selenone conformer in neat solid and as selenol tautomer on colloidal
Ag NPs surface. Both tautomeric forms, selenol and selenone, are simultaneously
prevalent on colloidal Au NPs surface (Fig. 13.41).
Here, SeU is also used to form sandwich nanoassemblies within Au and Ag NPs.
The SP-assisted SERS of Ag–SeU is found to be affected by the addition of Au NPs
as shown in Fig. 13.42a. It is observed that gradually increasing the concentration of
the Au NPs (12.5–50 μM), the SERS peaks at 1483 and 1655 cm−1 due to the CN str
and NH2 sci bands decrease in intensity and disappear totally upon addition of higher
concentrations of Au NPs (100–250 μM). Moreover, the Ag–N str band appearing at
228 cm−1 steadily shifts to 239 cm−1 (shown as the shaded region in Fig. 13.42a. This
alteration is possibly owing to the break in the Ag–N bond along with the creation
of Au–Se. The SERS spectrum indicates a strong affinity of binding of the Au NPs

Scheme 13.3. Schematic representation of catalytic oxidation of HAA on the colloidal Ag NPs
surface to form the trans azo derivative followed by its isomerization. (Reprinted with permission
from Ref. [221] Copyright 2014 American Chemical Society.)
13 Synthesis of Functionalized Noble Metal Nanoparticles 561

Fig. 13.41 a The SERS spectrum of a SeU bound to Ag, b colloidal Ag particles and c the
subtracted (a, b) spectrum. Theoretically computed Raman spectrum of (I and III) selenol bound
to Ag4 and (II) selenone bound to Ag4 and (b) the optimized structures. c The SERS spectrum of
a SeU bound to Au and b colloidal Au particles. Computed Raman spectrum of (I and II) selenone
bound to Au4 and (III) selenol bound to Au4 along with d the optimized structures. Reprinted with
permission from Ref. [220] Copyright 2016 The Royal Society of Chemistry

towards the softer Se atom with the interaction being relatively stronger than the Ag
NPs binding with the (borderline) N atom.
Addition of Ag NPs to Au–SeU is monitored by the SP-assisted SERS at 632 nm,
which is shown in Fig. 13.42b. Upon gradual increase in the concentrations of Ag NPs
(12.5–100 μM), the SERS band seen at 239 cm−1 (Au–Se str) and the bands at 346,
633, 966, 1112 (389), and 1395 cm−1 that are ascribed to N–C = Se bend, C = Se str,
NH oop bend, NH2 rock, and NCN bend, respectively, are found to gradually reduce
in strength. These vibrations totally disappear upon adding 150 μM concentration
of Ag NPs. The emergence of a weak band at 318 cm−1 is seen upon the addition
of 50 μM concentration of Ag NPs. This band gradually gains intensity with an
increase in the concentration of Ag NPs (shown as the shaded area in Fig. 13.42b).
The above-mentioned vibration is assigned to the Se–Se str that emerges possibly
owing to the catalytic oxidation of the selenol conformer to its diselenide on the
surface of metal NPs. Even in literature, the Se–Se str mode of the diselenides [226]
was observed at 290–330 cm−1 that is in consistent with our observations. The
562 A. Das and N. Maiti

(a) (b)

Fig. 13.42 The SERS spectrum of the nanoassemblies; a Ag–SeU–Au and b Au–SeU–Ag.
Reprinted with permission from Ref. [220] Copyright 2016 The Royal Society of Chemistry

arrangement of the Ag–SeU–Au and Au–SeU–Ag nanoassemblies is schematically

displayed in Fig. 13.43a and b. It is seen from the figure that on the colloidal Ag
NPs surface, selenol tautomer is the major contributor, which on the addition of Au
NPs leads to the arrangement of a sandwich Ag–SeU–Au nanoassembly. It is also
seen from Fig. 13.43b that both the selenol and selenone conformers co-exists on the
Au NPs surface, which upon Ag NPs addition leads to the diselenide formation as a
result of catalytic oxidation of the selenol conformer.
Noble metal NPs immobilized in solid substrates can also be used for SERS-
based sensing. Formamide-reduced Ag NPs deposited on glass substrates are used for
SERS-based sensing of thioflavin T (TFT) [208]. Ca-Fe crosslinked Au NPs loaded
alginate films are also used as SERS substrate [148]. It can be seen in Fig. 13.44
that upon reducing the concentration of crystal violet (CV) adsorbed on the Au NPs
loaded alginate films, the SERS signal intensity decreases. The area under the peak
at 1400 cm−1 is found to be proportional to the change in concentration of CV.
This method is found to be successful in quantitative detection of CV in the range
of concentration from 1 nM to 10 μM. The slight enhancement of overall SERS
intensity from 10 to 1 μM CV can be ascribed to the formation of a monolayer on
the Au NPs surface.
Hybrid Ag NPs such as Ag/AgCl NPs are found to show photocatalytic activity
[168]. AgCl/Ag NPs formed by 0.03 M HCl solution due to the chlorination of Ag
NPs is found to show light-induced surface reaction, which can be monitored by the
SERS technique [124]. Sildenafil citrate (SC) is a renowned scheduled medicine used
for treating erectile dysfunction [227]. SC exists in three known tautomeric forms that
13 Synthesis of Functionalized Noble Metal Nanoparticles 563

Fig. 13.43 Schematic illustration showing the creation of nanoassemblies; a Ag–SeU–Au and
b Au–SeU–Ag. Reprinted with permission from Ref. [220] Copyright 2016 The Royal Society of
Chemistry

-9
(e) 10 M CV

-8
(d)10 M CV
Intensity (a.u.)

-7
(c)10 M CV
-6
(b)10 M CV

-5
(a)10 M CV

400 600 800 1000 1200 1400 1600 1800

-1
Raman shift (cm )
Fig. 13.44 SERS spectrum of varying CV concentrations (1 nM to 10 μM) adsorbed on Au NPs
loaded crosslinked alginate film
564 A. Das and N. Maiti

are named 6H-PPO, 4H-PPO and enol [124]. Theoretical calculations suggest that
SC remains as 6H-PPO in solid, which is also confirmed from the Raman spectrum.
Varying concentrations of SC adsorbed on borohydride-capped Ag NPs are studied by
UV–vis absorption spectroscopy that suggests that AgCl/Ag formation is influenced
by the sorption of SC on Ag NPs. Here, the chlorinating agent HCl is added after
adding SC to the Ag NPs. In the presence of high SC concentration (100 μM), HCl
could not effectively oxidize Ag NPs to AgCl due to efficient functionalization of Ag
NPs by SC, whereas in the presence of a low SC concentration of ≤ 1 μM, HCl could
easily chlorinate the Ag NPs, forming AgCl NPs adjacent to each Ag NPs. 1 μM SC
chemisorbed on AgCl/Ag NPs showed completely different SERS spectrum at 514
and 632 nm excitation and is shown in Fig. 13.45. This variation in SERS spectra is
not observed when 10–4 M SC is adsorbed on Ag NPs. This phenomenon is attributed
to the light-induced reduction of SC, which occurs as a result of the expansion of
plasmon from Ag NPs to the conduction band of AgCl NPs. The above phenomenon
is further confirmed by the pulse radiolysis method and the time-dependent density
functional theoretical calculations (TD-DFT).
Pt as well as Pd NPs, similar to Ag and Au NPs also exhibit SERS activities for
detection of analytes. Pd nanoparticles grown on Au surface are reported to show
SERS activity. The SERS activity is mainly due to the Pd overlayer [228]. The SERS
activity of Pd NPs of different sizes is displayed in Fig. 13.46.

Fig. 13.45 Comparing the Raman/SERS spectrum of a 100 μM SC functionalized Ag NPs (SC-
Ag) with λext : 632 nm, b 10 μM SC-Ag with λext : 632 nm, c 1 μM SC-Ag with λext : 632 nm,
d 100 μM SC-Ag with λext : 514 nm, e 10 μM SC-Ag with λext : 514 nm, f 1 μM SC-Ag with λext :
514 nm, and g solid SC with λext : 514 nm. Reprinted with permission from Ref. [124] Copyright
2019 Elsevier
13 Synthesis of Functionalized Noble Metal Nanoparticles 565

Fig. 13.46 SERS spectrum of 4-mercaptobenzoic acid chemisorbed on Pd NPs of sizes varying as
a 110, b 62 and c 33 nm. The peak from the Si substrate is assigned “*”. Reprinted with permission
from Ref. [228] Copyright (2010) American Chemical Society

Structured substrates fabricated using Pt and Pd NPs showed SERS activity at

633 nm. Spherical voids on the metal surface are usually created that act as SERS
hotspots. The fabrication is found to be quite reproducible [229]. Pd dendrites are
also reported to show SERS activity [230].
Catalytic Activity
Multi-spiked Au NPs are synthesized at RT in ethylene glycol by controlling the
pH with added NaOH without any external reducing agent [231]. These NPs with
high monodispersity and a mean diameter of 75 ± 10 nm are obtained in good
yield. The optical absorption spectrum of the multi-spiked Au NPs is tunable by the
addition of PVP as a stabilizer. PVP addition enhances the stability of the particles.
The catalytic activity of the PVP stabilized Au NPs is investigated to monitor the
reduction reaction of o-nitro aniline. Here, the catalytic reduction reaction of o-
nitro aniline to benzenediamine in the presence of NaBH4 in excess is studied. The
catalytic reaction rate is observed to be pseudo-first-order relative to the concentration
of o-nitro aniline.
The addition of NaOH to the HAuCl4 in ethylene glycol gradually changes the
colour of the solution to deep violet from light yellow, indicating the development
of Au NPs. The growth of the particles is monitored by recording the absorption
spectrum as a function of time and is given in Fig. 13.47a. It is observed that the
absorbance at λmax reaches a maximum showing a high yield of the particles, which
remain invariable with time, indicating that the HAuCl4 are completely reduced. It is
observed from the figure that the absorption band shows a time-dependent blue shift
566 A. Das and N. Maiti

along with the colour change to magenta and wine red gradually from bluish violet.
The blue shift is possibly owing to the alteration in the contour or the adsorption
characteristics of the stabilizer on the Au NPs surface. The shape or contour of the
particles is characterized by TEM measurements. In Fig. 13.47b is shown the TEM
image of the Au NPs taken after a day (24 h) of the initial reaction. The surface
morphology of the particles shows a multi-spiked pattern both in the presence and
absence of PVP. The particles were found to be stable for almost 3 months. The blue
shift observed in the absorption band is attributed to the PVP chemisorbed on the Au
NPs surface. The pattern seen in SAED confirmed the presence of multi-spiked Au
NPs. Varying the Au3+ ions concentration (from 0.1 to 1 mM) and NaOH although
changed the yield of the particles formed, but did not alter the SPR band of the
particles.
The chemical reduction of nitro aniline with NaBH4 without a catalyst is excep-
tionally sluggish. Hence, metal NPs were explored to study the catalytic reduction
of nitro anilines. The reduction procedure of the nitro anilines can be effortlessly
visualized with the discolouration of the yellow colour that is characteristic of the
nitro aniline solution. In these experiments, the concentration of NaBH4 is main-
tained higher than the concentration of nitro aniline, thereby treating the reduction
reaction kinetics as pseudo-first-order relative to the concentration of nitro aniline.
Moreover, excess amount of NaBH4 accounts for the sluggish but noticeable reagent
hydrolysis at pH 10. Here, the multi-spiked Au NPs prepared in ethylene glycol have
been investigated for studying the catalytic reduction reaction. Since the concentra-
tion of Au NPs is maintained to be low in the reaction system, the o-nitro aniline
absorption spectrum is not affected by the presence of Au NPs. The strong peaks
that appear in the UV–vis absorption spectrum at 412 and 283 nm are character-
istic of o-nitro aniline. In the absence of a catalyst, the spectrum reveals a very
slow decrease in the absorbance of o-nitro aniline. However, adding Au NPs to the
reaction mixture containing NaBH4 in excess and o-nitro aniline, fast decay in the
absorbance at 412 nm is observed. Furthermore, the gradual time-dependent red
shift of the 283 nm peak to 289 nm indicated the steady formation of benzenedi-
amine from o-nitro aniline as shown in Fig. 13.48a. The progress in the reduction
reaction is investigated by recording the UV–vis absorption spectrum at various time
intervals, t, with different Au NPs concentrations. It is observed that with the increase
in the Au NPs concentration, the absorbance at 412 nm reduced steadily as shown
in the inset of Fig. 13.48a. In Fig. 13.48b the reduction rate of o-nitro aniline is
displayed. A reasonable linear correlation between ln(At /A0 ) and time is observed
(where At is the absorbance at different time intervals and A0 is the absorbance at
the initiation of the experiment), which indicates the reaction is pseudo-first-order.
The observed rate constant (kobs ) can be directly approximated from the slope of the
linear plots as given in the inset of Fig. 13.48b. The Au NPs catalyzed o-nitro aniline
reduction reaction is elucidated by an electron relay mechanism [147, 232–234]. The
metal surface catalyzes the transfer of electrons to the reactants from BH4 − since the
potential of the metals lies in between that of the electron acceptor (o-nitro aniline)
and the electron donor (BH4 − ). The capture of the pre-solvated electrons by the Au
NPs has also been explained using Cerenkov radiation [235]. The increase in the
13 Synthesis of Functionalized Noble Metal Nanoparticles 567

Fig. 13.47 a The time-dependent SPR band of Au NPs produced by mixing of HAuCl4 (500 μM),
NaOH (1 mM) and PVP (0.1% w/v) in ethylene glycol (neat) at time intervals of 3 min (i), 24 h (ii),
3 days (iii) and 17 days (iv). b TEM photograph of the multi-spiked Au NPs produced after 24 h of
the initial reaction. Reprinted with permission from Ref. [231] Copyright 2012 Elsevier
568 A. Das and N. Maiti

Fig. 13.48 The change in the optical absorption spectrum (time-dependent) of o-nitro aniline in
the presence of NaBH4 and 2.5 μg/mL Au NPs after (i) 1, (ii) 3, (iii) 5, (iv) 7, (v) 9 and (vi) 11 min.
In the inset is shown a variation in the absorbance at 412 nm as a function of time and b the relative
absorbance as a function of time (logarithmic plot). Reprinted with permission from Ref. [231]
Copyright 2012 Elsevier

concentration of Au NPs from 1 to 2.7 μg/mL in the dispersion and maintaining all
other parameters constant is found to amplify the reaction rate by a factor of 5.
The effect of ligands on the catalytic activity and its relationship with the surface
coverage was also studied [98]. Ligands such as EDTA, HEDTA, TTHA, NTA and
IDA are found to influence the available surface coverage of the Ag NPs.
Pt NPs show excellent promise in the field of heterogeneous catalysis. It is well
known that Pt is used as a catalyst for the conversion of carbon monoxide to carbon
dioxide. It is observed that Pt surface under realistic catalytic conditions, 300–538 K
and 1–5 bar O2 , is prone to oxide formation [236]. This problem of oxide formation
in Pt NPs can be easily averted. Pt NPs also play a vital role in various organic
catalytic reactions such as hydrogenation [237], hydrosilylation [238], etc. Pd/PS
nanocomposites are found to show the surface-assisted reduction of 4-nitro phenol
by NaBH4 .

13.4 Conclusion and Future Prospects

During the past, new technologies in the field of nanoscience have prompted the
development of new and improved materials necessary for biomedical applications
with prime importance to diagnostics and therapy. Research is being undertaken
for advancement in the areas of nanotechnology for developing nanocarriers for
13 Synthesis of Functionalized Noble Metal Nanoparticles 569

drug delivery, photothermal treatment, cancer therapeutics, etc. where conventional

methods lack specificity and do not efficiently discriminate between cancerous and
normal cells. Moreover, nanoscale carriers for drug delivery offer great advantages,
i.e. higher intracellular uptake over the conventional forms of drug delivery systems.
Due to their miniature size, NPs can intermingle with the biomolecules both inside
cells and at the surface, yielding targeted specificity for therapeutics and diagnostics.
Designing novel nanocarriers that are conjugated with ligands such as antibodies may
be favourable for targeted therapeutic strategy or drug delivery. Thus, a variety of NPs
functionalized with diverse biomolecules are also being investigated for biomedical
applications, viz., drug and gene delivery and silencing, radiotherapy, thermal abla-
tion as well as imaging assays. Thus, the development of novel functionalized NPs
for the above-mentioned biomedical applications is expected to revolutionize the
field of targeted therapeutic strategy and treatment. However, during the process of
designing these nanosized drug formulations for targeted therapy or drug delivery, a
major concern regarding the short-term and long-term toxicity of these formulations
should be addressed before these nanosized formulations are taken up for clinical
trials.

Acknowledgements The authors thank Dr. A. K. Tyagi, Director, Chemistry Group, BARC and
Dr. Awadhesh Kumar, Head, RPCD, BARC, for their kind encouragement and support.

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Chapter 14
Synthesis and Surface Functionalization
of Nanostructured Biomaterials
Santosh L. Gawali, Bijaideep Dutta, Jagriti Gupta, P. A. Hassan,
and K. C. Barick

Abstract Nanostructured biomaterials are finding their way into medicine, phar-
maceutics and medical technology. Synthesis and processing parameters play a vital
role in the creation of a biomaterial with the desired nanostructure. Especially in the
development of nanostructured organic (polymers, hydrogel), inorganic (Au, SiO2 ,
ZnO, Fe3 O4 and hydroxyapatite) as well as organic–inorganic hybrid biomaterials,
the interface properties contribute decisively to the performance of the material. To
achieve higher therapeutic efficacy, it is important to realize the relations of bioma-
terials with the biological structures (physical, chemical and biological characteris-
tics). Thus, the designing of efficient modern biomaterials needs their surface to be
modified with desired biocompatible molecules. Further, the conjugation of specific
functional moieties on biomaterial surfaces offers stimuli-responsive shell that is
vulnerable to exterior factors like pH, temperature and ionic strength. These surface-
functionalized nanostructures act as smart carrier material for therapeutic agents
such as drugs and biomolecules since they are small enough to evade their uptake
by macrophage and offer enhanced absorption, retention and bioavailability of ther-
apeutic agents. They can also be conjugated with receptors and imaging probes for
cell-specific targeting as well as cellular imaging at the molecular level. In addition to
therapeutic applications, these surface-functionalized biomaterials have tremendous
applications in diagnosis, tissue engineering, and medical implants and devices.

Keywords Surface functionalization · Nanomaterials · Biomaterials ·

Therapeutics · Diagnostics · Tissue engineering · Device and implants

S. L. Gawali · B. Dutta · J. Gupta · P. A. Hassan · K. C. Barick (B)

Chemistry Division, Bhabha Atomic Research Centre, Mumbai-400085, India
e-mail: [email protected]
S. L. Gawali · B. Dutta · P. A. Hassan · K. C. Barick
Homi Bhabha National Institute, Mumbai-400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 581
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_14
582 S. L. Gawali et al.

14.1 Introduction

Nanostructure is the structure with at least one of the dimensions in the nano-regime,
usually from 1 to 100 nm. A variety of materials with nanostructures has been devel-
oped due to the rapid growth of nanoscience and nanotechnology. Generally, any
material or a combination of materials irrespective of natural or synthetic having
potential applications in the field of medicine, either therapeutic or diagnostic, are
called biomaterials. These materials have the capacity of being in touch with biolog-
ical mediums and tissues for extended periods of time without any adverse effect
[1, 2]. In addition to the naturally occurring biomaterials, various organic (poly-
mers, hydrogel), inorganic (metals, oxides and ceramics) and organic–inorganic
hybrid biomaterials were developed by soft-chemical approaches. Among others,
the development of biomaterials with nanostructure (nanostructured biomaterials,
NBMs) is rapidly progressing as an integration of nanostructures into biomaterials
not only provides exclusive chemical, physical and biological properties but also
creates advanced materials that find promising applications in diagnosis, tissue engi-
neering and drug delivery. Although NBMs have been used in many biomedical
applications, the exact interaction between cells/tissue and NBMs is not so far clear.
The interaction of biomaterial with its environment is mainly determined by its
surface chemistry and topography. The surface characteristics of NBMs contribute
decisively to the performance of the material and play a tremendous role in bioap-
plications [3]. For example, the efficacy of synthetic implants in the human body
is decided primarily by their surface distinctiveness such as surface microstructure,
composition, morphology and properties. It is well reported that surfaces having
nano-features in a well-organized manner significantly affect cellular and sub-cellular
functions. The surface properties of NBMs can be altered to augment solubility,
biocompatibility and cellular uptake. The restrictions of conventional drug carriers
include reduced effective targeting, low bioavailability and budding cytotoxicity. The
structural control at the nanoscale regime is the key factor in tailoring the bioavail-
ability of the biomaterials. NBMs have been widely used as a carrier for the controlled
release of drug molecules and synthetic matrices for tissue engineering. Various drug
delivery systems can be developed using NBMs of different composition, size, shape
and morphology. Further, the clinical applications of NBMs can be enhanced by
functionalizing their exterior with suitable ligands.
Surface functionalization of NBMs with suitable ligands for binding drugs,
biomolecules, targeting moieties, or fluorescent probes can be attained through
various processes such as electrostatic binding, physical adsorption, covalent
coupling and complementary recognition during synthesis (in-situ) or post-synthesis
(ex-situ) processes. The surface modification is extremely essential for biological
applications as the degree of adhesion of cells is tailored by non-specific adsorption
of proteins. Further, prolonged stability of the NBMs in blood is crucial for targeted
therapy and theranostic applications. Therefore, the development of novel NBMs
for these applications requires complete characterization and optimization of their
properties, and a thorough understanding of their interaction with biological systems.
14 Synthesis and Surface Functionalization … 583

14.2 Characteristics and Properties

Nanostructured materials exhibit significantly different optical, magnetic, mechan-

ical and electrical properties compared to their bulk analogues. These materials have
a superior specific surface area, which is beneficial for greater biochemical reac-
tions. Further, NBMs possess physico-chemical properties similar to local tissue with
nanometer hierarchical components. These unique properties enable NBMs to be a
suitable candidate for biomedical applications. Especially, the design and selection
of NBMs for specific applications depend on their long-term stability of structural
(mechanical, physical and chemical) and biological properties. NBMs should not
have adverse toxic effects and allergic symptoms to the body. The surface of NBMs,
being precisely exposed to the living systems, plays a decisive role in biocom-
patibility. NBMs should have a high degree of compatibility when in touch with
organs and tissues. The best possible way for enhancing the degree of tolerance is by
maneuvering the surface properties of the biomaterials through surface alterations.

14.2.1 Structural Properties

The understanding of structural properties is fundamental to know the interaction

of surfaces of NBMs with biomolecules, drugs as well as cells. The preferential
gathering of biomolecules and cells at the surface is called adsorption which is
basically a surface phenomenon. The nature of adsorption is generally determined
by the strength by which these molecules are interacted/attached with the NBMs’
surface. In general, there are two types of adsorption, namely physisorption and
chemisorption. Physisorption (physical adsorption) is mainly long-range and weak
van der Waals attraction energy in nature in the range of 10–50 kJ/mole. Generally,
there is no activation barrier attached to it and it is fast and reversible in nature.
However, chemisorption includes irreversible short-range and higher energy (200–
400 kJ/mole) bonding between molecules and the surface. In addition to the protein
and surface properties described above, adsorption also depends on the accessi-
bility of molecules for interaction with the substrate. There are four major ways for
transporting molecules to the surface: diffusion, convection, flow and combination
of convection and diffusion. Other variables such as temperature, concentration and
molecular size have a significant role in transporting drugs, biomolecules and cells to
the NBMs’ surfaces. The physical and chemical interactions of these molecules with
the surface are greatly controlled by various parameters such as surface characteris-
tics of NBMs, physiochemical response of biomolecules, drugs or cells and external
factors like temperature, pH, ionic strength, etc. The NBMs used for bioapplica-
tions are mainly non-toxic materials with desired surface modifications to which
biomolecules, molecular probes, drugs, etc., are conjugated. The NBMs’ surface
characteristic includes wettability (hydrophobicity/hydrophilicity), roughness, soft-
ness and chemical composition [4, 5]. The physiochemical properties of NBMs are
584 S. L. Gawali et al.

extremely reliant on the types, structures and orientations of the materials. With
respect to surface charge, both positive and negative ions are used to coat on the
surface of biomaterials for enhanced biocompatibility and cellular affinity [4].
The chemical stability as well as mechanical strength of NBMs are also important
parameters for applications of NBMs, especially in implants and devices. Corrosion
of NBMs in biological fluids affects both chemical stability as well as mechan-
ical integrity [6]. The surface modification of NBMs is essential when degradation
of materials occurs. NBMs with Young’s modulus near to that of bone are gener-
ally suggested for implant [7]. The NBMs with desired characteristics such as high
mechanical strength and wear resistance are primarily used for dental, orthopedic
and cardiovascular implants.

14.2.2 Biological Properties

The binding of proteins at NBMs’ surfaces has a crucial role in shaping the nature
of the tissue–biomaterial interface and uses on nanomedicine [8, 9]. Proteins are
comprised of distinct building blocks (amino acids) assembled into hierarchical
structures. The heterogeneity in the amino acid side chain is displayed in protein
surface characteristics. The charged and non-charged polar end form hydrophilic
surface, whereas the non-polar non-charged side chain ends up with a hydrophobic
surface. Hydrophobic surfaces are more prone to adsorption of protein compared to
hydrophilic ones due to the occurrence of favorable hydrophobic interactions at the
surface [9]. In addition to hydrophobic interaction, protein molecules can interact
with the NBMs’ surface through other forces, like ionic bonding and charge–transfer
interactions. The interfacial behavior is mostly guided by the property of both the
protein and the surface with which the biomolecules are interacting. The property
of proteins that stimulate the surface action is linked to the sequence of amino acids
which mainly controls the protein–NBMs surface interaction. Larger size molecules
have more sites to interact with the surface. Similarly, molecules in their isoelectric
point adsorb more easily. At the isoelectric point, reduction of repulsion between
charged molecules leads to enhancement in protein binding. Not only the charge but
also the charge distribution pattern governs the protein adsorption greatly. Stability of
proteins and their unfolding rate also have an effect on surface interaction. Relatively
less-stable proteins, i.e., those having less intramolecular cross-linking can unfold to
larger amount and form more contact points with the surface. Likewise, molecules
with higher unfolding rates enhance the probability of interaction with the surface
by exposing more sites. Other properties of NBM surfaces which have an effect on
the adsorption process are surface chemical composition (chemical composition of
a surface will govern the types of intermolecular forces leading to interaction with
proteins), various types of functional groups (such as carboxyl, hydroxyl, amine,
thiol and other aromatic rings) present on the surface, etc. On a microscopic scale,
surfaces of NBMs are not homogeneous. Thus, surface topography such as pores,
14 Synthesis and Surface Functionalization … 585

patches, domain and channels present on NBMs’ surfaces can influence the interac-
tion of biomolecules and proteins with the surface. Furthermore, chemical species
existing in these textures have also affected the surface characteristics.
The adsorbed protein layer (so-called “protein corona”) has many kinds of effects
ranging from blood coagulation, platelet adhesion/activation to bacterial to cellular
adhesion, etc. It also has an impact on NBMs’ degradation. It is well recognized that
the creation of protein corona on the NBMs’ surface reduces their cellular uptake,
targeting capability and biodistribution due to the changes in solubility, size and
surface chemistry. For instance, dysopsonin proteins such as albumin and apolipopro-
teins aid in the prolonged flow of NBMs in the living system, while opsonin proteins
such as IgG endorse phagocytosis [10]. NBMs are safe and effective for practical uses
only when their physiological relation with living organisms is well-studied. There-
fore, the understanding of the biological identity of NBMs and their physiological
stability is important. In order to enhance, the physiological stability of NBMs and
their circulation time in blood, poly(ethylene glycol) (PEG) is extensively used as a
coating material due to its immunogenicity, almost zero surface charge, high water
solubility, extensive hydrogen bonding and extreme protein-resistant characteristics
[11, 12].
Biomaterials can be obtained either naturally or by synthesizing in a laboratory
using different chemical approaches involving various metallic and non-metallic
components as well as their hybrids. NBMs have potential applications in surgery,
drug delivery and dental applications. These applications required NBMs to be highly
biocompatible and hemocompatible [13]. The notion of biocompatibility is an enor-
mous issue which is under investigation for a prolonged period of time. The exact
meaning of biocompatibility varies from researcher to researcher typically. However,
the competence of a biomaterial to execute its role as per the medical treatment
selected with maximum efficiency in contact with the body without any local side
effects is termed as biocompatibility. Approximately, all medical devices are prepared
from several biomaterials, and thus inspecting of their compatibility with the biolog-
ical system is required. Various kinds of efforts have been made to understand the
dealings of these biomaterials with human tissue and how their mode of interactions
affect the enactment of the imbedded devices [14, 15]. Biocompatibility test only on
one type of cell line or tissue is never satisfactory as the human body is made up of
so many types of tissue and is very much complex. After the in vitro testing is done,
an in vivo experiment should be performed based on the intended use of the device
material. Time for these testing can vary from weeks to several months based on the
amount of data required before implantation. There may be some substances that
leach out from NBMs’ surface, and therefore all potentially harmful leachable mate-
rials should be removed and analyzed. NBMs ought to be non-toxic, unless otherwise
they has been specially designed for any particular requirements like cancer treat-
ment. To outline whether any material is biocompatible, or not, there are certain
rules, regulations and protocols. The standard institute such as International Stan-
dards Organization (ISO) and American Society for Testing and Materials (ASTM)
formulated a series of in vitro test standards. Although the in vitro tests cannot exclu-
sively confirm the biocompatibility of a device or a material, they offer precious data
586 S. L. Gawali et al.

for the subsequent steps which are ideally in vivo tests followed by a human clinical
trial. Having a consistent set of in vitro biocompatibility data can result in the cutback
of animal uses and also facilitate setting the platform for human trials [16].
Blood ingredients usually do not interact with intact vascular endothelium.
However, mechanical disruption of the blood vessel wall due to interaction with
implants and particles may cause localized hemostatic responses [17]. The contact
of blood with an unknown foreign element promotes the adsorption of protein and
platelets. Hemocompatibility investigation is the estimation of critical interactions
of foreign materials with blood to look for possible unfavorable effects arising from
the exposure of the foreign element to blood cells and proteins. These adverse effects
are common and can lead to serious health problems. Thus, hemocompatibility
testing is very important for the introduction of new theranostic agents, medical
implants/devices and medicines. Further, the deep knowledge and understanding of
the interaction between nanostructures with biological components is essential for
the practical applications of NBMs.

14.3 Different Types of Nanostructured Biomaterials:

A Glimpse Toward Synthesis Aspects

Generally, any substance (not necessarily drug) or group of substances of a nano-

sized dimension suitable for biomedical applications either as therapeutic, diagnostic
agent or medical implants can be called NBMs. These materials have the capability
to be in contact with biological fluids, cells and tissues for a long time, without any
adverse side effects. Typically, these materials can be obtained either from nature or
synthesized using different chemical methods. The development of NBMs finds many
applications in diagnosis, tissue engineering, antimicrobial field, dental, surgical and
medical implants [18–20]. These fields are highly interdisciplinary, requiring knowl-
edge and expertise in chemistry, materials science, chemical engineering, biotech-
nology and medical sciences. Based on the material characteristics, NBMs can be
classified into three major groups: organic biomaterials, inorganic biomaterials and
organic–inorganic hybrid biomaterials. The ongoing advances in nanobiotechnology
developed various methodologies to prepare NBMs from various materials, including
ceramics, metals, metal oxides, composites, polymers, hydrogel, etc. Depending
upon the preparation methods and origin, NBMs have unique physiochemical and
structural features, which are vital for different applications in biomedical fields.
Among the variety of available morphologies, nanostructured or nanoparticulate
forms of biomaterials are widely employed as drug carriers and diagnostic agents as
well as tissue engineering.
14 Synthesis and Surface Functionalization … 587

14.3.1 Organic Nanostructured Biomaterials

“Organic biomaterials” can be either natural or synthetic in origin. Often, they

comprise naturally occurring biomaterials produced by an organism for itself. Poly-
mers and hydrogels are two major classes of organic biomaterials. Various natural
polymers such as chitin, starch, cellulose, chitosan, hyaluronic acid and dextrin are an
interesting class of biomaterials which have gained considerable attention [21, 22].
All cellulose-forming organisms, namely algae, bacteria and higher plants, contain
cellulose synthase proteins, which polymerize the glucan chains to form cellulose
[22]. Similarly, the biosynthesis of chitin is catalyzed by the enzyme chitin synthase
[23]. Most of these polymers are the main components of various natural products.
For instance, lignin and chitin are the main ingredients of natural polysaccharides
and represent the most abundant polymer in nature next to cellulose [24]. In 1996,
researchers for the first time developed a methodology for the chemical synthesis of
cellulose in a laboratory [25]. Polymeric biomaterials have numerous benefits over
other biomaterials due to viable large-scale synthesis procedures, cost-effectiveness,
easy processability for most of them and availability with preferred mechanical and
physical properties. The polymer-based biomaterials are extensively synthesized by
different mechanisms like radical polymerization, condensation polymerization and
catalyzed polymerization. In radical polymerization, the reaction proceeds through a
controlled reaction using free radicals, while condensation polymerization ends with
the formation of well-defined products such as an ester, an amide or a urethane bond
as a result of the polymerization process. However, enzymes act as a catalyst in a
catalyzed polymerization process. Recently, the advancement of polymer nanopar-
ticles (PNPs) has accorded a great amount of attention in drug delivery owing to
their capability to improve solubility, bioavailability and pharmacokinetic properties
of a drug molecule. It is also playing a key role in other fields such as photonics,
electronics and environmental sciences. PNPs are mainly composed of biodegrad-
able and biocompatible polymers of natural or synthetic origin. The most exten-
sively used natural polymers for the preparation of PNPs are gelatin, chitosan, algi-
nate and albumin. Among the synthetic polymers, polylactide (PLA), polyglycolide
(PGA), poly (lactide co-glycolides) (PLGA), polyorthoesters, polycaprolactones,
poly(methyl methacrylate) (PMMA) and polyacrylates are extensively explored. The
properties of PNPs have to be revamped depending on the meticulous application.
Hydrogels are also a promising class of materials for biosensing, drug delivery,
tissue engineering, etc. Hydrogels have a hydrophilic three-dimensional network
structure with voids which made them competent in carrying hefty amounts of water
via hydrogen bonding. On the other hand, it is a polymer network having the ability
to swell and keep hold of a considerable fraction of water (>20%) within its construc-
tion [26]. The hydrophilic property of hydrogel minimizes non-specific adsorption
of proteins, thereby imparting “non-fouling” characteristics. Many hydrogels are not
homogenous in nature as different polymeric domains are created within the gel
microstructure. Such features make these materials amenable for different indus-
trial, biomedical and environmental applications. For instance, the elastic network
588 S. L. Gawali et al.

Fig. 14.1 Schematic representation of volume phase transition of a stimuli responsive hydrogel

structure of hydrogel can encapsulate various drugs and biomolecules. Further, the
density of the network structure can be modified to provide better mechanical prop-
erties of the desired application. In addition, certain hydrogels undergo a volume
phase transition (Fig. 14.1) depending on the change in the local environment such
as light, temperature, pH, ionic strength and the presence of macromolecules [27–
29]. Recently, the development of nano-sized hydrogels (hydrogel nanoparticles or
nanogels) received considerable attention due to their prospective applications in
drug delivery, biosensors and tissue engineering, etc. [30]. Interestingly, hydrogel
nanoparticles have integrated characteristics of hydrogels (hydrophilicity, flexibility
and biocompatibility) as well as nanoparticles (stability, long-term circulation and
targeting ability) at the same time. Hydrogel nanoparticles can be made up of a
variety of natural and synthetic polymers as well as their blending through chemical
bonding or noncovalent physical cross-linking.

14.3.1.1 Synthesis Strategies of Organic Nanostructured Biomaterials

The method of preparation of PNPs plays a fundamental role in obtaining desired

properties. The PNPs can be synthesized directly from a preformed polymer or
polymerization of monomers using classical polymerization [31, 32]. Direct poly-
merization of monomers can be achieved by polymerization processes such as emul-
sion, microemulsion, miniemulsion, surfactant-free emulsion, interfacial polymer-
ization and controlled/living radical polymerization. The preparation of PNPs from
preformed polymers can be obtained through dialysis, salting out, solvent evapora-
tion, nanoprecipitation and super-critical fluid technology. The schematic represen-
tation of different PNP preparation techniques is shown in Fig. 14.2. However, the
choice of choosing an appropriate method for preparing PNPs depends on the types
14 Synthesis and Surface Functionalization … 589

Fig. 14.2 Schematic representation of different polymer nanoparticle preparation techniques

of solvents and polymers used in the synthesis process, particle size requirement as
well as area of application.
Mostly used techniques for the synthesis of PNPs are briefly reviewed here.
The techniques used for the preparation of PNPs from preformed polymers did
not engage any polymerization processes. Among others, solvent evaporation is
extensively used to prepare nanoparticles of polymers from a preformed polymer
(in the dispersed state) (Fig. 14.3a). In solvent evaporation, polymer solutions are
first prepared in volatile solvents (acetone, chloroform, dichloromethane or ethyl
acetate) and emulsions are formulated by two general methods: the first one namely
single-emulsions, i.e., oil-in-water (o/w), secondly double-emulsions, i.e., (water-
in-oil)-in-water, (w/o)/w using high-speed ultrasonication or homogenization. The
emulsion is transformed into a nanoparticle suspension on the removal of the solvent
by evaporation [33]. The solidified PNPs are usually gathered through ultracen-
trifugation followed by washing with water. Various stabilizers such as poly(vinyl
pyrrolidine) (PVP), span, poloxamer, sucrose and sodium cholate are added during
the preparation of PNPs via solvent evaporation. The mixing time and technique,
polymer concentrations and nature of the solvent used in the making of emulsion
strongly influence the properties of the PNPs made by solvent evaporation. The main
drawback of this simple method is the necessity of a long time and the risk of possible
coalescence of nanodroplets during the evaporation process.
The PNPs of desired properties can be synthesized by means of monomer poly-
merization. Emulsion polymerization is broadly employed for the preparation of
590 S. L. Gawali et al.

Fig. 14.3 Schematic presentation showing the preparation of PNPs by a solvent evaporation and
b emulsion polymerization method

polymers from monomers (Fig. 14.3b). This method is broadly classified into two
categories such as surfactant-free and conventional emulsion polymerization based
on the use of surfactant [34]. In conventional emulsion polymerization, the compo-
nents are water, a monomer with little water solubility, an initiator (water-soluble) and
a surfactant. This polymerization process can be initiated by the use of initiators. Initi-
ation reaction starts upon collision of monomer molecules dissolved in the continuous
phase with an initiator molecule (i.e., ion or free radical). Application of high-energy
radiation (γ-radiation, ultraviolet or strong visible light) can also lead to the conver-
sion of monomer molecule into an initiator radical. Before or after the termination of
reaction, the phase separation occurs and solid particles are generated. The PNPs of
typical size ~ 100 nm can be obtained by this process. Different polymer nanoparti-
cles formed by this method are PMMA, polystyrene (PS), poly(butylcyanoacrylate)
and poly(ethylcyanoacrylate). The conventional emulsion polymerization process
has become less important because of the heavy usage of toxic organic solvents,
surfactants, monomers and initiator. These toxic components need to be removed
However, the surfactants’ removal is quite difficult and a time-taking process. There-
fore, it is preferable to prepare PNPs without using added surfactants as an alternative
method. The production of PNPs without using surfactant is known as emulsifier-free
14 Synthesis and Surface Functionalization … 591

polymerization or surfactant-free polymerization. The reagents used in this process

are monomers (primarily acryl or vinyl monomers), initiator which is water-soluble
and deionized water.
Hydrogel networks can be formed by the reaction of one or more hydrophilic
monomeric components using multifunctional cross-linkers via single or multi-
step procedures like polymerization. A variety of different polymerization methods
such as copolymerization and cross-linking free-radical polymerizations have been
utilized for the preparation of hydrogel networks. Further, these structures can also
be formed by interacting polymers with suitable cross-linking agents to promote
the formation of the network. In general, hydrogel nanoparticles are formed when
hydrogel preparation is carried out at higher temperatures or by using stabilizing
agents. Explicitly, the use of ionic surfactants has produced hydrogel nanoparticles
via precipitation polymerization. The features of hydrogels are exceedingly reliant
on the cross-linking network. Both naturally occurring polymers like proteins and
synthetic polymers with water-loving characteristics may be used as starting mate-
rials for preparing hydrogel [35]. Among the naturally occurring polymers, chitosan,
chitin and alginate have been widely used for making hydrogel nanoparticles. Simi-
larly, from synthetic polymers, poly (vinyl alcohol), poly (ethyleneimine), poly
(ethylene oxide) and poly-N-isopropylacrylamide are employed for the development
of hydrogel nanoparticles. Recently, hydrogel nanoparticles have acknowledged an
immense deal of attention in drug delivery due to their unique physiochemical prop-
erties [36]. The schematic representation of the synthesis of colloidal chitin nanogel
and the drug loading in chitin nanogels are shown in Fig. 14.4 [37].

14.3.2 Inorganic Nanostructured Biomaterials

Due to the intrinsic physico-chemical and tunable surface properties, inorganic

NBMs presents novel platforms to build sophisticated theranostic agents for supe-
rior detection and more efficient treatment of many diseases. In particular, inorganic
nanoparticulates of metals (Au, Ag), oxides (SiO2 , TiO2 , ZnO, Fe3 O4 ), hydroxya-
patite (HAp) and layer double hydroxide (LDH) possessing unique physiochemical
properties and non-toxicity are showing the way for developing advanced technology.
The main attractive feature of using inorganic nanoparticles in bioapplications is due
to their inherent physical properties, like superparamagnetism [38], surface plasmon
resonance [39] and luminescence properties [40], which can be tailored by modifying
the shape and size of particles. The other striking appeal arises from the huge surface-
to-volume ratio of nanoparticles that provides an active site for conjugating imaging
and therapeutic agents [41]. Owing to these characteristics, inorganic nanoparti-
cles can provide an excellent platform for establishing multifaceted biomaterials
for therapeutic and diagnostic applications. For instance, clinically approved inor-
ganic nanoparticle-based agent ferumoxytol is used to cure iron deficiency anemia in
humans, and ferucarbotran is used as a magnetic resonance imaging (MRI) contrast
agent for revealing the small focal liver lesions [42]. The clinical trials are undergone
592 S. L. Gawali et al.

Fig. 14.4 Schematic representation of the synthesis of colloidal chitin nanogel and the drug loading
in chitin nanogels (reproduced with permission from Priya et al., Carbohydrate Polymers 136 (2016)
609–617, Copyright ©2015 Elsevier Ltd. [37])

with various inorganic nanoparticles like aurimmune CYT-6091, an agent made up

of gold nanoparticles bound with PEG and rhTNF (tumor necrosis factor) [43].

14.3.2.1 Synthesis Strategies of Inorganic Nanostructured Biomaterials

The synthesis strategies of inorganic NBMs can be broadly classified into two cate-
gories, such as top-down and bottom-up approaches. Mostly, the bottom-up chemical
14 Synthesis and Surface Functionalization … 593

processes are widely employed for the synthesis of NBMs. Among others, bottom-
up chemical approaches commonly used in the synthesis of NBMS are colloidal
precipitation (Fig. 14.5a), hydrothermal synthesis, thermal decomposition method
(Fig. 14.5b), polyol method, microemulsions (Fig. 14.5c), sonochemical approach
and sol–gel processing (Fig. 14.5d).
The colloidal precipitation method provides a dependable route to synthesize
various types of inorganic nanoparticles. It relies on the precipitation of nanoparti-
cles from an aqueous solution of metal ions under controlled temperature. Metal salts
like nitrate, chloride and sulfate are used as starting materials for the synthesis of
inorganic nanoparticles. The dissolved metal ions in water exist as metal hydrate and
nanoparticles precipitated out by the addition of a base such as NaOH or NH4 OH at
mild temperature (60–90 °C). By controlling the pH and temperature of the reaction
medium, it is very much likely to obtain different shapes and sizes of nanoparti-
cles. Gupta et al. prepared shape-controlled ZnO nanostructures via reflux of zinc
precursor in ethanol using different concentrations of NaOH as catalyst [44]. They
have demonstrated that the amount of OH− ions in the reaction medium controls
the shape of ZnO nanostructures. Verma et al. developed hydroxyapatite nanopar-
ticles by precipitation method using rod-like micelles of cetyltrimethyl ammonium
bromide (CTAB) and sodium salicylate [45]. Similarly, the co-precipitation method
is used for the preparation of different complex hydroxide and oxide nanoparticles
of metals. Using the co-precipitation method, Massart [46] first synthesized Fe3 O4
nanoparticles by adding base to an aqueous solution of ferrous (Fe2+ ) and ferric (Fe3+ )
ions in an oxygen-free environment [47]. Basically, aqueous colloidal synthesis is the
easiest method for synthesizing aqueous stable nanoparticles. The control of crystal
growth in the chemical precipitation method is the vital challenge to prepare nano-
sized particles. Barick and co-workers developed various surface-functionalized
Fe3 O4 nanoparticles of average sizes about 10 nm using co-precipitation method
[38, 48–52].
Sol–gel method is a simple, cost-effective way to produce different materials with
predetermined properties. It involves first conversion of a liquid (sol) into a gel state
followed by successive post-treatment to obtain solid material. The steps involved in
the sol–gel method are mixing, casting, gelation, aging, drying and densification. The
major advantages of the sol–gel method are the high purity, economic viability and
uniform nanostructure attainable at low temperatures. The sol–gel process occurs
via hydrolysis and condensation reactions as follows:
Hydrolysis: M–O-R + H2 O → M-OH + R-OH.
Water condensation: M-OH + M-OH → M–O-M + H2 O.
Alcohol condensation: M–O-R + M-OH → M–O-M + R-OH.
where M = Si, Zr, Ti, etc., and alkyl group R = CH3 , C2 H5 , etc.
For instance, Dubey et al. synthesized silica nanoparticles by the sol–gel route
using tetraethylorthosilicate (TEOS) as a precursor and PVP as a stabilizer [53].
Bessekhouad et al. described the preparation of TiO2 nanoparticles via sol–gel route
using tetraisopropylorthotitanate as a starting precursor [54].
The hydrothermal method involves synthesis of metal oxide nanoparticles under
high temperature and elevated pressure from aqueous solution of precursors. This
594 S. L. Gawali et al.

Fig. 14.5 Schematic representation of different routes for the production of superparamagnetic iron
oxide (SPION) nanoparticles. a co-precipitation, b thermal decomposition, c reverse microemulsion
and d sol–gel method (reproduced with permission from Dadfar et al., Adv. Drug Del. Rev. 138
(2019) 302–325, Copyright ©2019 Elsevier Ltd. [47])
14 Synthesis and Surface Functionalization … 595

reaction can be performed in a batch or continuous method. The batch hydrothermal

process is used to perform in a system with preferred ratio phases, whereas the
continuous method allows a superior rate of reaction to be attained at a shorter time
period. This method is rationally inexpensive and has the capability to produce a large
number of nanoparticles of optimized size, shape and composition. For instance, Gao
et al. [55] developed carboxyl-modified Fe3 O4 nanoparticles using the hydrothermal
method. Recently, Sharma et al. prepared nano-sized pure and doped ZnO particles by
the hydrothermal process at room temperature [56]. The preparation of nanoparticles
using organic solvent instead of an aqueous solution under analogous conditions is
termed as solvothermal method. Qiu et al. prepared core–shell Fe3 O4 @ZnO@mSiO2
nanocarriers by the solvothermal method for the delivery of chemotherapeutic agent
[57].
The polyol method is a robust strategy for the preparation of well-defined metal
and metal oxide nanoparticles by dissolving the metal precursor in a polyol solvent
(high-boiling, multivalent alcohols) and subsequently heating them for several hours
at the refluxing temperature of the solvent. The polyol acts both as a solvent as
well as a reducing agent and ligand to prevent aggregation particles. The choice of
polyol used during synthesis is dictated by the optimum reflux temperature. Several
kinds of polyols used for the preparation of nanoparticles by the polyol method are
ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol. Sun and
Xia [58] prepared silver nanoparticles (cubes, wire and irregular shaped) of various
dimensions via reduction of silver nitrate with ethylene glycol in the presence of PVP
at 160 °C. They have observed that the size and structure of nanoparticles depend on
various parameters like reaction temperature and concentration of precursor. Further,
they prepared hollow gold nanoboxes using silver nanocubes as sacrificial templates.
Barick et al. developed pure and metal-doped ZnO nanoassemblies by heating acetate
precursors in diethylene glycol medium at 160–170 °C [59]. Fe3 O4 nanoassemblies
were also prepared by refluxing Fe-chloride precursors for 6 h in the presence of
ethylenediamine and sodium acetate in ethylene glycol [60].
Nano-sized water droplets dispersed in the oil phase acted as nanoreactors for
the preparation of nanoparticles in the microemulsion method [47, 61–63]. Both
the metal ion and reducing agents are soluble in the water medium, where one
microemulsion contains metal ion and the other contains the reducing agent. The
precursor and reducing agents captured inside the reverse micelles are mixed thor-
oughly by the exchange process, which is primary to the preparation of nanoparticles
in microemulsion. Therefore, precursors precipitated out in the aqueous phase are
mainly situated at the core of micelles. Thus, the micelles in these systems provide an
appropriate condition for controlled nucleation and growth of particles, which in the
later stage form a robust coating on the nanoparticle. Various metal and metal oxide
nanoparticles were effectively prepared by microemulsion methods. For instance,
Zhang et al. developed hollow Fe3 O4 nanospheres in reverse microemulsion using
sodium dodecyl benzene sulfonate [61]. Lee et al. prepared highly crystalline γ-
Fe2 O3 nanoparticles of nano-sized by the microemulsion method at elevated temper-
ature with iron (III) acetyl acetonate as a precursor [62]. Bose and Saha discussed
the preparation of hydroxyapatite nanoparticles by a microemulsion method and
596 S. L. Gawali et al.

observed that the composition of microemulsion and synthesis parameters signifi-

cantly control the phase purity of hydroxyapatite formation, and their surface area
and morphology [63]. Ultrafine nanoparticles of diameter in the range of 5–50 nm
can be synthesized by water-in-oil microemulsions.
The high-temperature thermal decomposition of organometallic precursor in high
boiling point medium is known as “thermolysis”. It produces excellent quality, highly
crystalline, monodispersed inorganic nanoparticles [47, 64–67]. Specifically, in this
process metastable organic compounds are decomposed in the organic medium
at high temperature (260–320 °C) in the presence of surfactants. For instance,
metastable organic compounds such as Fe (III) acetylacetonate [64, 65], Fe (III)
oleate [66] and iron pentacarbonyl [67] are used for the synthesis of iron oxide
nanoparticles. Barick et al. fabricated highly monodispersed Fe3 O4 nanoparticles by
thermal decomposition of Fe (III) acetylacetonate in the presence of laurylamine,
lauric acid and 1, 12-dodacane diol in benzyl ether solvent at high temperature [64].
Hyeon et al. synthesized monodisperse maghemite nanocrystallites of high crys-
tallinity by thermolysis of iron–oleic acid complexes [68]. Sun et al. demonstrated
the synthesis of ultra-small Fe3 O4 nanoparticles using iron (III) acetylacetonate by
the thermal decomposition method [69]. Liu and Swihart reported controllable prepa-
ration of colloidal ZnO nanocrystals from thermal decomposition of zinc acetylaceto-
nate precursor [70]. There are a few drawbacks to the thermal decomposition method.
For instance, it employs costly organometallic compounds as precursors, high reac-
tion temperature and tedious procedures. Further, surface engineering is essential
for nanoparticles synthesized by this method to enable them water-dispersibility and
biocompatibility.
A current advancement in the preparation of inorganic nanoparticles is the utiliza-
tion of the sonochemical approach [71–74]. In this method, a high-energy ultrason-
ication is used to create acoustic cavitations which produce localized heating up to
a temperature of ~ 5000 K. The nucleation and subsequent growth of nanoparticles
take place at this temperature via collapsing of bubbles. Monodisperse metal and
oxide nanoparticles of various shapes and sizes can be synthesized by this approach.
For instance, Okits et al. prepared Au nanoparticles of different sizes by sonochem-
ical reduction of Au3+ in an aqueous solution having 1-propanol and observed that
the chemical effect of cavitation controls the particle size and the reduction process
[72]. Mukh-Qasem and Gedanken reported the preparation of stable hydrosol of
amorphous Fe3 O4 nanoparticles by sonolysis of iron pentacarbonyl in the presence
of sodium dodecyl sulfate [73]. Even though various metal and metal oxide nanopar-
ticles are prepared by the sonochemical approach, large-scale synthesis is intricate
to accomplish by this method.

14.3.3 Hybrid Nanostructured Biomaterials

Organic–inorganic hybrid biomaterials have received a great deal of attention due

to their exceptional properties arising from the combinatorial effect of organic and
14 Synthesis and Surface Functionalization … 597

inorganic materials. Normally, hybrid materials exhibit higher mechanical, optical,

magnetic and optoelectronic properties depending upon the materials involved.
However, the overall properties of hybrid biomaterials rely on the individual
constituents, their volume fraction, shape and size. Thus, they are extensively used
in a variety of applications such as tissue engineering matrices, drug delivery and
imaging. Most of these applications require good colloidal stability and biocom-
patibility of hybrid materials. Thus, it is most important to design and develop
colloidally stable and biocompatible materials that optimize bio-interfaces with
a suitable response. The researchers are seeking hybrid biomaterials having low
mechanical disproportion and lesser side effects with good colloidal stability.
Recently, various research groups developed nanoparticle–hydrogel hybrid mate-
rials with enhanced adhesiveness, thermal response, mechanical properties and bioac-
tivity [75–78]. The enhancement in these properties mainly arises due to the combi-
nation of two or more materials, Recently, the design of different supramolec-
ular hydrogel–nanoparticle composites is proposed. For instance, the micro- or
nanogels stabilized by using single/multiple nanoparticles through their noncovalent
and covalent immobilization in hydrogel matrix were reported [79, 80]. Magnetic
hydrogel composites were also developed by immobilizing magnetic nanoparticles
into the hydrogel matrix by three different methods such as (a) blending, (b) in situ
co-precipitation and (c) grafting method (Fig. 14.6) [80].
Inorganic–organic hybrid nano-sized layered double hydroxide (LDH) can be
prepared by top-down exfoliation and bottom-up direct preparation routes. The most
developed and widely used method for the synthesis of LDHs is top-down exfoliation.
Exfoliation of layered materials is a simple two-step process: first, the intercalation of
the layered materials with subsequent exfoliation steps to delaminate the layers. The
bottom-up approach is normally a one-step process in which inorganic nanostructured
materials were prepared directly from suitable precursors. Various methods were
designed to create LDHs with diverse sizes such as exfoliation co-precipitation,
electrodeposition methods and hydrothermal/solvothermal synthesis [81–84]. For
example, Liang et al. reported the preparation of NiCo LDH nanoplates using a
hydrothermal continuous flow reactor at high temperature and high pressure [82].
Recently, Jaśkaniec et al. [85] reported the preparation of hexagonal flakes of Ni–Fe
LDH having high crystallinity by homogeneous precipitation route.
598 S. L. Gawali et al.

Fig. 14.6 Schematic representation of methods to prepare magnetic hydrogels. a blending; b

in situ co-precipitation and c grafting method. Magnetic nanoparticle (MNP) is represented by
black spheres. Red and white X symbols represent cross-linker and functional groups, respectively
(adapted from Frachini and Petri., J. Braz. Chem. Soc. 30 (2019) 2010–2028 [80], an open-access
article distributed under the terms of the Creative Commons Attribution License)

14.4 Surface Modification of Nanostructured Biomaterials

Designing surface functionalized NBMs is significantly important for potential

biomedical applications. Most of the biomedical applications require NBMs to be
chemically and colloidally stable in complex biological fluids. The surface properties
like surface chemistry and surface charge mostly play important roles in upgrading of
chemical and colloidal stability of NBMs [86, 87]. Further, the interaction of NBMs
with the living matter at the cellular level is an important issue for their biomedical
applications [88]. The interaction of proteins with NBMs’ surface leads to an associ-
ated protein layer that mostly defines the biological identity of the NBMs. This protein
corona determines the ability of NBMs to interact with the living organism and hence
modifies their cellular internalization. Thus, there is a requirement to provide stealth
14 Synthesis and Surface Functionalization … 599

coatings on NBMs’ surface with desired materials for prolonged circulation time in
blood. Recently, surface modification has received considerable attention because of
its significance in reduction of toxicity of materials at the nano level and prevention
of opsonization in the biological medium [89]. Further, nanoparticles can be easily
detected by the lymphatic system via the body’s natural immune response to foreign
substances. Therefore, suitable surface functionality needs to be introduced onto
the nanoparticles to provide hydrophilicity characteristics that enhance their blood
circulation time.
Surface modification not only enhances the stability, hydrophilicity, monodisper-
sity and biocompatibility of materials but also provides different surface functional
groups (-COOH-, -NH2 , -SH and so on) or charges that can be advantageous for
the conjugation of biomolecules or drugs [90]. The interaction between atoms at the
surface of nanoparticles with incoming ligands/coating agent is the key parameter for
surface modification [91]. There are mainly two kinds of interaction such as noncova-
lent and covalent interactions that occur between nanoparticles and the coating agent
during surface modification. The noncovalent modifications of nanoparticles occur
through hydrophobic interaction, electrostatic attraction and van der Walls forces.
However, sometimes, such conjugation between particles and coating agent is not
adequate to form stable surfaces to overcome the barriers like multi-step washing
during their preparation as well as long-term incubation in biological mediums.
Therefore, it is essential to consider the influence of ionic strength and pH while
employing a noncovalent approach for surface modification. In contrast, covalent
modifications provide greater stability in the ionic and biological media through the
use of immediate strong chemical conjugation between nanoparticles and coating
agents (chemisorption). In general, surface modification can be achieved during
their synthesis (in situ) or post-synthesis (ex situ) methodology [3, 51, 52, 92, 93].
Various surface coating agents, for example, long-chain polymers/organic molecules,
biomolecules and inorganic materials, were widely used for surface modification of
NBMs.
Organic molecules having chelating functional moieties like thiol, carboxylic,
amine and phosphate groups can bind to nanoparticle surfaces to stabilize them as
well as control their agglomeration [3, 38, 51, 52, 86, 94–99]. The organic molecules
like citric acid, dimercaptosuccinic acid and tripolyphosphate conjugated to the
surface of nanoparticles through chemical conjugation of some of its functional
groups, whereas the remaining freely exposed groups furnished colloidal stability
to particles in the aqueous medium. For instance, Nigam et al. prepared highly
water-dispersible Fe3 O4 nanoparticles via chemisorption of citrate molecules onto
the surface of nanoparticles during the synthesis process [52]. The cyclic (sodium
hexametaphosphate) and chain-like (sodium tripolyphosphate) phosphate molecules
are also utilized for the preparation of aqueous stable and biocompatible Fe3 O4
nanoparticles by Sharma et al. [97] and Majeed et al., respectively [51]. Gorbatsevich
et al. synthesized aqueous-dispersible silica nanoparticles by hydrolytic polyconden-
sation of tetraethoxysilane followed by modification through grafting of triethylene
oxide moieties [98]. Tang et al. developed aqueous stable ZnO nanoparticles by one-
pot polyol hydrolysis of zinc stearate in the presence of triethylene glycol (TREG).
600 S. L. Gawali et al.

They have demonstrated that the conjugation of in situ formed ester compound onto
the surface of ZnO provides aqueous colloidal stability [99].
The coating of nanoparticles with long-chain polymers/copolymers or surfactants
are widely used for colloidal stabilization [100–102]. Among others, the use of
polyethylene glycol (PEG) and PEG-based copolymers, for instance, polyoxamer,
poloxamine and polysorbate 80 as coating agents is most popular and highly effective
with respect to in vivo applications [41, 102, 103]. Rana et al. [66] synthesized
aqueous stable carboxyl PEGylated Fe3 O4 nanoparticles by conjugating bifunctional
PEG-diacid molecule, whereas Rezayan et al. [104] prepared Fe3 O4 nanoparticles
coated with carboxyl functionalized PEG through dopamine cross-linker. Barick et al.
[64] developed water-dispersible triblock-copolymer, Pluronic 123 stabilized Fe3 O4
nanoparticles via hydrophobic interaction. Rahme et al. [105] prepared water-stable
Au nanoparticles by grafting of PEG-based thiol polymers onto the nanoparticle
surface. These PEG-based polymers hinder the opsonization of nanoparticles and
thereby prevent the undesired uptake of nanoparticles by the reticuloendothelial
system (RES) [106]. Additionally, biopolymers such as carbohydrates (chitosans,
dextran, gelatin, ethyl cellulose and alginate) and proteins (bovine serum albumin
and lipoproteins) as well as other synthetic polymers such as polyvinyl alcohol (PVA),
polyethylenimine (PEI), polyaniline and polyacrylic acid (PAA) are often used as
coating agent during nanoparticles synthesis processes [50, 107–111].
The hydrophobic nanoparticles (HMNPs) are generally converted to water-
dispersible through ligand addition and ligand exchange methods. In ligand addi-
tion method, an additional layer of the ligand is introduced onto the HMNPs surface,
whereas the hydrophobic molecules conjugated to the nanoparticle surface are substi-
tuted by hydrophilic molecules in the ligand exchange method. Both short-chain
organic molecules such as dopamine (DA), mercaptosuccinic acid (MSA), DMSA
and lipoic acid, and long-chain dendron and polymer molecules were used for stabi-
lizing HMNPs [112–117]. Moreover, the hydrophilic inorganic shell can also be
introduced onto the surface of nanoparticles via the formation of a core–shell struc-
ture [118, 119]. For example, Lai et al. developed a colloidally stable Fe3 O4 /SiO2
core/shell structure for multifunctional applications by introducing an inorganic SiO2
shell [119]. Xu et al. developed Au-coated Fe3 O4 nanoparticles via the formation
of Au shell on Fe3 O4 by reduction of HAuCl4 in the presence of oleylamine and
then transferred them into a water medium by using sodium citrate and CTAB [120].
Further, they have introduced an Ag shell onto the surface of Fe3 O4 /Au by the addition
of AgNO3 to the reaction container.
In addition to the colloidal stabilization of nanoparticles, surface passivation also
creates sites for conjugation to different biomolecules such as proteins, enzymes and
antibodies. Sapsford et al. discussed the abundant chemistry available on the conju-
gation of nanoparticles with biomolecules for the development of nanoprobes [121].
Generally, bioconjugation can be performed via covalent or noncovalent interac-
tions between biomolecules and surface-modified nanoparticles. The nanoparticles
having amine, carboxyl and thiol functional groups can be conjugated covalently with
biomolecules and drugs directly or via a linker molecule. Rana et al. [122] developed
folic acid conjugated Fe3 O4 nanoparticles through amide linkage between amine
14 Synthesis and Surface Functionalization … 601

groups of nanoparticles and the carboxyl group of folic acid using carbodiimide cross-
linker chemistry. Similarly, Dixit et al. [123] prepared folate receptor-targeted Au
nanoparticles by conjugating PEG with nanoparticles through the disulfide group of
thioctic acid. Recently, the cell membrane components like platelets, red blood cells
(RBC), macrophage cells and stem cells bounded nanoparticles have been evolving
as a potential platform for in vivo therapeutic and diagnostic applications [124–126].
Gao et al. [125] developed Au nanoparticles functionalized with cellular membranes
originated directly from natural RBC to provide immunosuppressive functionalities
for effective escaping of macrophage uptake. Similarly, RBC-functionalized Fe3 O4
nanoparticles were also prepared in a similar way that shows enhanced circulation
time and diminished accelerated blood clearance through CD47 marker (a cell surface
glycoprotein) [126].
The noncovalent electrostatic attachment also offers rapid and facile bioconjuga-
tion between nanoparticles and biomolecules. It is the simplest process to conjugate
biomolecules, which are solely dependent on the attraction among two opposing
charged moieties. For instance, CTAB-modified Au nanoparticles having a high posi-
tive charge can be easily conjugated with negatively charged nucleic acids [127].
The ionic strength and pH value play a significant part in such charged mediated
interaction between nanoparticles and biomolecules [128].

14.5 Applications of Nanostructured Biomaterials

The aptitude to introduce biological property into synthetic materials significantly

upsurges the potential applications of NBMs. Millions of patients, world-wide, are
benefited with biomaterials-based implants and devices, drug delivery systems and
imaging agents. The advancement in understanding the disease and tissue regenera-
tion in association with recent technology have created new openings for the use of
functional biomaterials. Therefore, functionalized NBMs have received a great deal
of attention in the biomedical community. The applications of NBMs in therapeutic
and diagnostic, tissue engineering, and medical implants and devices are discussed
below.

14.5.1 Therapeutic and Diagnostic Applications

NBMs are used in several therapeutic applications such as hyperthermia therapy,

drug delivery, photothermal and photodynamic therapy, and diagnostic applica-
tions in magnetic resonance imaging (MRI) and computed tomography (CT). Drug
delivery systems based on nanostructured materials have proved to be a great route
for targeting drugs to tumor sites where conventional therapy is not much effective.
These drug delivery systems are capable of delivering therapeutic agents which other-
wise exhibit poor solubility and poor pharmacokinetics. The encapsulation efficiency
602 S. L. Gawali et al.

of drug molecules as well as their release characteristic primarily depends upon the
ability to create novel NBMs.
Organic NBMs such as hydrogels and PNPs are extensively used as a carrier for
drug delivery [129, 130]. PNPs made of pH-sensitive biodegradable and biocom-
patible polymers are used for oral delivery of drugs, which are poorly water-soluble
[131]. One of the most significant ultimatums in drug delivery is to deliver therapeu-
tics agents to the central nervous system (CNS) and brain. The PNPs of chitosan,
chitosan-PEG and PLA-poloxamer 188 are used for CNS delivery of tacrine, caspase-
3 inhibitor and breviscapin. [132–134]. The PNPs are susceptible to transcytosis
across the blood brain barrier (BBB) mainly dictates the systemic delivery of the drugs
to the CNS. This delivery process can be enhanced by conjugating cell-penetrating
ligands and/or peptides onto PNPs surfaces [135]. Further, PNP-mediated targeted
drug delivery can conquer the problems associated with conventional chemotherapy
[136].
Like PNPs, hydrogels are used for oral drug delivery [137], gastrointestinal (GI)
drug delivery [138] and ocular delivery [139] as well as for topical and trans-
dermal applications [140, 141]. As compared to microgels, nanogels have high
payload capacity owing to their high degree of porosity. Among others, nanogels
made up of thermoresponsive polymers are widely investigated for the delivery of
drugs [142–144]. For example, Cho et al. [143] developed thermosensitive poly
(D,L-lactide-co-glycolide)-block-poly(ethylene glycol)-block-poly(D,L-lactide-co-
glycolide) (PLGA-b-PEG-b-PLGA) nanogels for the delivery of feebly water-soluble
drugs and biomolecules. Chen et al. [144] delivered an anticancer drug, placli-
taxel, using pH and thermoresponsive self-assembled nanogel composed of mPEG-
isopropylideneglycerol. Further, the nanogel can also be functionalized with targeting
molecules such as peptides and receptors for tumor-specific targeting [145] of drug
molecules. In addition to drug delivery, nanogels are also used for the delivery of
siRNA and oligonucleotides [146, 147].
Inorganic NBMs such as Au and its compounds are widely used for various
bioapplications including biosensors, bioimaging and photothermal therapy due to
their tunable optical and electronic properties as well as easy chemical synthesis and
functionalization [148–152]. By controlling the shape, size and surface morphology,
the plasmon absorption wavelength of Au nanoparticles can be tuned to overlap with
the spectral zone, where the depletion of photons by physiological fluids and tissues
is low. Au nanoparticles with specific surface functionality can easily get conjugated
with antibodies and peptides for active as well as passive drug delivery [153–156].
For instance, Zong et al. discussed the probable applications of peptide-modified
gold nanoparticles in drug delivery and biosensing [155]. Chanda et al. employed
bombesin peptide-tagged gold nanoparticles to aim the gastrin-releasing peptide
receptor, which is overly expressed in various cancer cells such as breast, prostate
and small-cell lung carcinoma [156]. Au nanoparticles can deliver biomolecules such
as siRNA that are prone to enzymatic deterioration, as well as those that exhibit lesser
intracellular uptake [157]. Gold nanoparticles are also widely used in photothermal
and photodynamic therapy of cancer treatment [158]. Similarly, nanoparticulate of
Ag and its compounds have also been used for various biomedical purposes such
14 Synthesis and Surface Functionalization … 603

as biosensors and therapeutic applications [159–161]. The inorganic oxides such as

TiO2 and ZnO nanoparticles are also used as a potential agent for photo-induced
therapy [162].
The commonly used oxide materials for drug delivery are iron oxide, zinc oxide,
silica nanoparticles, etc. [48–52, 57, 66, 87, 97, 122, 163]. The research on these
oxide materials has achieved an immense deal of consideration due to their unique
physico-chemical and biological properties, and non-toxicity. In these systems, the
drug molecules are either physically rooted or bound onto the surface of nanopar-
ticles by electrostatic/covalent immobilization. For instance, Cheng et al. [164]
demonstrated the physical entrapment of cisplatin into the porous hollow nanoparti-
cles (PHNPs) of Fe3 O4 and investigated their release characteristics. Puvvada et al.
[165] developed folic acid-tagged biocompatible ZnO hollow nanocarrier (HZnO)
for précised delivery of paclitaxel and observed their preferential accumulation in
breast cancer cells (MDA-MB-231). Further, ZnO nanoparticles have been reported
to shown antitumor activity toward cancer cells [166]. Recently, Zhou et al. [167]
discussed the uses of mesoporous silica nanoparticles as efficient delivery systems
for feebly soluble drugs, anticancer agents and therapeutic genetic substances. The
surface-functionalized Fe3 O4 nanoparticles were also used for covalent binding of
an anticancer drug via the formation of amide and azo bonds [168, 169]. In addition,
a cationic anticancer drug such as doxorubicin hydrochloride has been effectively
conjugated to negatively charged Fe3 O4 nanoparticles through electrostatic forces
[52, 94, 97]. Both electrostatic as well covalently conjugated drug molecules are used
to release under the influence of temperature, light, pH, ultrasound and magnetic field
[3, 170–173]. However, the drug delivery systems generated by covalent approaches
give better stability to the drug molecules as well as their controlled release than
those formed by noncovalent interaction.
Among the various magnetic nanoparticles, Fe3 O4 nanoparticles have been exten-
sively examined for their uses in hyperthermia therapy [38, 97, 174]. Barick and co-
workers described the uses of different surface-functionalized Fe3 O4 nanoparticles
as a heating source for magnetic hyperthermia [38, 48–52, 93, 97, 174]. It is well
reported that the heating efficiency of these nanoparticles relies on the concentra-
tion of particles, magnitude of applied AC magnetic field and frequency along with
the physical parameters such nanoparticle size, size distribution and their magnetic
moment [38]. Further, the heat produced during magnetic hyperthermia through the
relaxation loss process can also increase the toxicity of anticancer drugs in some
cancer cells that are otherwise resistant to drugs. In addition to drug delivery and
hyperthermia therapy, Fe3 O4 magnetic nanoparticles are also investigated as MRI
contrast agents and several preparations have been permitted for clinical use [86,
174, 175]. Similarly, Au nanoparticles are also made to be used as a contrast agent
for computed tomography (CT) imaging of cancer owing to its various benefits over
conventional CT contrast agents based on iodine [176]. Further, multimodal imaging
is required for the precise diagnosis of disease. In this aspect, Au nanoparticles are
used for dual-mode CT/MR imaging applications [177].
604 S. L. Gawali et al.

14.5.2 Tissue Engineering Applications

Tissue engineering is an integrative research field devoted to the development or

identification of appropriate materials to facilitate cell behavior and tissue function.
The surface-functionalized NBMs play an essential constituent of tissue engineering.
They are intended to grant direct mechanical interactions with cellular components
and cell surface receptors, and served as temporary extra-cellular matrices (ECMs)
for cell growth and eventual tissue regeneration. The main intention of tissue engi-
neering is to reinstate tissue and organ functions with nominal host rejection. Further,
the materials used for tissue engineering should be resorbed and replaced over time.
Thus, the development of biomaterials with desired surface functionality is impor-
tant for tissue regeneration by efficient transferring of therapeutic molecules and cell
populations. Among others, regeneration of cartilage and bone has received a great
deal of interest [178]. A broad range of inorganic materials similar in composition to
bone such as β-tricalcium phosphate (TCP), calcium phosphate ceramics (hydroxya-
patite (HAP) and biphasic calcium phosphate (BCP)), bioactive glasses and metal-
based biomaterials are used as scaffolds for regeneration [179–182]. The three
major steps involved in tissue engineering are transplantation of isolated bone cells
(osteogenic) at the defected site, introduction of isolated tissue producing molecules
and designing of 3D scaffold [183]. These scaffolds are temporary porous structures
for boosting new tissue generation and provide support to cell growth during the
regeneration process [184]. The well-designed 3D scaffold with the capability to
imitate the ECM of bone promotes the generation of new tissue by enhancing cell
adhesion and proliferation, which is dependent on the porosity, biomechanical and
physical properties of scaffolds [185]. The biomaterial used for regeneration should
have sufficient mechanical strength and it should be degradable at an equivalent rate
to the growth of new tissue at the implementation site. The synthetic biomaterials
are smart as they can be reproduced with the ability to manage structure, mechanical
strength and degradation rate. However, the naturally produced materials have certain
advantages due to the presence of embedded functional and structural molecules as
well as favorable immune recognition by a beneficiary.
Recently, NBMs have been used in tissue engineering for enhanced mechan-
ical and biological performances. The advantage of using NBMs in tissue engi-
neering is mainly associated with its ultra-small size and huge surface-to-volume
ratio. Thus, NBMs with specific surface characteristics can enhance cellular uptake
by easily penetrating through cell membranes. Further, they can also impersonate
the natural nanometer-sized ECM components of tissues. Among others, hydroxya-
patite nanoparticles (HANPs) have been widely used in different forms and shapes
as an ideal synthetic material in bone tissue engineering [186]. Various HANP-based
composite materials having hydrogels and polymers have been developed for the
revival of different parts of the bone systems, particularly those under major mechan-
ical tension [187, 188]. Maji and Dasgupta [189] developed a nano-β-TCP inte-
grated gelatin-chitosan-based composite matrix for bone renewal. Chen et al. [190]
reported that biphasic calcium phosphate nanoparticles/collagen porous composite
14 Synthesis and Surface Functionalization … 605

loaded with dexamethasone have a strong affinity for bone tissue. Wang et al. [191]
demonstrated that combining stem cells with nanostructured calcium phosphate
biomaterials accelerates bone regeneration.
Other than calcium phosphate ceramics, Au, TiO2 , ZnO and Fe3 O4 nanoparticles
have also been used to improve the rate of cell growth for bone and cardiac tissue
revival. It has been reported that Au nanoparticles support osteogenic differentiation
of an osteoblast precursor cell as well as promote neuronal differentiation and matu-
ration [192, 193]. Au nanoparticles are also found to control osteoclast construction
from hematopoietic cells while granting protection to mitochondrial malfunction
in osteoblastic cells [194, 195]. Kumar et al. [196] developed nano-TiO2 -doped
chitosan scaffold and observed that chitosan and nano-TiO2 interaction makes it
highly porous and brittle for bone tissue engineering. Liu et al. [197] developed a
scaffold where TiO2 nanoparticles were 3D-printed with PLGA polymer to precisely
map the nanostructured roughness of bone. Biocompatible hybrid chitosan-PEG-
nanohydroxyapatite-ZnO composite scaffolds were also prepared by Bhowmick et al.
[199] for the proliferation of osteoblast-like MG-63 cells [198]. Further, magnetite
cationic liposomes (MCLs) were used to construct 3D tissue by magnetic force-based
tissue engineering without scaffolds.

14.5.3 Devices and Implants

Biomaterials have been widely used since long in dental fillings and intraocular lens
replacement. However, the recent developments in cellular and molecular biology,
chemical sciences and engineering offer ample opportunity for their clinical use.
Biomaterials are also used to physically swap hard or soft tissues that suffered damage
or get destroyed in the course of some pathological process. Sometimes, body tissue
undergoes infection, fracture and specific diseases which create disfigurement, pain
or loss of specific function. Under these conditions, damaged tissue is used to be
replaced (repair) with biomaterials. Among others, NBMs’ implants and devices
are extensively used in dental, orthopedic, ophthalmic and cardiovascular applica-
tions. The NBMs used for the above purposes should be biocompatible, resistant
to corrosive biological conditions, sufficient mechanical strength and wear resis-
tance. The commonly used biomaterials in medical devices and implants are metals,
polymers, ceramics and composites. Metals are mostly exploited for load-bearing
implants such as screws and wires to artificial joints for knees, hips and shoulders.
Different metals as well as their alloys are also employed as implants in dental,
maxillofacial and cardiovascular surgery. The most commonly used implants are
silver, gold, stainless steels, titanium and titanium alloys. Various polymers such as
polyethylene, polypropylene, polyethylene terephthalate, polyamides, polytetraflu-
oroethylene, polyesters, polyurethanes, poly(vinyl chloride) and PMMA are used in
different medical applications varying from facial prostheses to tracheal tubes, from
liver to kidney parts to heart components, and from hip to dentures and knee joints.
Ceramic-based materials (zirconia, alumina and calcium phosphate) and composite
606 S. L. Gawali et al.

materials are used as restorative materials in dental applications. The composite

materials have also found wide applications in bone repair and joint replacement.
When these biomaterials are placed in the human body, the tissue responds toward
the devices/implant in several ways depending on the material properties [200, 201].
The employment of implantable devices is an essential part of medical care. In
the clinical field, the biomaterial is mostly used to prepare medical devices to safely
reinstate a part or a function of the body in an economically and physiologically
tolerable way [202]. The use of Ag nanoparticle-based antimicrobials coatings can
endorse a long-lasting antibacterial effect on medical devices [203]. Kose et al.
[204] recently developed Ag nanopowder coating which significantly reduces the
bacterial colonization on coated titanium implants. In addition, the manufacturing of
auto-sanitizing products for healthcare applications is extremely required to prevent
infections associated with health care [205]. The use of NBMs as scaffolds can help
in creating a constructive interaction between native bone and orthopedic implants.
Moreover, nanotechnology has the capability to modernize medical diagnostics as
well as orthopedic surgery [206].

14.6 Summary and Future Prospects

The unique physiochemical and biological properties of NBMs provide a strong

platform for the development of nanotechnology-based novel biomedical applica-
tions. Among others, organic (polymer, hydrogels) and inorganic (Ag, Au, SiO2 ,
ZnO, TiO2 , Fe3 O4 , hydroxyapatite and LDH) as well as their hybrid NBMs have
been fruitfully used in drug delivery, diagnosis, tissue engineering, and medical
implants and devices. The synthesis methodology, structural and surface features
of NBMs, and their interactions with the complex biological systems decide the
performance of NBMs. In order to achieve better efficacy, surface modification of
NBMs with biocompatible molecules having stimuli-responsive behavior, targeting
and imaging capability is highly essential. Surface modification not only provides
long-term colloidal stability, targeting and imaging capability to NBMs but also
prevents the non-specific adsorption of proteins, which are crucial for the delivery
of therapeutic molecules. At the same time, surface modification helps in direct
biological and mechanical interactions of NBMs with cellular components and cell
surface receptors, and serves as temporary ECMs for cell growth and eventual tissue
regeneration.
In view of ongoing research activities across the globe, it may be expected that
human beings will significantly benefit from nanotechnology and NBMs in near
future. However, the effect of nanotoxicity on human health and the environment
should be thoroughly understood. The biodistribution and release kinetics of NBMs
used for therapeutic and diagnostic applications should also be investigated in detail.
Further, complete characterization and optimization of NBMs properties as well as
a thorough understanding of their interaction with biological systems is required.
14 Synthesis and Surface Functionalization … 607

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Chapter 15
Implications of Synthesis Methodology
on Physicochemical and Biological
Properties of Hydroxyapatite

Mural Quadros, Munira Momin, and Gunjan Verma

Abstract Hydroxyapatite (HAp) is a well-known ceramic biomaterial, which has

widely been used in various biomedical applications. It has garnered the atten-
tion of researchers mainly due to its chemical and mechanical similarities with the
apatite phase present in the bones and teeth of humans. Owing to its biological simi-
larity, HAp has excellent biocompatibility and can trigger both osteoconduction and
osteoinduction activities. Therefore, HAp has been employed in a wide range of thera-
peutic applications ranging from simple dental fillings, bioactive coatings on implants
to strategically designed drug delivery systems, and even for tissue engineering appli-
cations. Synthesis methodology plays an important role in determining the physic-
ochemical properties of HAp, which in turn affects its mechanical and biological
performance. The desired characteristics of HAp can be achieved by choosing an
appropriate method of synthesis with optimized reaction conditions. This chapter,
in depth, will discuss the various methods of synthesizing HAp, along with their
advantages and disadvantages and implications on physicochemical characteristics
and biological performance.

Keywords Hydroxyapatite · Synthesis methods · Particle morphology · Chemical

precipitation · Hydrothermal method · Drug delivery · Biomaterials

M. Quadros · G. Verma (B)

Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India
e-mail: [email protected]
M. Quadros · M. Momin
Dr. Bhanuben Nanavati College of Pharmacy, Vile Parle, Mumbai 400 056, India
G. Verma
Homi Bhabha National Institute, Mumbai 400 094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 617
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_15
618 M. Quadros et al.

15.1 Introduction

HAp is the most commonly occurring calcium phosphate belonging to a class

of mineral compounds, called apatite. It is represented by the chemical formula
Ca10 (PO4 )6 OH2 or (Ca5 (PO4 )3 OH) with a calcium to phosphorous (Ca/P) molar ratio
of 1.67. The crystal structure of stoichiometric HAp is monoclinic with P21/b space
group, while non-stoichiometric HAp has a hexagonal structure with P63/m space
group. Most of the methods of HAp synthesis results in to slightly non-stoichiometric
HAp; therefore, they are observed to have hexagonal crystal structures [1, 2]. Biolog-
ical apatite is also a non-stoichiometric form of HAp, characterized by Ca2+ defi-
ciency but contains trace elements such as Na+ , Mg2+ , Zn2+ , Sr2+ , K+ , F− , Cl− ,
CO3 2− , and Si [3]. Carbonated and calcium-deficient HAp nanocrystals form major
inorganic constituents of the bone, whereas the organic part is mainly composed of
the collagen matrix.
In recent times, a great deal of attention has been paid to develop synthetic HAp, as
it possesses excellent properties such as biocompatibility, bio-integration, bioactivity,
non-toxicity, and biological degradation, which makes it a promising candidate for
various biomedical applications. HAp is a versatile biomaterial that can be used for
bone cavity filling, repair and reconstruction of damaged and degenerative bones,
bioactive coating of metallic implants, for tissue engineering applications, and more
recently it has also been viewed as a drug delivery vehicle. Each of these applications
requires a different set of physicochemical properties, which ultimately determine its
biological performance. For instance, when used as a drug delivery vector, the size of
HAp particles is a major determinant of its in-vivo pharmacokinetics, while the shape
of the particle is another physical parameter, which has implications on its cellular
uptake and bio-distribution [4]. In addition to this, homogenous dispersion and good
colloidal stability of synthesized HAp are also key parameters to be considered for
drug delivery applications. Besides these prerequisites, slow dissolution of the carrier
material, the feasibility of high drug payload, and sustained release of the drug are
some desired features of an ideal drug delivery system. On the other hand, while using
HAp as a bioactive coat on metallic implants, it is required to be stable in biological
fluid for a long period of time. The success of HAp-coated implant majorly depends
on its durability, coating thickness, micro topography, and bond strength of HAp
and implant. Further, the porous nature of HAp is also advantageous, as it helps
in compact fixation of the implant by allowing in-growth of bone tissues and its
integration with the living bones.
A wide variety of experimental techniques, including dry and wet chemical
methods, have been used for the synthesis of HAp. Through several studies, it has
been established that structural and morphological characteristics of synthetic HAp
can be controlled by optimizing the reaction conditions. For example, the crystallinity
of HAp particles, in general, depends on the reaction temperature, period of ageing,
and calcination temperature. In almost all the methods of HAp synthesis including,
chemical precipitation, hydrothermal, sol–gel, emulsion technique, etc., the crys-
tallinity of HAp particles seems to increase with increasing temperature and ageing
15 Implications of Synthesis Methodology on Physicochemical … 619

time. Several research groups have successfully tailored the structural and morpho-
logical parameters of HAp nanostructures by experimenting with different synthesis
methodologies and reaction parameters.
It is noteworthy to mention that different synthesis techniques result in HAp
with varied architecture and properties, which may not be universally compatible
for all types of biomedical applications. For example, biomimetic method, sol–gel
method, electrochemical methods, and plasma spraying are the preferred techniques
for coating implants. On the other hand, chemical precipitation being a simple process
provides an opportunity to perform several modifications in HAp nanostructures
during synthesis by involving functionalizing agents, targeting ligands, etc., along
with optimizing reaction parameters to enhance its suitability for drug delivery
applications. Therefore, an appropriate choice of synthesis methodology plays a
pivotal role in determining the biomedical success of HAp. This chapter provides a
comprehensive background on various techniques employed for the synthesis of HAp
including their advantages and drawbacks. The effect of variable reaction parame-
ters on the physicochemical properties of synthesized HAp will also be discussed
and correlated with its biological performance. Thereby, we will be addressing the
implications of different synthetic techniques on the development of HAp for various
biomedical applications.

15.2 Classification of Synthesis Methodologies for HAp

With growing interest in HAp for biomedical applications, various methods have been
devised for its synthesis. The synthesis methods of HAp can be broadly classified
into two categories, viz., dry and wet chemical methods as shown in Fig. 15.1.
Dry methods are simple processes as compared to wet methods. These methods
have top-down approach and generally employ the application of external force
such as temperature or pressure to aid the reaction. Due to their simplicity, dry
methods are often used for large-scale production of HAp. However, the limitation
of dry methods is poor control of the size and morphology of the synthesized HAp
[5]. Wet chemical synthesis methods generally have bottom-up approach. During
wet chemical synthesis, the desired characteristics of HAp in terms of size and
morphology can be achieved by experimenting with reaction parameters such as
reaction temperature, duration of reaction, and pH [5]. However, each method of
synthesis has its own advantages and limitations, which will be discussed at length.
Apart from conventional dry and wet chemical methods of synthesis, there are other
methods that involve different trigger mechanisms for the precipitation of HAp,
which have been categorized under miscellaneous methods.
620 M. Quadros et al.

Fig. 15.1 Different approaches for the synthesis of hydroxyapatite

15.3 Synthesis Methodologies: Effect on Physicochemical

and Biological Properties

Over the years, researchers have experimented with variable reaction parameters
such as temperature, pH, and solvent and correlated them with the physicochemical
properties of synthesized HAp such as size, shape, and crystallinity. Variation in
these physicochemical properties is further reflected in the biological performance
of HAp. Hence, it is very crucial to use appropriate methodology for the synthesis
of HAp [5–7].

15.3.1 Dry Methods/Physical Methods

These are called dry methods as there is no involvement of any solvent during HAp
formation. Dry methods can be further classified as solid state synthesis and mechano-
chemical synthesis.

15.3.1.1 Solid State Method

Solid state technique is one of the simplest methods for the synthesis of HAp. This
method involves diffusion of ions among the powdered raw materials to form HAp,
thus it requires a high reaction temperature such as 1200–1300 °C for initiation of
the reaction. Briefly, the starting materials, i.e., calcium and phosphate precursors
15 Implications of Synthesis Methodology on Physicochemical … 621

are weighed in a stoichiometric amount to maintain the Ca/P molar ratio of 1.67.
The powders are mixed and ground together with a binder or solvent (e.g., acetone)
that evaporates during the sintering phase or they are simply pressed into pellets
before sintering [8]. Figure 15.2 shows a diagrammatic illustration of solid state
method of synthesis of HAp. The choice and ratio of precursors as well as sintering
temperature have a significant effect on HAp properties in terms of phase purity and
particle size. Rao et al. experimented with varying ratios of tricalcium phosphate

Fig. 15.2 Flow sheet of

hydroxyapatite synthesis by
solid state method
622 M. Quadros et al.

(TCP) and calcium hydroxide (Ca(OH)2 ) at 1000 °C. They observed the presence
of a biphasic mixture of HAp and TCP at low concentrations of Ca(OH)2 , while
pure HAp was produced at equimolar ratios (3:3). However, a further increase in the
concentration of Ca(OH)2 (3:4) led to the formation of a secondary calcium oxide
(CaO) phase as an impurity [9]. Pramanik et al. demonstrated the need for sintering
during the synthesis process. The presence of unreacted CaO was seen in unsintered
samples, while samples sintered at 1250 °C exhibited monophasic HAp particles
with a well-connected granular structure and average grain size of 7–8 μm [10].
The temperature used for sintering has also been observed to have an effect on
the morphology of HAp, more specifically the particle size. Ezerskyte-Miseviciene
et al. noted that particles ranging from 200 to 300 nm were formed when the sintering
temperature was 800 °C, while beyond this temperature, the particle size increased
up to 400 nm as observed by scanning electron microscopy studies. The difference
in the particle size as a function of temperature was attributed to the agglomeration
of particles [11]. Similar results were reported by Guo et al., as an increase in HAp
particle size was observed with an increase in sintering temperature [12].

15.3.1.2 Mechano-Chemical Technique

The mechano-chemical method is another dry method used on a commercial scale

for the synthesis of HAp. It is capable of producing nanoscale HAp powder with
better control on morphology as compared to solid state synthesis method. This
method majorly employs a rotating ball mill to mix the precursor reactants followed
by annealing at elevated temperatures to form HAp. Figure 15.3 shows a diagram-
matic illustration of solid state method of HAp synthesis. The collision between
balls (usually made up of stainless steel or zirconia) or ball and wall of the mill
exerts intense mechanical stress on the precursor powders resulting in mechanical
deformation and increased local temperature. The high temperature coupled with
structural deformation increases the reactivity of calcium and phosphate precursors
to form HAp [13–15]. Other advantages of the mechano-chemical method include
low reaction temperature and comparatively inexpensive equipment. Some param-
eters that need to be monitored during this process are period of milling, choice of
precursors, mass to ball ratio, etc. Optimization of these parameters can result in
desired morphology of the material. Silva et al. observed a change in crystallinity of
HAp as a function of milling time when synthesizing HAp–titanium ceramic system.
They noted a slight improvement in crystallinity as milling time was increased from
5 to 15 h; however, an increase in particle size was also observed indicating the
formation of agglomerates [16]. Serraj et al. experimented with different calcium
and phosphate precursors at various Ca/P ratios. They observed that the choice of
precursors and ratio have a significant effect on the formation of the HAp phase [17].
The weight of precursor powders can also affect the reaction kinetics. For example,
Briak-Ben Abdeslam et al. used calcium oxide and dicalcium phosphate dehydrate
(DCPD) as calcium and phosphate precursors, respectively, and they noted that the
15 Implications of Synthesis Methodology on Physicochemical … 623

Fig. 15.3 Diagrammatic illustration of HAp synthesis by the mechano-chemical method

time for the complete disappearance of DCPD increased linearly with the mass of
powder ground. The rate constant for conversion of 30 g DCPD was half of the one
obtained for 15 g [18]. In another study, the same group co-related the influence
of instrumental parameters with reaction kinetics. They concluded that the rate of
reaction of DCPD was dependent on the rotation velocity of the mill, the eccentricity
of the vial on the rotating disk, and the product of the total mass and surface area
of the balls [19]. Another parameter that can be optimized to control the morpho-
logical parameters of HAp is annealing temperature; Fahami et al. demonstrated the
thermal annealing process to be an important step in ensuring high crystallinity. The
samples synthesized without annealing step exhibited a lesser degree of crystallinity
as compared to the annealed samples [20, 21]. Although the mechano-chemical
method is a dry process, Otsuka et al. theorized water of crystallization present in
precursors to largely affect its activity. They showed that the mixture of DCPA and
CaO, which contains 2.0 mol of crystalline water, less actively transformed into HAp
as compared to DCPD and Ca(OH)2 mixture that contained 3.0 mol of water [22].
In spite of having many advantages, the main drawback of the mechano-chemical
method is the risk of contamination during the milling process due to high mechanical
attrition. For instance, when milling was performed in a biocompatible polymeric
vial, it provided better safety in terms of contamination as compared to metallic
vials [23]. A comparative study of products prepared using metallic and polymeric
vials indicated that HAp crystals synthesized in polymeric vials had more product
efficiency and uniformity than those produced in metallic vials [24].
Although dry processes, like solid state and mechano-chemical methods, are very
much feasible for large-scale industrial synthesis, they lack control on the size and
morphology of the synthesized material as well the presence of heterogeneity in
624 M. Quadros et al.

the phase composition. Moreover, other disadvantages of dry processes are batch to
batch variability and the presence of process impurities mainly from wear and tear
of grinding equipment, e.g., ball mill. Due to these reasons, dry methods remain
an unattractive synthesis option for HAp, especially for biomedical applications. To
overcome these shortcomings, the use of wet chemical methods is gaining increasing
popularity.

15.3.2 Wet Methods

During wet chemical synthesis, calcium and phosphate precursors are mixed in molar
stoichiometric ratios in the presence of either water or other organic solvents and
the reaction is carried out at elevated or room temperature. Generally, the pH of the
reaction is maintained at an alkaline value of 8–11, throughout the reaction, followed
by ageing, washing, and calcination of precipitated HAp particles. For any synthesis
method, with an increase in the number of steps, the opportunities for optimizing
the reaction parameters also increases, which in turn provides more control on the
physicochemical properties of the product. By experimenting with different reaction
parameters such as pH, temperature, ageing period, calcination temperature, choice of
calcium and phosphate precursors, as well as the addition of organic modifiers during
wet chemical processes, the physicochemical properties of synthesized HAp can be
tuned to the desired extent. Wet chemical synthesis can be further classified as co-
precipitation, sol–gel emulsification method, hydrothermal method, and hydrolysis
method [25–27].

15.3.2.1 Co-Precipitation Method

Co-precipitation or chemical precipitation is the most conventional and most

commonly used method for the synthesis of HAp and can be scaled up to produce
HAp in large quantities at a reasonable cost [28]. It is one of the most applicable tech-
niques with multiple reaction variables, which can be tuned easily to attain desired
HAp morphology. Moreover, low reaction temperature, usually <100 °C, is another
advantage of this process. The solubility of HAp in acidic pH and stability at alka-
line pH form the basis of this method and can be explained as nucleation–aggre-
gation–agglomeration followed by growth of HAp nanoparticles. The reactants are
calcium and phosphate precursors, namely calcium hydroxide, calcium nitrate, or
calcium carbonate as the calcium source, while orthophosphoric acid or diammo-
nium hydrogen phosphate are used as phosphate precursors. The procedure of HAp
synthesis during chemical precipitation begins with the gradual addition of phosphate
precursor to a solution of calcium precursor at room temperature or slightly elevated
temperature under constant stirring to avoid agglomeration. An alkaline pH of > 9.0
is maintained for the rest of the reaction followed by ageing at the desired reaction
temperature to form mature HAp crystals. This is followed by multiple washings to
15 Implications of Synthesis Methodology on Physicochemical … 625

remove unreacted reagents and finally the drying of the product [29–31]. Figure 15.4
shows a diagrammatic illustration of the chemical precipitation method of HAp
synthesis. Care should be exercised while weighing the reactants and during their
addition so as to get the final stoichiometric molar ratio (Ca/P) of 1.67.
The careful management of reaction parameters such as pH, temperature, stir-
ring speed, rate of reactant addition, time period for ageing, calcination temperature,
and proper selection of precursor materials that are thought to be important param-
eters during synthesis as they directly affect the composition and physicochemical
properties of the synthesized product is done [32]. Optimizing the reaction temper-
ature is one of the simplest parameters to control the morphology of HAp. Bouyer

Fig. 15.4 Diagrammatic

illustration of hydroxyapatite
synthesis by chemical
precipitation method
626 M. Quadros et al.

et al. observed that the increase in the synthesis temperature results in the transi-
tion of crystal morphology from needle to spherical shape. This transition of shape
was attributed to temperature-dependent characteristics of crystalline materials, i.e.,
at low temperatures (<45 °C), crystal growth follows the c-axis of HAp structure.
However, at higher temperature (>85 °C), they tend to grow uniformly around all
axes, thus resulting in spherical crystals [33]. In another study, Bouyer et al. demon-
strated that the rate of addition of reactants also affects HAp characteristics. With a
high addition rate (2400 ml/min) of precipitating agents such as phosphoric acid, the
pH of the reaction decreases drastically, resulting in incomplete dissociation of phos-
phoric acid, and due to the unavailability of sufficient phosphate ions, the formation of
HAp is compromised. With the slow addition of phosphoric acid (100 ml/min), 100%
calcium hydroxide was converted into HAp [33]. The period of ageing, also known as
ripening time, is a crucial parameter in determining the crystallinity of HAp particles.
Pang et al. demonstrated that the crystallinity of HAp increases with time and can
be corroborated by clear and sharp diffraction peaks observed in X-ray diffraction
patterns [34]. By controlling the concentration and pH of the reaction, HAp with
various morphologies such as wires, platelets, and needles can also be obtained [35].
The co-precipitation method has also been modified to increase its efficiency. For
instance, Peng et al. were able to synthesize HAp nanorods with a narrow particle
size distribution by employing high-gravity precipitation technology. In this process,
the calcium and phosphate precursors were pumped onto a rotating bed at a rotating
speed of 1600 rpm. The high rotation speed generates a high-gravity environment,
resulting in the formation of tiny liquid droplets enabling better contact of precursor
reagents [36]. Overall, the controllable morphology, good reproducibility, and indus-
trial scale-up feasibility coupled with reasonable cost makes chemical precipitation
a very feasible method for the synthesis of HAp.
There are reports which suggest that the size and shape of nanoparticles influ-
ence their biological performance. For instance, Palazzo et al. demonstrated that
HAp nanoparticles with plate morphology have 1.3 times higher loading efficiency
for anticancer drugs (platinum–bisphosphonate complexes) than their needle-shaped
counterparts. This selective preference of drug adsorption was theorized to be because
of differences in drug-crystal plane interaction [37]. Iafisco et al. studied the influence
of the size of HAp crystals synthesized by the chemical precipitation method on the
time taken for its resorption when used as a subcutaneous implant. They observed
that HAp with a particle size of 100 nm was completely resorbed within 4 weeks of
implantation in mice, while the presence of HAp with size 50 nm was noted up to a
period of 8 weeks. The longer resorption time of smaller particles was related to its
high tendency to form large agglomerates with strong electrostatic interactions, which
delays its breakdown for the resorption process [38]. Guo et al. demonstrated that
nanostructured HAp exhibits better osteoblastic proliferation activity as compared
to its microscale counterpart [39]. This interplay of size and osteoblastic activity can
be ascribed to a higher surface area of nanostructured HAp for enhanced cellular
adherence and proliferation [40]. The topology of the implant surface is a crucial
interface that influences the reaction of tissue to the implant material. Osteoblast
15 Implications of Synthesis Methodology on Physicochemical … 627

cells “sense” surface morphology of implant by means of filopodia, a slender cyto-

plasmic projection of cell to collect spatial information. These protrusions also help
the cell to adhere and move along the solid surface [41]. Zhou et al. synthesized HAp
implants with different crystal morphologies, i.e., rod-like and spherical nanocrystals
by using the chemical precipitation method. They noted that implants composed of
spherical nanocrystals have a large number of filopodias indicating higher activity of
osteoblast cells. This discrimination of osteoblastic cells towards spherical nanocrys-
tals was attributed to higher contact points of the spherical surface as compared to
rod-shaped morphology [42].
Since chemical precipitation is a simple and feasible process, several modifi-
cations can be performed on HAp during synthesis by addition of functionalizing
agents, targeting ligands, polymers, etc. Along with optimizing reaction parame-
ters, researchers have also incorporated various additives during precipitation to
further improve the physicochemical characteristics of HAp. The colloidal stability
of nanoparticles is a very crucial parameter, especially for drug delivery applica-
tions. HAp nanoparticles due to their high surface energy have a tendency to form
aggregates. To avoid this, physical methods like mechanical stirring and sonica-
tion are employed during the synthesis and processing of HAp [43, 44]. However,
these methods are temporary and do not provide long-term stabilization. Another
approach for increasing colloidal stability is by modifying the surface of HAp with
stabilizing agents [45]. Such surface modifications can be classified as electrostatic
stabilization, steric stabilization, and a hybrid of both, i.e., electrosteric stabilization.
Figure 15.5 depicts different approaches used for enhancing the colloidal stability of
HAp nanostructures. Electrostatic stabilization involves surface modification with
charged molecules, which induces electrostatic repulsion between nanoparticles and
helps in imparting them colloidal stability [46]. Leah et al. demonstrated that modifi-
cation of HAp surface with calcium, citrate, and phosphate ions confer electrostatic

Electro-steric stabilization

Surface Passivation
for colloidal stability
Electrostatic Stabilization Steric Stabilization

Fig. 15.5 Schematic illustration of different approaches used for enhancing colloidal stability of
hydroxyapatite nanostructures
628 M. Quadros et al.

stabilization under physiological conditions [47]. Tan et al. added sodium citrate and
sodium hexametaphosphate along with calcium precursors, which resulted in func-
tionalized HAp nanoparticles, exhibiting colloidal stability in aqueous media, with no
visible sedimentation or agglomeration for a period of 7 months [48]. Surface modi-
fication with alkyl phosphates exhibited electrostatic repulsion due to the presence
of a larger number of surface P-OH groups on the HAp surface conferring greater
negative electrophoretic mobility compared with the unmodified material [49, 50].
Steric stabilization can be achieved by using capping reagents or polymerization and
esterification reactions on the HAp surface [51]. Huang et al. used block co-polymer
F127 as a stabilizer to inhibit nanoparticle aggregation during synthesis of HAp by
chemical precipitation method [52]. Electrosteric stabilization involves surface modi-
fication with molecules that provide both electrostatic and steric repulsion. Organic
molecules like chitosan, gelatin, collagen, etc. form a protective barrier around the
HAp nanoparticles, thus discouraging the Van der Waals interactions with adjacent
particles. Additionally, the functional groups such as carboxyl and amine present in
these molecules offer electrostatic stabilization. Zhou et al. modified HAp nanoparti-
cles with polyphenols using the chemical precipitation method. These nanoparticles
exhibited colloidal stability due to electrostatic repulsion between the particles (zeta
potential: −26.1 mV) as well as the presence of steric barrier offered by branched
polyphenolic structure [53]. In another study, HAp particles were coated with gelatin,
and the thick gelatin layer on HAp particles resulted in increased stability through
spatial stabilization, as well as through electrostatic repulsive interaction [54].
The chemical precipitation method not only allows easy incorporation of surface
functionalizing moieties for providing colloidal stability to HAp nanoparticles, but
also helps in improving its drug delivery efficiency. Through surface functionaliza-
tion, a large number of organic molecules having functional groups such as hydroxyl,
carboxyl, amine, and phosphate can be incorporated on the surface of HAp nanos-
tructures, which provides binding sites for biomolecules and drugs. Several groups
have incorporated different functionalities on HAp nanostructures during synthesis
by chemical precipitation method and investigated their drug delivery behaviour. A
high loading efficiency for DOX along with pH-responsive release was reported in
citrate functionalized HAp nanoparticles as compared to pure HAp. The high drug
loading was attributed to electrostatic interaction between the negatively charged
citrate molecules and positively charged DOX [55]. Li et al. anchored polyacrylic
acid (PAA) on the surface of HAp particles by chemical precipitation method for
delivery of DOX. PAA acted as a pH-controlled switch, which retarded the release of
DOX at physiological pH (pH 7.4) due to strong electrostatic interactions between
DOX and PAA. However, under an acidic environment (pH 5.0), the electrostatic
interactions weekend resulting in dissociation of DOX in the media [56]. The pH-
responsive drug delivery systems are of great importance, in particular for cancer
therapy. Due to the acidic microenvironment of tumour cells, a selective and targeted
release of drugs can be achieved using pH-responsive drug carriers, which helps in
reducing the potential side effects of drugs. In addition to this, HAp nanoparticles can
be conjugated with site-specific ligands such as folic acid (FA), hyaluronic acid (HA),
and transferrin, which are abundantly expressed on cancer cells. The incorporation of
15 Implications of Synthesis Methodology on Physicochemical … 629

these ligands increases the uptake probability of drug nanocarriers by the cancer cells,
which are over-expressed with the receptors. This helps in decreasing the side effects
of the drug on healthy tissues by mostly localizing the drug in cancerous tissue. Kong
et al. used the chemical precipitation method to incorporate HA ligand on the surface
of HAp nanoparticles to bind over-expressed CD44 receptors on cancer cells. They
observed enhanced cellular uptake of nanocarriers in CD44 receptors over-expressed
A549 cells as compared to U87 cells having low CD44 receptors expression [57, 58].
Verma et al. prepared glycine-coated HAp nanoparticles by co-precipitation method
and functionalized them with FA. The results indicated higher uptake of DOX-loaded
nanoparticles by KB cancer cells, which are over-expressed with folate receptors as
compared to folate-receptor deficient, WRL-68 cells [59]. Similarly, Venkatasubbu
et al. used folic acid as a targeting ligand for site-specific delivery of paclitaxel [60].
Along with drug delivery, HAp can also be used for the theranostic activity, i.e.,
therapeutics conjugated with diagnostics. The concurrent delivery of drug as well as
imaging increases the accuracy and efficiency of HAp as a therapeutic agent. There-
fore, researchers have attempted incorporating various molecules that are capable of
being detected by magnetic resonance imaging, fluorescence imaging, positron emis-
sion tomography (PET), single-photon emission computed tomography (SPECT),
etc. in HAp. Victor et al. fabricated a theranostic HAp system doped with neodymium
by chemical precipitation method for the delivery of 4 acetyl salicylic acid to treat and
simultaneously monitor colon cancer. The system was functionalized with alginic
acid polymer to impart pH-responsive drug release in colonic alkaline medium.
While neodymium doping conferred near-infrared fluorescence capability, thereby
making simultaneous imaging possible [61]. In another study, Europium-doped HAp
nanoparticles were fabricated as theranostic near-infrared luminescent carriers for
delivery of DOX [62]. Et al. designed HAp nanoparticles labelled with radionuclides
technetium-99 m and radium-223, for diagnostics and therapeutic activity, respec-
tively [63]. Figure 15.6 shows the schematic diagram of different methodologies
used for the fabrication of HAp-based nanostructures for targeted drug delivery and
theranostics.

15.3.2.2 Hydrothermal Method

The hydrothermal method for HAp synthesis is the next most frequently used method.
The hydrothermal method is similar to chemical precipitation, except that the ageing
step is carried out under high pressure at a reaction temperature, normally between
90 °C–150 °C [64]. The high pressure and temperature accelerate the dissolution and
crystallization process of precursors and HAp, respectively, which alter the crystal
growth mechanism and habit. As a result, the HAp crystals formed using this method
seem to have large and well-defined sizes with lesser chances of particle agglomer-
ation [65]. The pressure and temperature can be optimized to allow the formation
of HAp with controlled morphology [66]. If the solvent used is water, then it is
termed as hydrothermal and in the presence of other organic solvents, it is called
solvothermal. This is a simple process beginning with thorough mixing of calcium
630 M. Quadros et al.

sli

Magne c
nanopar cles

Linker molecule

Drug Polymer

Passive Stimuli Sensitive

Targeting targeting
HAp
Active
Targeting Theranostic

Folic acid MRI contrast agent

Hyaluronic acid Radioac ve agent

An body Fluorescent agent

Fig. 15.6 Schematic diagram showing different methodologies for fabrication of HAp-based
nanostructures for targeted drug delivery and theranostics

and phosphate precursors in the required stoichiometric amount. The mixture is then
transferred to a Teflon-lined stainless steel hydrothermal autoclave and heated at the
desired temperature for about 12 h, following which, the powder is calcined, washed,
and dried to remove residual reactants [67–69]. The hydrothermal reaction inside the
autoclave can be described in two steps, first formation of nuclei, i.e., nucleation in the
supersaturated solution followed by its gradual growth to form the final product [70].
Figure 15.7 shows the diagrammatic illustration of HAp synthesis by hydrothermal
method. The product obtained using this technique has high crystallinity and phase
purity and is often seen to have rod-shaped morphology. The formation of rod-like
particles using this technique is attributed to the slow growth of crystals in one-
dimensional orientation [71]. However, using specific reaction conditions and in the
presence of additives, other morphologies can also be obtained. The pH of the reac-
tion is also considered as a prime factor in deciding the morphology of the HAp
particles. At high pH, the degree of crystallinity is seen to increase, which can be
attributed to the presence of an increased number of phosphate ions [72].
15 Implications of Synthesis Methodology on Physicochemical … 631

Fig. 15.7 Schematic

representation of the
synthesis of HAp by
hydrothermal method

In order to synthesize more diverse structures, different types of additives have

also been examined, which in a way regulate the morphology of HAp. Jiang et al. used
ethylenediaminetetraacetic acid (EDTA) and citric acid as double chelating agents
and fluoride ions as crystal growth inhibitor during the hydrothermal method of HAp
synthesis, resulting in flower, shuttle, rod, whisker, and prismatic shaped microcrys-
tals. The final shape of the HAp microcrystal was governed by the molar ratio of
calcium ions with EDTA and citric acid [73]. When citric acid was incorporated in the
reaction, the morphology of HAp particles transformed from nanosheets to nanorods
with an increasing concentration of citric acid [74]. Whisker-like morphology was
obtained by the introduction of additives like acetamide and urea, which gradually
632 M. Quadros et al.

raise the reaction pH, thereby increasing the rate of hydrolysis which causes super-
saturation [75, 76]. In a study, Shojai et al. elucidated the role of urea to be more
than just a pH modifier during the preparation of HAp. They theorized urea to form
complexes with calcium ions, subsequently decreasing the number of nucleation
sites, which allows the small crystallites to grow into larger particles [72].
As discussed in the chemical precipitation method, the surface functionaliza-
tion enhances the drug delivery efficacy of HAp due to the presence of surface
moieties. Another modification that can increase the drug delivery efficiency of HAp
particles is the formation of hollow microspheres. The high surface area of HAp
particles coupled with hollow structure provides more binding sites for drug attach-
ment. Lin et al. demonstrated hollow microspheres prepared by the hydrothermal
method enabled high loading of antimicrobial drug vancomycin than that of the tradi-
tional HAp nanoparticles [77]. In another study, Cipreste et al. used the surfactant-
assisted hydrothermal method to synthesize folic acid functionalized HAp nanorods
with gadolinium doping. The folic acid provided targeted ability, while gadolinium
provides radiotherapy as well as acts as a magnetic resonance imaging contrast agent,
therefore, functioning as a theranostic agent with the capability of radiotherapy and
bio-imaging [78].

15.3.2.3 Sol–gel Method

The sol–gel method of HAp synthesis involves molecular interaction of calcium and
phosphorus precursors thereby asserting greater control over the purity of the formed
HAp phase [79, 80]. In general, sol–gel technique is a rather complex method with
a series of steps; first, the hydrolyzed precursor solution (sol) is transformed into
a 3D gel structure by poly-condensation or poly-esterification reaction. The gel is
aged to allow conversion into a solid mass, and this period of ripening is generally
long (24 h) due to the slow reaction of calcium and phosphorus precursors. Next, it
is dried at temperatures greater than >800 °C, which collapses the network to form
the final product [68, 81–83]. This method is also used for coating metallic implants
with HAp. In this process, the surface to be coated is dipped into the precursor sol or
the sol is spin coated on the implant. The sol is aged to form a gel, which is in turn
heated at 500–1000 °C to form xerogel, i.e., dried gel with unhindered shrinkage
and high porosity. Further, heating and sintering of xerogel at elevated temperatures
results in the bonding of HAp to the metallic surface. This process is repeated until
the coating of desired thickness is achieved [84]. Figure 15.8 shows the diagrammatic
illustration of HAp synthesis by sol–gel method.
The reaction temperature plays an important role in regulating the phase impurity
of HAp. By using sol–gel method, Santosh et al. synthesized HAp with the Ca/P ratio
of 1.67 at temperatures below 600 °C, beyond which they observed the formation
of calcium oxide (CaO) phase indicated by an increased Ca/P ratio of 1.75 [85, 86].
Since the presence of CaO impurity may possibly affect the biological performance
of HAp, many attempts have been made to decrease or eliminate it. For instance,
Jillavenkatesa et al. proposed neutralizing CaO with dilute hydrochloric acid to form
15 Implications of Synthesis Methodology on Physicochemical … 633

Fig. 15.8 Diagrammatic illustration of hydroxyapatite synthesis by sol–gel method

water-soluble calcium chloride that can be removed by filtration [87]. In another

study, in order to avoid the use of alkoxide catalyst, ethanol was used, and the resulting
HAp was stable up to 1200 °C without the formation of any by-products [88, 89].
The size and shape of HAp can also be controlled by optimizing the calcination
temperature. Padmanabhan et al. observed that at 700 °C, the HAp crystals increase
in size and elongate in an anisotropic direction, resulting in the formation of rod-
shaped particles [90]. Also, the introduction of polyethylene glycol as an organic
modifier was used to control the size of the particles by virtue of the interaction
between the ether bonds of polyethylene glycol and HAp crystal [91]. HAp fibres
have also been formed using sol–gel method, using calcium acetate and phosphorous
pentoxide as the starting precursors [92]. The major limitation of sol–gel method for
the synthesis of HAp is the poor hydrolysis of phosphates, since phosphate esters are
very stable in water they cannot be hydrolyzed easily and hence require a metal-ion
catalyst, which considerably increases the cost of the reaction. Another drawback is
the long ageing period and sintering process. However, researchers have managed to
cut down this time by 50-fold to 200-fold by avoiding ageing and using fast rotary
evaporation instead [93]. Another alternative is to employ microwave-assisted drying
that takes only 2 h if the temperature is around 150 °C [94].
Sol–gel method is widely used for coating of HAp on metallic or ceramic implants
[95, 96]. Biomedical implants are medical devices, which are used to replace or
support a damaged biological structure or simply enhance the structural integrity of
an existing biological structure. Most implants are composed of metallic materials
like stainless steel (316L) [97–99], cobalt [100–102], and titanium-based alloys [103–
106]. These metal alloys are used as implant material due to their good structural and
mechanical strength; however, their low biocompatibility and osteointegration ability
limit their application. Moreover, on prolonged contact with physiological fluids,
they may corrode or leach out metallic ions which, in turn, would elicit an immune
response [107]. A most widely used approach to increase the biocompatibility of
these implants is to create a barrier between the metallic and tissue interface, i.e.,
to coat the metal surface with biocompatible materials. In this context, HAp has
634 M. Quadros et al.

been extensively tested as a coating material for implants by virtue of its excellent
biocompatibility, chemical stability, and osteo-conductivity. Upon implantation, it
is crucial that the implant remains in the designated place throughout its intended
lifespan, and any change in position is undesirable. Therefore, to avoid this, the
patient’s mobility is restricted for a period of about 100 days to allow the implant
to fixate strongly with surrounding tissues. However, this period can be reduced to
only 20 days by using HAp-coated implants [107]. The success of the HAp-coated
implant majorly depends on its durability, coating thickness, microtopography, the
bioactivity of surrounding tissue cells, and adhesion of bonding strength of HAp and
implant.
Zhang et al. coated titanium (Ti) implant with HAp using sol–gel method, using
triethyl phosphite and calcium nitrate as phosphorus and calcium precursors, respec-
tively. The Ti implants were dipped in the sol and withdrawn at a speed of 20 mm/min.
After drying at 80 °C to evaporate the residual solvent, the implants were annealed at
450 °C for 2 h. This process was repeated six times until a HAp coat of 1–2 μm was
obtained. The biocompatibility and osteointegration of these HAp-coated implants
were studied by immersing them in an SBF solution, which mimics the biological
environment. Formation of apatite crystals was observed only on HA- coated implant
as compared to an uncoated implant, thus indicating that HAp coat favours apatite
formation possibly due to the release of calcium ions from HAp [108]. The bond
strength of the HAp coat on the implant material is of critical importance to with-
stand the stress of the growing bone. The strength of the human bone is noted to be
about ∼18 MPa; hence, it is ideal to have the coating on the implant with greater
bond strength than 18 MPa. Piveteau et al. were able to attain an adhesion strength of
>25 MPa using sol–gel coating method. In another study, dense and adhesive HAp
coatings on SS implants were obtained using sol–gel method and heat treatment at
375–500 °C to obtain crystalline morphology. However, micro-cracks were observed
at an annealing temperature of 500 °C resulting in compromised bonding strength
of HAp-SS [109]. Considering theoretical aspects, implants such as hip prostheses
experience a great amount of bending stress, and the HAp coats on such implants
should, therefore, exhibit high bending strength. In such cases, thick HAp layers have
a high risk of being damaged by forming surface cracks; therefore, thin HAp layers
are more suitable for these purposes. Sol–gel method has the capability of producing
thin ceramic coatings with a nano-range thickness of 70–200 nm [110]. Breme et al.
fabricated thin HAp layers (1 μm) on Ti alloy substrate using sol–gel method with
good cohesion with implant surface which was tested to be about 70 N mm2 [107].
Owing to the molecular interaction of reactants, the sol–gel method has been also
increasingly used for the incorporation of other elements like sodium [111], fluo-
rine [112], cerium [113], strontium [114], zinc, chromium [115], and so on to form
doped HAp. These elements are chosen intentionally to change the crystal lattice of
HAp or simply for added biological activity. Incorporation of additives has also been
observed to increase the bonding of HAp with the metal implant. For instance, the
addition of fluoride ions increased the adherence of the HAp coat with Ti alloy up to
35%. This improvement in adherence was attributed to improved chemical bonding
of Ti and fluoride containing HAp at the interface [116]. The surface morphology
15 Implications of Synthesis Methodology on Physicochemical … 635

of the implant plays an important role in the attachment of osteoblast cells. In a

study, Feng et al. demonstrated that rough and porous implant surfaces aid in adher-
ence and stimulation of osteoblast cells [117]. Additionally, the surface composition
also determines osteoblast adhesion as hydroxyl groups favour osteoblast attach-
ment and proliferation [118]. Feng et al. noted that adhesion of osteoblast cells on
the HAp layer is via interaction with calcium ions [119]. The presence of hydroxyl
groups promotes osteoblast proliferation and also increases the production of osteo-
calcin (a biomarker for osteoblast differentiation) [120]. HAp coatings prepared via
sol–gel method displays rough and porous morphology, and thereby have enhanced
biological activity.

15.3.2.4 Emulsion Method

Most chemical methods have poor control over the particle size of HAp and other
microstructural heterogeneities. However, the synthesis of HAp via the emulsion
method has been found to provide greater control on morphological parameters of
HAp. Typically, emulsions are dispersions of two or more immiscible liquids, made
miscible by the addition of surfactants at the critical micellar concentration (CMC)
to form globular micelles. If the volume of water in oil is very low, it is called a
microemulsion which has thermodynamic stability and is optically transparent. The
emulsion method, particularly the microemulsion method for synthesis of HAp, is
an effective method for regulating the size and size distribution of HAp particles as
the growth of the particles is strictly restricted to the microreactors, i.e., the emulsion
droplets. These microreactors also discourage the agglomeration of particles due
to the presence of surfactants forming an interfacial barrier between aqueous and
organic phases [121]. HAp synthesized by emulsion methods have been observed
to have a smaller HAp particle size than the ones prepared by the co-precipitation
method [122–124]. Moreover, the microemulsion globules act as nanosized reac-
tors that favour the growth of spherical HAp particles instead of instinctive rod-like
structures. The procedure for HAp synthesis using this method is fairly simple with
stepwise mixing of organic, surfactant, and aqueous phase containing calcium and
phosphate precursors. The solution is stirred thoroughly or homogenized while main-
taining the pH between 9 to 11, which results in precipitation of HAp. This is further
dried and calcined at elevated temperatures to remove excess reactants [125, 126].
Figure 15.9 provides a schematic representation of the synthesis of HAp by emulsion
method and Table 15.1 renders the details of the chemical composition of emulsion
systems employed for the synthesis of HAp nanoparticles.
Precise control on the size and shape of HAp can be obtained by varying primary
parameters like surfactant type, surfactant concentration, water to oil ratio, synthesis
temperature, reaction time, solvent type, and pH of the reaction. For example, Sun
et al. demonstrated that as the molar ratio of solvent and surfactant increases,
the length of HAp nanorods increases. This phenomenon was attributed to the
increased flexibility of the interfacial film, allowing the growth of HAp nanorods
[127]. Bakhtiari et al. demonstrated that by increasing the concentration of pore
636 M. Quadros et al.

Fig. 15.9 Schematic representation of the synthesis of hydroxyapatite by emulsion method

Table 15.1 General composition of emulsion and microemulsion systems with reported
hydroxyapatite particle size range
Organic solvents Surfactant Calcium and Size Ref
phosphate precursors
1-dodecanethiol CTAB Calcium nitrate, 23–40 nm [128]
Orthophosphoric acid
Cyclohexane Span-80 Calcium nitrate, 70 nm [125]
Diammonium
phosphate
Iso-octane, Span-20, Tween-80 Calcium 10 μm [130]
n-caproic acid chloride,Diammonium
phosphate
N-butanol TX-100, CTAB Calcium nitrate, 200 nm [129]
Diammonium
phosphate
Iso-octane Sodium salt of Calcium hydroxide, 100 nm [122]
dioctylsulfosuccinate Orthophosphoric acid
1-butanol, CTAB Monocalcium 50–200 nm [132]
n-octane phosphate, Calcium
chloride,
Cyclohexane Poly(oxyethylene) Calcium chloride, 20–40 nm [123]
nonylphenol ether Diammonium
phosphate
(continued)
15 Implications of Synthesis Methodology on Physicochemical … 637

Table 15.1 (continued)

Organic solvents Surfactant Calcium and Size Ref
phosphate precursors
Ethanol, pure vegetable Triton X-100 Calcium hydroxide, 10–50 μm [124]
oil Orthophosphoric acid
Petroleum ether Ethoxylated lauryl Calcium chloride, 10 nm [133]
alcohol (KB6ZA) Diammonium
phosphate
Dodecane, ethanol Pentaethyleneglycol Calcium hydroxide, 20–100 nm [126]
dodecyl ether (C12E5) Potassium dihydrogen
phosphate
Petroleum ether Tomadol Calcium nitrate, 160 nm [131]
Diammonium
phosphate
Cyclohexane Poly(oxyethylene) Calcium nitrate, 30–50 nm [134]
nonylphenol ethers Orthophosphoric acid
Cyclohexane, CTAB Calcium nitrate, 100 nm [135]
n-octyl alcohol Diammonium
phosphate
N-butanol, CTAB Calcium nitrate, 30–90 nm [136]
n-octane Diammonium
phosphate
Cyclohexane Poly(oxyethylene) Calcium chloride, 5–10 nm [137]
nonyl phenol ethers Diammonium
phosphate

expander, 1-dodecanethiol changed the morphology from rod-like micelles to spher-

ical HAp structures [128]. A similar shape transition from rod to spherical was seen
by increasing the pH of the reaction from neutral to alkaline [129]. In another study,
the effect of reaction temperature was noted to have decreased the surface area of
synthesized HAp from 227 to 98 m2 g−1 implying an increase in particle size [130].
The choice of calcium precursor also affects the quality of HAp produced. Chen et al.
observed that when calcium nitrate was used as a calcium precursor, it transformed
into β-tricalcium phosphate (β-TCP) impurity thus exhibiting low thermal stability at
high temperatures. While the presence of β-TCP was not detected in HAp prepared
using calcium hydroxide as a calcium precursor [131]. Although HAp synthesis by
emulsion and microemulsion technique has been shown to offer control on the forma-
tion of homogenous nanoparticles with minimum agglomerations, the requirement
of large quantities of organic solvents not only acts as a limitation for industrial
scale-up but also stands as a non-green process.
638 M. Quadros et al.

15.3.2.5 Hydrolysis Method

The hydrolysis method for synthesizing HAp is one of the simplest methods as
compared to other wet methods. As the name suggests, it involves hydrolysis of
other calcium phosphate(CaP) phases such as dicalcium phosphate (DCPA), dibasic
calcium phosphate dehydrate (DCPD) [1, 138, 139], and tricalcium phosphate (TCP)
[26]. Acidic calcium phosphates like DCPA and DCPD are thermodynamically
unstable above pH 6.0–7.0; therefore, they undergo transformation into more stable
calcium phosphates, like HAp. The synthesis of HAp using the hydrolysis method
follows two stages; the first is the dissolution of calcium phosphate precursor resulting
in a supersaturated solution to form HAp, followed by precipitation of HAp with
phosphate precursor. The synthesized HAp is then washed with deionized water and
dried [140]. Hydrolysis of calcium phosphate precursor, α-TCP, has been commonly
used for the synthesis of HAp. When used for bulk HAp synthesis, the procedure is
characterized by an initial dissolution of the α-TCP powder, i.e., an induction period,
followed by growth of HAp, where the transformation of α-TCP to HAp occurs [141].
The variable factors that govern the morphology of HAp are pH and temperature
of the reaction [1]. Park et al. prepared whisker-shaped HAp from the hydrolysis
of α-TCP at pH 9.0; however, at pH 11.5, it transformed into an ellipsoidal shape
[142]. Ito et al. demonstrated that at high pH 11.0–13.0, HAp produced was in the
form of bundled needles, while at comparatively low pH of 9.0–10.0, elongated
HAp nanosheets were formed. This change in morphology in response to varying
pH was attributed to the different mechanisms of DCP hydrolysis to form HAp
[143]. Similar attempts have been made by incorporating additives that can act as
morphology modulating agents. In one such scientific exploration, Shih et al. studied
the effect of surfactant CTAB in HAp synthesis from precursor dicalcium phosphate
dehydrate (DCPD). They observed that HAp nanoparticles decreased in size with
increasing CTAB concentration, which was explained by the formation of CTAB
micelles that inhibit the further growth of crystals [144]. Durucan et al. demonstrated
the effect of temperature on HAp morphology. Smaller crystallites were formed at low
temperatures, i.e., 37 °C as compared to those formed at 56 °C, which was attributed
to microstructural coarsening at high temperatures [141]. A similar observation was
noted by Fulmer et al., where the morphology of HAp formed by DCPD hydrolysis
varied from needle-like at 25 °C to globular shape at 60 °C [145]. The type of solvent
system used for the hydrolysis method has also been seen to affect reaction time
and morphology of synthesized HAp. For example, HAp produced using a hydro-
alcoholic solvent system with a polar solvent like ethanol was found to delay the
hydrolysis of α-TCP, thereby increasing the reaction time up to 120 h. In this reaction,
the high miscibility of ethanol with water was theorized to reduce the hydrolytic
activity of water. Similarly, experimenting with other alcoholic solvents, a trend was
observed, which correlated increasing solvent polarity with increasing reaction time.
In other words, non-polar (hydrophobic) solvents form a biphasic system, as a result,
they do not interfere with the ongoing hydrolytic process in the aqueous phase [146].
In the hydro-alcoholic solvent system, Sakamoto et al. observed the formation of long
needle-shaped crystals in the presence of 1-octanol as compared to platelet crystals,
15 Implications of Synthesis Methodology on Physicochemical … 639

which were obtained when only water was used as a solvent. In order to further
understand this phenomenon, 1-octanol was replaced with its alkane counterpart,
i.e., n-octane, and the HAp crystals produced were smaller in size. Since the only
difference between 1-octanol and n-octane is the presence of −OH group, it can be
assigned to have some interaction with the aqueous phase resulting in inhibition of
crystal growth. Similar results were obtained with other solvents without OH groups
such as cyclooctane and toluene [147]. These examples suggest that the size and
shape of HAp crystals can be controlled by solvent properties, i.e., hydrophobicity
and the presence of −OH groups.

15.3.3 Miscellaneous Methods

In addition to the above methods, there are several other methods, such as sonochem-
ical, biomimetic, combustion, plasma spray, and electrodeposition, which are widely
being employed for the preparation of HAp for various biomedical applications.

15.3.3.1 Sonochemical Method

The sonochemical method is generally used when HAp particles are to be synthesized
at the nanoscale. As the name suggests, this method involves powerful ultrasound
radiation to accelerate the reaction of calcium and phosphate precursors. Therefore,
HAp nanocrystals with highly crystalline, uniform, and narrow particle size distri-
bution are synthesized at a rate that is 5.5 times greater than conventional techniques
[148]. The ultrasonic energy is provided by the ultrasonic horn, a metallic bar with
a tapered end, which is powered by an ultrasonic transducer. The principle of the
sonochemical method is based on acoustic cavitation, i.e., formation and collapse of
bubbles when subjected to intense sound. Here, calcium and phosphate precursors are
theorized to be adsorbed onto or inside the bubble. On application of ultrasound, as
the bubble collapses, enormous energy is released, which in turn heats the contents of
the bubble [149]. This localized high energy in the form of temperature and pressure
functions as a small chemical reactor accelerating the reaction of precursors to form
HAp [150–152]. On comparing sonochemical method with conventional precipita-
tion method under identical reaction conditions, Jevtic et al. observed co-precipitation
method to form a multiphase system, consisting of various calcium phosphate phases
such as calcium hydrogen phosphate hydrate, calcium phosphate, calcium phosphate
hydroxide, and monetite, while HAp synthesized with the sonochemical method was
monophasic in nature [150].
Some variables that can be optimized in sonochemical synthesis are ultrasound
frequency, intensity, power and horn tip size, horn immersion depth, the volume of
ultrasonicated solution, and duration of ultrasound [153, 154]. Kim et al. studied HAp
synthesis by the sonochemical process using phosphoric acid and calcium hydroxide
640 M. Quadros et al.

as precursors. They observed that before the formation of monophasic HAp, dical-
cium phosphate hydrate (DCPD) is formed as an intermediate at the beginning of the
reaction, which disappears completely after 60 min of ultrasound irradiation. It can
be conceived that prolonging the irradiation time increases the reactivity of DCPD to
form monophasic HAp effectively [155]. Along with ultrasound radiation, increasing
the reaction temperature up to 80 °C seems to further aid the dissolution and reactivity
of precursors [154]. To control the morphology of HAp crystals, researchers have
experimented with various additives. For instance, the addition of urea as a precipi-
tating reagent resulted into platelet-shaped HAp crystals [156], while needle-shaped
crystals obtained with carbamide were used as a precipitating agent [157]. The sono-
chemical method has been shown to significantly reduce agglomeration, which is one
of the major drawbacks of other conventional methods. This has been assigned to
the involvement of three consecutive processes in sonochemical synthesis; first, the
shockwave caused by cavitation pushes the crystals away from each other to the extent
of prohibiting their bonding together. Second, as the crystal nuclei grow in size, their
surface area comparatively increases and they become more stable; therefore, they
need not form agglomerate to decrease their surface energy. And the third is the mini
reactors created by ultrasound, which inhibit aggregation through control of the local
nucleus population [153]. To further decrease agglomeration, non-ionic dispersing
agents like glycerol and glucose have also been incorporated, which adsorb on HAp
nuclei via hydrogen bond and electrostatic interaction. Additionally, the HAp crys-
tals preferentially grow along the c-axis resulting in whisker-like morphology [158].
Although the sonochemical method provides highly crystalline, nanoscale HAp crys-
tals with a narrow size distribution, its scalability to industrial level remains a barrier,
as the penetration capability of the power ultrasound in the liquid is limited, which
is about 0.1 m when generally used for a batch size of 500 mL precursor mixture
[159]. However, increasing the number of ultrasonic probes or making the mixture
flow through probes in a tube can be thought of to use the sonochemical method for
HAp synthesis at an industrial scale.

15.3.3.2 Biomimetic Method

The biomimetic method for HAp synthesis impersonates biological HAp formation
[160]. The HAp produced with this technique mimics bone HAp that is known to
be calcium deficient and has the presence of inorganic ions [161]. The biomimetic
method is a fairly simple process, similar to that of the chemical precipitation method
with exception of the first step, i.e., incubation of calcium and phosphate precur-
sors in simulated body fluid (SBF) for the formation of fine precipitates also called
“seeds”. The SBF is prepared in such a way that it mimics the human body fluid,
containing various inorganic ions with concentrations identical to those found in
human blood plasma. Both calcium and phosphate precursors are dissolved in SBF
separately, followed by dropwise addition of phosphate solution to calcium solution
15 Implications of Synthesis Methodology on Physicochemical … 641

under magnetic stirring. The pH of the reaction is maintained throughout at an alka-

line range of 7–11. The precipitated HAp is then aged, washed, filtered, and calcined
at elevated temperatures to improve the levels of crystallization seeds [162–164].
The quality of SBF used for the precipitation process is of utmost importance,
as even a slight change in pH can severely affect the characteristics of synthesized
HAp crystals such as phase purity and stability [162]. Tas et al. synthesized HAp
powders using SBF solutions at physiological conditions of pH and temperature (i.e.,
7.4 and 37 °C, respectively) [165]. Mavis et al. modified the SBF solution by varying
the ionic strength in order to accelerate the precipitation of HAp [166]. For further
increasing the precipitation rate, Demirtaş et al. employed microwave radiation to
improve energy transfer throughout the volume of solution [167]. Similarly, Altınsoy
et al. combined the biomimetic method with microwave irradiation to produce HAp
with high purity, small particle sizes, and narrow size dispersion [168]. Another
variable is the choice of calcium and phosphate precursors used, as they too affect
the crystallinity and phase content. For instance, when calcium chloride was used
as a calcium precursor, the chloride ions were seen to be incorporated in HAp and
resulting into chloroapatite phase [162]. Similar to other synthesis methods, addi-
tional reagents, i.e., modifiers can be added in the biomimetic process to control HAp
morphology. The addition of 2–6% polyethylene glycol (PEG) resulted in HAp with
higher crystallinity than those produced without PEG [169, 170].
The biomimetic method is a widely used technique for coating implants to render
them biocompatible with surrounding tissue [171]. Jiang et al. used the biomimetic
method to coat nickel–titanium (NiTi) implants with HAp to reduce the leaching
of Ni ions. The implants were first treated with aqueous HNO3 followed by quick
immersion in boiling NaOH solution to activate the surface before immersion in
SBF. Briefly, a layer of titanium oxide (TiO2 ) is formed on the surface due to the
reaction of Ti with HNO3. Next, the NaOH treatment results in many Ti-OH groups,
which absorb calcium and phosphate ions from SBF, to precipitate a layer of HAp
on the implant surface. The formation of HAp coat on implant resulted in the release
of significantly less amount of Ni, when compared with its uncoated counterpart,
suggesting that HAp forms a barrier between SBF and metal interface. Further, the
incubation period, i.e., the period of implant being immersed in SBF was observed
to determine the quality of the HAp coat. The incubation period of 3 days resulted
in a discontinuous HAp layer, while a uniform film was observed after incuba-
tion of 5 days [172]. Zhang et al. synthesized spherical HAp micro-particles using
the biomimetic method and using polymer polylactic acid as a physical scaffold to
provide multiple nucleation sites for HAp [173].

15.3.3.3 Combustion Method

The principle of the combustion method is to generate a vigorous exothermic redox

reaction between the oxidizer (e.g., nitrate) and fuel (e.g., citric acid) to increase
the reactivity of calcium and phosphate precursors for the formation of HAp [174].
Its key features include quick synthesis, high purity, high homogeneity, and the
642 M. Quadros et al.

formation of ultrafine powder. The process is similar to that of sol–gel process, the
fuel agent, e.g., citric acid is mixed with calcium and phosphate precursor solution
(sol), and the pH of the solution is adjusted as 2–3 by nitric acid. The reaction
mixture is heated to evaporate the solvent to form a gel, which is dried at 110–
120 °C followed by calcination at 200 °C to form HAp following Eqs. (15.1) and
(15.2) [175, 176]. Simply put, the reaction begins at a comparatively low temperature
and rapidly rises during the combustion period followed by subsequent fast cooling.
All these processes ensure the formation of numerous crystal nuclei resulting into
fine particulates towards the end of the reaction [177].

9Ca(NO3 )2 + 5C6 H8 O7 → 30CO2 + 9N2 + 20H2 O + 9CaO (15.1)

10CaO + 6(NH4 )2 HPO4 → Ca10 (PO4 )6 (OH)2 + 12NH3 + 8H2 O (15.2)

The ratio of oxidizer to fuel is of paramount importance in this method as it

controls the exothermicity of the combustion. Sasikumar et al. used tartaric acid as
fuel to produce submicron-size particles of HAp. The rationale for using tartaric acid
was for two main reasons; first, it acted as a chelating agent preventing precipitation
of calcium ions, so that it can be transformed into a gel. Secondly, a large amount
of heat is evolved when tartrate gel undergoes combustion, which provides local
heating to the precursors for the formation of HAp. Further, they optimized the
metal ions to fuel ratio, i.e., calcium to tartaric acid ratio to be 1: 2 in order to avoid
the formation of calcium phosphate phases other than HAp [178]. Similarly, succinic
acid was also studied as a reducing agent, moreover, it also formed a polymer matrix
to avoid precipitation of calcium ions [179]. Tas et al. synthesized HAp using urea
as a fuel in less than 15 min reaction time. Urea decomposes into a gaseous mixture
of nitrous oxides, which ignite spontaneously at 500 °C, thereby increasing the local
temperature of dried gel to 1300 °C instantly. This high temperature increases the
reactivity of calcium and phosphate precursors to form submicron-size (0.45 mm)
HAp powder [180]. The concentration of nitric acid (oxidizer) also seems to affect
the purity of the end product. Aghayan et al. demonstrated that at a lower nitric
acid concentration (0.1–0.3 mol), both HAp and β-TCP were formed, while as the
concentration of nitric acid is increased beyond 0.7 mol, the HAp phase was seen
to be more predominant [181]. The combustion method can be considered for large-
scale synthesis as the high exothermic chemical reaction becomes self-sustaining
after only a short energy pulse initiating the reaction. Thus, the reduced synthesis
energy and materials cost have the advantage of being extremely time and energy
efficient [182].

15.3.3.4 Electrodeposition Method

Electrodeposition is based on the principle of electrophoresis, i.e., the application of

an electric field to move charged molecules in a liquid medium towards an electrode.
15 Implications of Synthesis Methodology on Physicochemical … 643

This method is used to coat metallic implants using preformed HAp (electrophoretic
deposition) or by a series of electrochemical reactions using calcium and phosphate
precursors (electrochemical deposition). Both techniques offer uniform layers with
high coating efficiency and easy control at a relatively low expense, thereby making it
an industrially viable technique. The electrochemical method for deposition of HAp
on a substrate involves immersion of electrodes (typically an anode and cathode) in
an electrolyte containing calcium and phosphate precursors with/without SBF. The
material to be coated forms one electrode, the pH is adjusted to 6–9, and a potential
is applied across the electrodes using a potentiostat, which results in deposition of
HAp on the implant surface. The freshly prepared HAp-coated implants are then
sintered at high temperatures to densify and form a cohesive bond with the implant.
The mechanism of deposition of HAp can be explained by two steps; first, nucleation
of HAp at the metallic surface followed by growth of the HAp crystals to form a
film. Chemically, it can be explained by a series of electrochemical half-reactions,
acid–base reactions, and precipitation reactions shown in Eqs. 15.3–15.6. Briefly,
the electrolysis of water at the cathode forms hydrogen gas and hydroxide ions,
which increase the local pH around the cathode. Further, the hydroxide ions react
with phosphate precursor, e.g., dihydrogen phosphate to form dicalcium phosphate,
which later converts into HAp [183].

2 H2 O + 2e− = H2 + 2OH− (15.3)

OH− + H2 PO−
4  H2 O + HPO4
2−
(15.4)

Ca2+ + HPO2−
4 + 2H2 O  CaHPO4 .2H2 O (15.5)

5CaHPO4 .2H2 O + 6 OH−  Ca5 (PO4 )3 OH + 2PO3−

4 + 15 H2 O (15.6)

As observed in other synthesis methods, the temperature of HAp synthesis and

processing plays a major role in determining the morphology and composition of
HAp coatings. Yuang et al. observed that coatings formed on stainless steel (SS) at
65 ºC were more crystalline in nature than coatings deposited at 25 °C. Additionally,
they also observed that the temperature of sintering post HAp formation determines
the chemical composition of the coating layer as at high temperatures of about 600 °C,
HAp decomposes into TCP. To avoid the formation of TCP, Yuang et al. employed
a vacuum for the sintering process. Their results demonstrated the absence of TCP
even at a sintering temperature of 800 ºC [184]. The pH at the surface of the device
can be tuned by controlling the current density that passes through the electrodes,
which in turn would control the deposition rate and morphology of the HAp layer.
In order to increase the cohesion of HAp to the implant, Stoch et al. fabricated an
intermediate layer of calcium–silica between the Ti surface and HAp layer. They
observed improved adhesive strength of HAp with implant due to the formation of
CaTiO3 and CaSiO3 intermediates [185].
644 M. Quadros et al.

For electrophoretic coating, preformed HAp powder is suspended in an electrolyte

(e.g. water, organic solvent, etc.) to form a colloidal suspension. On application of
potential difference, the colloidal HAp particles migrate towards the counter charged
electrode (coating substrate), on which the deposition needs to be performed. The
HAp-coated implants are then sintered at high temperatures to allow bonding of
HAp with the implant surface. Since coating occurs by movement of HAp particles
towards the electrode, it is crucial that the HAp particles be colloidally stable as
aggregated particles would result in the non-uniform coating. Using this technique,
Wei et al. formed a thick layer of about 500 μm on the implant surface [186]. Eliaz
et al. studied both electrochemical and electrophoretic deposition of HAp on implant
surfaces. They observed that in the case of electrophoretic deposition, the applied
potential and time affect the development of HAp coatings. The coating weight and
thickness both were found to increase with the increase in applied potential and
period of deposition, respectively. On the other hand, in the case of electrochemical
deposition, the pH of the solution, applied cathodic potential, and bath temperature
were found to influence the nature of coatings [187]. Some drawbacks of electrode-
position techniques are the involvement of the post-synthesis annealing process of
HAp-coated implants, which result in the appearance of decomposition products such
as tricalcium phosphate, tetracalcium phosphate, oxyhydroxyapatite, brushite, and
so on. Huang et al. skipped the sintering step after electrochemical deposition of HAp
and instead used the hydrothermal method. They observed the formation of needle-
like and plate-like crystals on the Ti-6Al-4 V alloy substrate [188]. In order to have
better nucleation conditions for HAp crystals on implants, Kar et al. pre-treated Ti
implants with NaOH to increase the surface pH of Ti during electrodeposition. They
observed that samples prepared by alkali pre-treatment had greater bond strength of
25 MPa as compared with samples without alkali treatment (19 MPa) [189].

15.3.3.5 Plasma Spray Method

The plasma spray technique is another widely adopted method for coating implants
and similar substrates with HAp. It has the ability to construct sufficiently thick
and adherent bioactive HAp coatings on implants [190–192]. This method involves
spraying the precursor solutions through a thermal plasma jet, towards the substrate
to be coated. The calcium and phosphate solutions undergo thermochemical reactions
inside the plasma jet to form HAp. The HAp particles go through a series of complex
thermal changes and melt to form a molten or semi-molten state while propagating
through the plasma jet, which typically has a temperature of 10,000 K and can even
be as high as 30,000 K [193]. The plasma jet accelerates and propels the molten HAp
particles towards the substrate resulting in flattened splats that cover the substrate
surface. Candidato et al. used an aqueous solution of calcium nitrate and triethyl
phosphite as calcium and phosphate precursors to coat stainless steel substrates [194].
In some of the studies, suspensions containing HAp particles were directly injected
into the plasma jet [195, 196]. Aruna et al. compared HAp coating produced by
both solution precursor method and suspension method. They reported that although
15 Implications of Synthesis Methodology on Physicochemical … 645

both techniques produced HAp with similar crystallinity, the coating formed using
HAp suspension exhibited marginally higher biocompatibility with osteoblast-like
cells. Moreover, it also showed better corrosion and wear resistance compared to
the solution precursor method [197]. The solution precursor method of plasma spray
coating allows easier incorporation of dopant elements [198].
Livingstone et al. used the factorial design of experiments to analyse the effect
of process parameters such as current, gas flow rate, and powder feed rate on the
roughness, crystallinity, and purity of HAp coatings. They reported that high current
and powder feed rate accompanied with a low gas flow rate of spray resulted in
HAp coatings with high crystallinity [193]. Li et al. reported that the melting state
of sprayed HAp particles can be varied from minor melting, semi-molten to fully
molten state by varying the plasma power input. These melting state variations of
HAp were reflected in the deposited coatings as their morphology changed from a
porous loosed structure to a densified layer structure [199]. Candidato et al. reported
a higher coating of the substrate with HAp while using a shorter spray distance [194].
The chemical stability, i.e., the durability of the implant is one of the crucial param-
eters that determine the performance of the implant, especially for implants meant
for long-term use. In such cases, the coating of the implant with highly crystalline
HAp was thought to be stable for a long period of time due to its low dissolution
rate in physiological solutions. However, the use of highly crystalline HAp would
not result in the formation of the biological apatite layer, which is formed by local
supersaturation of calcium and phosphate ions near the implant surface. Without the
formation of the apatite layer, the implant might fail and elicit an immune response.
To avoid such a scenario, some amount of amorphous HAp is desirable as it would
provide the necessary calcium and phosphate ions to form apatite by undergoing
rapid dissolution. In this context, plasma spraying offers the formation of highly
crystalline HAp embedded in an amorphous phase. Additionally, at plasma temper-
ature, HAp is bound to undergo degradation to some extent into its more soluble
phases such as ACP, TCP, and OCP. The thickness of the HAp coat on the implant
surface needs to be in an optimal range, as very thick coatings result in its detachment
from the implant surface, while very thin layers may have poor crystallinity, and as
a result, the coating stability would be affected. Zhu et al. found that HAp coating
of 10 μm has enough adhesion with the titanium substrate in order to be stable in
the physiological medium [200]. Ji et al. fabricated a 200 μm-thick HAp coat on
Ti substrate using the plasma spray method [201]. A major drawback of the plasma
spray method is the presence of impurities resulting due to the decomposition of
HAp at high temperatures. Unabia et al. reported a significant presence of tricalcium
phosphate (TCP) along with traces of CaO [202]. Also, it produces a non-uniform
coating to implants with heterogeneous structures [203].
646 M. Quadros et al.

15.4 Conclusion

Over the past decades, various synthesis methods have been introduced for the
synthesis of HAp. These methods are broadly classified under two categories, namely
dry and wet chemical methods. Dry methods are relatively simpler and can be used
to produce HAp on a large scale; however, the poor control on HAp morphology,
batch to batch variability, and the heterogeneity in the phase composition limit their
usage for biomedical applications. On the other hand, wet chemical methods provide
better control over the physicochemical properties of HAp by tuning the reaction
parameters such as pH, temperature, calcination temperature, choice of calcium and
phosphate precursor, and solvent type. The wet chemical process of HAp synthesis
involves a number of methods, including chemical precipitation, hydrolysis, sol–gel
technique, hydrothermal, and emulsion method. The feasibility of incorporation of
surface modifiers on HAp nanoparticles during the chemical precipitation method is
very advantageous in increasing the colloidal stability and drug delivery efficacy of
HAp-based nanocarriers. Sol–gel method of synthesis is widely employed for coating
HAp on metallic implants in order to render them biocompatibility and osteointegra-
tion. Though wet chemical methods have the advantage of synthesizing nanoscale
HAp with precise control over the morphology and size, however, attaining intricate
characteristics such as crystallinity, phase purity, and stoichiometry requires consid-
erable time-consuming optimization of reaction parameters. Additionally, wide size
distribution and particles agglomeration are other limitations that make wet chemical
methods of synthesis very challenging for large-scale production. HAp synthesized
by microemulsion method has shown to offer control over size distribution with
minimum agglomerations; however, the requirement of large quantities of organic
solvents not only acts as a limitation for industrial scale-up but also stands as a
non-green process. In addition to the conventional method of synthesis, several other
methods of HAp synthesis such as biomimetic, electrodeposition, sonochemical,
and plasma spraying have acquired the attention of researchers, in particular for
bioactive coating of metallic implants with HAp. Biomimetic and electrodeposition
methods are considered to be very promising methods for implant coating as they
allow complete access to the liquid medium to reach all the surfaces of the implant,
i.e., both outer surfaces and inner surfaces at a low synthesis temperature. Overall,
the biological performance of HAp depends upon its physicochemical properties;
hence, it becomes very crucial to identify the appropriate method of synthesis with
optimized reaction parameters to achieve the biomedical success of synthesized HAp.

Acknowledgements Dr. Gunjan Verma thanks Dr. A. K. Tyagi, Associate Director, Chemistry
Group, BARC, and Dr. P. A. Hassan, Head, Nanotherapeutics and Biosensor Section, BARC, for
their constant support and encouragement. Ms. Mural Quadros thanks Mrs. Ozilia Quadros for
being a pillar of unwavering support, guidance, and motivation.
15 Implications of Synthesis Methodology on Physicochemical … 647

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Chapter 16
Synthesis and Processing
of Magnetic-Based Nanomaterials
for Biomedical Applications

Arunima Rajan, R. K. Chandunika, Femy Raju, Rashmi Joshi,

Niroj Kumar Sahu, and Raghumani Singh Ningthoujam

Abstract Recent developments in the design, synthesis, and processing of magnetic

nanomaterials have gained immense attention for various biomedical applications.
Magnetic nanomaterial-mediated therapy and diagnostic applications have opened up
new avenues for cancer therapy in terms of non-toxicity, biocompatibility, chemical
stability, size, shape, and composition. This chapter covers a detailed account of
the synthesis methods (chemical and biological) and the surface functionalization
process determining the physico-chemical properties of the nanomaterials favorable
for biomedical applications. Finally, a detailed overview of distinctive applications of
magnetic-based nanomaterials in the field of magnetic hyperthermia, photothermal
therapy, drug delivery, bioimaging and biosensing has been provided.

Keywords Synthesis · Magnetic nanomaterials · Biomedical applications ·

Magnetic hyperthermia · Drug delivery · Bioimaging · Biosensing

Abbreviations

ACMF Alternating current magnetic field‘

[bmim][BF4] 1-Butyl-3-methylimidazolium tetrafluoroborate
CL Chemiluminescence
CNT Carbon nanotube

A. Rajan · R. K. Chandunika · F. Raju · N. K. Sahu (B)

Centre for Nanotechnology Research, Vellore Institute of Technology, Vellore 632014, India
e-mail: [email protected]
A. Rajan · F. Raju
School of Advanced Sciences, Vellore Institute of Technology, Vellore 632014, India
R. Joshi · R. S. Ningthoujam (B)
Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
Homi Bhabha National Institute, Mumbai 400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 659
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_16
660 A. Rajan et al.

CPE Carbon paste electrode

c
RGD Cyclic arginine-glycine-aspartate
CRP C-reactive protein
CT Computed tomography
CTAB Cetyltrimethylammonium bromide
CV Cyclic voltammetry
DMSA Dimercaptosuccinic acid
DNA Deoxyribonucleic acid
DOTA 1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic acid
DOX Doxorubicin
DPV Differential pulse voltammetry
EC Electrochemical
EPR Enhanced permeability and retention
FDA Food and Drug Administration
FITC Fluorescein isothiocyanate
GO Graphene oxide
IONPs Iron oxide nanoparticles
IR Infrared
LOD Low limit of detection
LSPR Localized surface plasmon resonance
MF Magnetic field
MHT Magnetic hyperthermia
MNPs Magnetic Nanoparticles
MRI Magnetic resonance imaging
MWA Microwave-assisted
MWCNTs Multi-walled carbon nanotubes
NIR Near-infrared
NMR Nuclear Magnetic Resonance
NOTA 1,4,7-Triazacyclononane-N,N ,N -triacetic acid
NPs Nanoparticles
PAA Polyacrylic acid
PAA-b-PS Poly (acrylic acid)-b-polystyrene
PANI Polyaniline
PDA Polydopamine
PEG Polyethylene glycol
PEGDE Pentaethylene glycol dodecyl ether
PEI Polyethylenimine
PET Positron emission tomography
PMMA Poly(methyl methacrylate)
PS Polystyrene
PTT Photothermal therapy
PVA Polyvinyl alcohol
PVP Polyvinylpyrrolidine
QCM Quartz-crystal microbalance
SAR Specific absorption rate
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 661

SPIONs Superparamagnetic iron oxide nanoparticles

SPR Surface plasmon resonance
TEM Transmission electron microscopy
TMA Thiomalic acid
TOPSe Trioctyl phosphine selenide

16.1 Introduction

The global pervasiveness of cancer is a major health concern posing serious threats in
terms of mortality and incidence rates [1]. Nanomedicine employing efficient nano-
materials as therapeutic or diagnostic probes has been the prime focus of attention
during the past two decades in the area of cancer nanotechnology [2]. Recent advance-
ments in nanotechnology enabled the utilization of nanomaterials in two distinctive
fields of therapy and diagnosis. The development of multifunctional nanomaterial
platforms, capable of integrating therapy and diagnostics as a single entity, has been
proving its effectiveness in terms of remarkable progress in cancer research [3]. Such
nanomaterials are promising in terms of facilitating early diagnosis and delivering
effective therapy owing to their outstanding physico-chemical and biological char-
acteristics. Various organic/inorganic nanomaterials such as iron oxide [4], silica [5],
quantum dots of carbon, ZnS, [6], carbon nanotubes [7], manganese oxide [8] and
gold [9] have been used for diverse biomedical applications. Nanomaterials espe-
cially magnetic-based nanomaterials have occupied a pivotal position for targeting,
imaging and synergistic therapies for cancer. Owing to small size, easy function-
alization, ease of penetration, enhanced retention inside the targeted area, biocom-
patibility and biodegradability, magnetic nanoparticles (MNPs) or magnetic-based
nanomaterials are being extensively researched for various cancer theranostic modal-
ities such as magnetic hyperthermia, drug delivery, bioimaging and biosensing [10,
11]. The intrinsic magnetic properties and the ability to be driven by an externally
applied magnetic field make MNPs excellent materials as contrast agents for magnetic
resonance imaging (MRI) and as heating probes for thermal therapies. The ability
of MNPs for incorporating one or more cancer drugs to accumulate in the tumor
sites via the enhanced permeability and retention (EPR) effect is widely exploited
for drug delivery applications [12, 13]. Among the various MNPs, multifunctional
iron oxide nanoparticles (IONPs) still remain as the potential candidate to serve
as dual-purpose nanoplatform for clinical theranostics [14, 15]. IONPs, approved
by Food and Drug Administration (FDA), are commonly used as contrast agents for
bioimaging applications [16]. IONPs, specifically magnetite (Fe3 O4 ) and maghemite
(γ-Fe2 O3 ), and ferrites (MFe2 O4 where M = Mn2+ , Zn2+ , Co2+ ) are being exploited
for combined biomedical approaches such as image-guided drug delivery and image-
guided thermal therapy [17–19]. The functional aspects of IONPs are greatly influ-
enced by the synthesis routes for developing the MNPs with desired size, shape,
crystallinity and optimal magnetic properties including saturation magnetization
662 A. Rajan et al.

and superparamagnetism. Surface modification of nanoparticles (NPs) is crucial for

ensuring the colloidal stability of NPs. Surface-modified NPs enhance the thera-
peutic properties of bare NPs beneficial for specific targeting, imaging and ther-
apeutic purposes. Various strategies are being used for the preparation as well as
surface modification of MNPs suitable for biomedical applications. For example,
Khaledian et al. recently fabricated DOX-loaded polymer-encapsulated superpara-
magnetic IONPs for targeted co-delivery into tumor cells [20]. IONPs were prepared
by the co-precipitation method and subsequent polymerization for developing PLA–
PEG–FA co-polymer functionalized IONPs. Following this, the conjugation of DOX
(drug) on the PLA–PEG–FA IONPs (nanocarrier) was conducted via an emulsion
method. The targeted nano-system offers a synergistic chemo-thermal therapy.
Generally, MNPs of metal oxides (ferrites, hexa-ferrites, garnets and perovskites)
are used as sources of heat under AC magnetic fields (ACMF) for hyperthermia appli-
cation due to easy processing and stability in the biological microenvironment [21].
There are other sources of hyperthermia treatment using non-magnetic nanoparti-
cles such as Au, Ag, Cu and CuS through surface plasma resonance (SPR), which
is also included for comparison [22–25]. Generally, this type of treatment is called
photothermal therapy (PTT). Even, 2D materials absorb light in near-infrared (NIR)
range and can produce heat. 2D materials of carbides such as MXenes including
Ti3 C2 , Nb2 C, Ta3 C4 and Mo2 C have been reported for photothermal heating-based
hyperthermia [26]. Some of the magnetic compounds of metal carbides, borides,
nitrides and phosphides will be potential materials for hyperthermia-based treatment
under ACMF [27–30].
The present chapter presents an outline of commonly used synthesis methods to
generate monodispered highly stable MNPs with priority in terms of facile, low-
cost, highly reproducible techniques. Later, a section covering the importance of
surface modification/functionalization of NPs for enhancing the effectiveness for
specific biomedical applications has been summarized. Finally, recent progress in
the application of magnetic-based nanomaterials for several biomedical applications
such as magnetic hyperthermia, drug delivery, bioimaging and biosensors have been
addressed.

16.2 Synthesis Methods

Various synthesis routes have been employed to fabricate NPs with unique physico-
chemical characteristics such as size, shape, surface composition and stability.
Synthesis protocols have to be selected with utmost care ensuring the development of
NPs with required characteristics. Synthesis methods can be broadly categorized into
chemical (aqueous phase route and non-aqueous phase routes) and biological routes
as shown in Fig. 16.1 [31]. These belong to the bottom-up approach, where ions
or atoms are precipitated to the nanosized particles [21]. There is another method
known as the top-down approach, in which micron-sized particles are brought to
nanosized particles by grinding, ball-milling or bombarding high-energy particles
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 663

Fig. 16.1 Percentage estimation of the usage of various synthesis methods commonly employed to
produce magnetic-based nanomaterials. Reproduced with permission from DOVE Medical Press
[31]

on the target. The following section provides a brief overview of these commonly
used synthesis routes for fabricating magnetic-based nanomaterials with a specific
focus on biomedical applications.

16.2.1 Aqueous Phase Synthesis Routes

Aqueous synthesis routes are generally used to obtain hydrophilic NPs owing to the
ease of control over the thermodynamics and kinetics of the growth reactions. Major
aqueous phase synthesis routes are discussed in the following sections.

16.2.1.1 Precipitation or Co-Precipitation Method

In a chemical reaction, precipitation occurs when the ionic product is higher than
the solubility product. Precipitation of Fe(OH)3 can be obtained from an aqueous
medium of 0.05 M FeCl3 in 0.05 M HCl, as well as a solution of 0.05 M NaOH. At
room temperature, the solubility product (Ksp = [Fe3+ ][OH− ]3 ) is found to be 1.6
× 10–39 [32]. If the ionic product in the solution increases, supersaturation occurs.
The term co-precipitation is used when 2 or more metal ions are precipitated using
counter ions. Fe3 O4 MNPs can be precipitated using Fe3+ , Fe2+ ions in an alkaline
medium such as NH4 OH, NaOH and KOH [33–37].

Fe3+ (aq) + 3O H − (aq)  Fe(O H )3(solid/ pr eci pitate) (16.1)

664 A. Rajan et al.

2Fe3+ (aq) + Fe2+ (aq) + 8O H − (aq)  Fe3 O4(solid/ pr eci pitate) + 4H 2 O (16.2)

Co-precipitation is one of the most facile and extensively used methods for synthe-
sizing NPs owing to its high yield, easy reproducibility, high product purity and cost-
effectiveness [33–38]. The co-precipitation reaction products are generally insoluble
species formed under supersaturation conditions. The non-essentiality of hazardous
organic solvents, high pressure and temperature make it an eco-friendly method for
nanomaterial synthesis. This synthesis involving the addition of a mixture of metallic
ions in an alkaline solution [NaOH, KOH, NH4 OH, or N(CH3 )4 OH] at a temperature
below 100 °C was first proposed by Massart in 1981 [39]. Metal ferrite NPs by the
co-precipitation method are fabricated by mixing solutions of ferric cation [Fe(III)]
and M(II) salts (where M is a transition metal) in an alkaline solution forming parti-
cles of magnetic materials (known as precipitated particles) according to the reaction
given as follows:

2Fe3+ (aq) + M 2+ (aq) + 8O H − (aq)  M Fe2 O4(solid/ pr eci pitate) + 4H 2 O (16.3)

The processes involved in co-precipitation can be categorized into three steps: (1)
preparation of a liquid phase solution of metal ions, (2) thermal treatment (if required)
and (3) addition of a precipitating agent. The morphology, crystallinity and struc-
ture of the NPs are directly influenced by the thermal treatment, the precipitating
agent and other factors such as foreign particles or molecules or ions (reducing
or oxidizing), catalysts (homogenous and heterogenous types), types of capping
agents and pH of the medium. The processes of nucleation, growth, coarsening
and/or agglomeration occur simultaneously during a co-precipitation reaction. In
the homogeneous precipitation process when species concentration attains critical
supersaturation, rapid nucleation occurs and the diffusion of solutes to the surface on
the crystal leads to the slow growth of nuclei. Monodispersed NPs are obtained when
these two stages are ideally separated thereby avoiding nucleation during the period
of growth [40, 41]. The size, shape and structural composition of obtained NPs could
be fine-tuned by optimizing the reaction variables, viz., type of metal cation precur-
sors, alkaline agent concentration and reaction temperature. Surfactants or function-
alized polymers are used to protect the NPs from being oxidized in this protocol.
Peternele et al. synthesized Fe3 O4 and Fe2 O3 phases of IONPs via co-precipitation
using iron salts and alkali such as NaOH and NH4 OH as precipitants [42]. Trans-
mission electron microscopy (TEM) analysis suggested that NPs precipitated from
NH4 OH were more uniform than NPs precipitated from NaOH, and increasing the
reaction temperature limits the aggregation of NPs thereby reducing the size of NPs.
The mechanism and reaction pathway for synthesizing Fe3 O4 NPs through the co-
precipitation method have been proposed by Ahn et al. Formation of Fe3 O4 can occur
in two ways of nucleation, either by the (a) conversion of the akaganeite phase to
goethite to hematite to maghemite and finally magnetite or by the (b) conversion of
ferrous hydroxide to lepidocrocite to maghemite and finally magnetite. The pH of
this reaction as well as the type of precursors determine the reaction pathway for the
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 665

formation of magnetite NPs [43]. Chen et al. reported MnFe2 O4 NPs synthesized
through co-precipitation exhibiting a decrease in both Curie temperature and satura-
tion magnetization for small crystallite size particles [44]. Martina et al. employed
a co-precipitation technique to produce superparamagnetic liposomes suitable for
in vivo MRI imaging contrast agents [45]. The challenges such as tuning the size of
particles and chemical homogeneity limit the application of this method in several
circumstances.
Most of the MNPs prepared in an aqueous medium are associated with their
corresponding hydroxides which will get agglomerated due to the hydrophilic nature
as well as magnetic dipole interactions [46, 47]. Because of this, these particles
are unstable for keeping them in the ambient atmosphere for a longer duration.
It is necessary to use acetone to remove OH groups from particles. This makes
compounds stable [48]. In the case of preparation of Fe3 O4 nanoparticles, room
temperature synthesis can be performed from the Fe3+ and Fe2+ ions (mole ratio
of 2:1) in an alkaline medium (NaOH, NH4 OH). If N2 gas is passed through the
solution, the yield of MNPs can be increased [49]. Fe3 O4 (magnetite) can be converted
to γ-Fe2 O3 (maghemite) by partial oxidation, whereas the opposite reaction can
occur by partial reduction. Among iron oxides, α-Fe2 O3 antiferromagnetic phase is
thermodynamically stable. Fe3 O4 or γ-Fe2 O3 can be converted to α-Fe2 O3 partially
or fully after keeping them in an air or moisture environment. Magnetic and non-
magnetic particles in solution can be separated using a magnet.

16.2.1.2 Hydrothermal or Solvothermal Method

The hydrothermal/solvothermal synthesis technique is the process of conducting

chemical reactions in solvents, in which the solvent is heated to its critical point inside
a sealed reactor (autoclave) under autogenous pressure. This method is performed
under a temperature of 130–250 °C and a high vapor pressure of 0.3–4 MPa [50]. It
has been widely accepted as a classic method for synthesizing inorganic and metal–
organic nanomaterials. Water is employed as a solvent for the hydrothermal route
whereas other solvents such as ammonia, alcohol, ethylene glycol and glycerol are
used for solvothermal treatment. The solubility of salt precursors in hot water/other
solvents is a major factor influencing this type of crystal synthesis method. The
method is effective in making products of intermediate states, metastable states and
other novel compounds. Above the critical temperature and pressure of solvent,
many precursors that do not dissolve at normal atmosphere can be dissolved due to
change in the dielectric constant of the solvent. The dielectric constants of water at
room temperature are 78 and thus many polar salts can dissolve. Above the critical
point, water can have dielectric constants in the range of 2–10, in which less-polar
organic compounds can dissolve in water. Also, the solubility product is reduced
and precipitation occurs faster. Nucleation and growth mechanisms are different in
different temperatures and pressure in the hydrothermal or solvothermal method. In
this way, compounds of desired phase and compositions (including different sizes
and shapes of particles, metastable phase) can be prepared [51].
666 A. Rajan et al.

In the reaction mechanism, the crystallization process occurs via crystal nucleation
and subsequent growth. The ions to be nucleated are formed in the reaction solution
initially. Due to the temperature gradient along the top to bottom of the autoclave,
a driving force is produced which transports the ions toward the low-temperature
area. The process of transportation of ions continues until the solution becomes
supersaturated. When the solution becomes supersaturated, nucleation occurs and
the solute precipitates into clusters of crystals that are capable of growing to larger
sizes. The kinetics of the reaction is controlled by the solvent which modifies the
coordination of solvated species thereby inducing specific structures. Controlling
the factors such as reaction time, temperature, metal salts precursors, surfactants (if
any) and reducing agents is crucial for achieving precise control over size, shape and
crystallinity. Gyergyek et al. compared the size distribution of IONPs synthesized via
co-precipitation and hydrothermal method and found better control of size and shape
with hydrothermal condition (180 °C) [52]. Chen et al. used iron–oleate and zinc–
oleate precursors for synthesizing zinc-doped IONPs via the hydrothermal technique
for MRI applications [53]. Li et al. reported hydrothermally synthesized spherical
shaped 15 nm-sized PEI-coated IONPs for in vivo MRI of tumors [54]. However,
the synthesis of nanocrystals with size < 10 nm is found to be difficult through this
approach. Though the hydrothermal approach provides high crystalline mono-sized
NPs, the reaction kinetics of crystallization can be further accelerated when coupled
with microwaves.

16.2.1.3 Sonochemical Method

Sonochemical synthesis of NPs involves irradiating a liquid with high intensity

of ultrasonic waves (20 kHz–10 MHz) in order to generate extreme pressure and
temperature resulting in unique mechanisms and reaction pathways. Since acoustic
wavelengths are longer compared to molecular dimensions, there exists no direct
molecular-level interaction occurring between chemical species and ultrasound.
Instead, it behaves as being exposed to alternating acoustic waves subjecting the
liquid to dynamic tensile stress consequently changing the density of the liquid [55].
The ultrasonic waves break the chemical bonds by developing acoustic cavitation in
the liquid leading to the generation, growth and collapse of microbubbles in the solu-
tion. These microbubbles are generated from the pre-existing impurities and oscillate
according to the applied sound field. The bubbles grow to a certain size at the expense
of ultrasonic energy, and accumulated energy in the bubble will be released in a
very localized spot within a short time span leading to extremely high temperature
(~5000 K) and pressure (~1000 bar) which facilitate high-energy chemical reactions
[56, 57]. The heating and cooling rates are extremely fast (about 1010 K s−1 ) leading
to shock waves to the surrounding molecules of solvent or reaction. Figure 16.2
shows the schematic illustration of the development of acoustic cavitation in a liquid
irradiated with high intensity ultrasonic wave: the formation, growth and implosive
collapse followed by very fast cooling or rapid quenching [57]. This can produce free
radicals (H· and OH· ) in case of aqueous medium, which can reduce noble metal ions
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 667

Fig. 16.2 Schematic representation of the development of acoustic cavitation in liquid irradiated
with high-intensity ultrasound waves: formation, growth and implosive collapse followed by very
fast cooling or rapid quenching. Reproduced with permission from RSC publisher [57]

to metal nanoparticles. The sonication duration, power and frequency of ultrasoni-

cation significantly affect the size and shape of the obtained particles. Sonochemical
synthesis of nanomaterials can be classified as primary and secondary sonochemistry.
In primary sonochemistry, free metal atoms from volatile precursors are produced
via dissociation of bonds occurring at elevated temperatures created in the course
of bubble collapsing. These atoms could be injected into liquid phase followed by
nucleation to obtain NPs with the aid of suitable templates or stabilizing agents
existing in the solution. This requires nonvolatile solvents because additional vapor
absorbs the energy in the bubble. In secondary sonochemistry, nonvolatile precur-
sors are used and sonochemical reactions may occur even outside the collapsing
bubbles followed by diffusion into liquid phase initiating a set of reactions. Nanos-
tructured noble metals are commonly prepared by dissolving nonvolatile precursors
in a volatile solvent such as water or alcohols [57]. The radicals that could facilitate
redox reactions are generated by collapsing bubbles induced by the ultrasonic field.
For instance, Dolores et al. synthesized IONPs using ferrous–ferric salts in ethy-
lene glycol solvent at distinctive ultrasound frequencies of 581, 861 and 1141 kHz
with the equivalent acoustic power [58]. It was revealed that the generated hydroxyl
radicals oxidized Fe2+ to Fe3+ . In addition, the rate of Fe3+ generation reduced in
a linear manner with ultrasound frequency. Ultrasound waves used in the process
initiate the reactions without external reagents and mass transfer occurs at both the
microscopic and macroscopic levels. The mechanical effects generated by ultra-
sound enhance mass transfer within the medium which will further accelerate the
chemical reactions and other different processes. By tuning the ultrasound power
and frequency, better control on the size distribution of NPs can be obtained [59].
Moreover, the shape of NPs can also be controlled by this method. Monodispersed
iron oxide nanocubes of 80 nm size using iron sulfate salts have been fabricated
668 A. Rajan et al.

by Abbas et al. [60]. This high-intensity ultrasonic waves offer a facile synthesis
route for developing the NPs which are difficult to obtain using other conventional
methods. Albeit, this eco-friendly method is still associated with major challenges
such as scaling-up issues and energy efficiency.

16.2.1.4 Microemulsion Method

Amphiphiles are natural or synthetic molecules having a hydrophilic head group

(functional group such as –COOH, –SO3 , –NH2 and –NH3 ) and hydrophobic tail
group (long-chain hydrocarbons). These molecules are capable of self-assembling
to distinctive nanostructures such as micelles, emulsions, nanotubes, vesicles,
nanofibers and lamellae [61]. Such assembly is found in lipids and proteins of biolog-
ical systems. Different shapes and sizes of self-assembly can be controlled by pH,
ionic strengths, type of amphiphile molecules, temperature and dielectric constant.
In reversed micelle, there is a nanoreactor where many chemical reactions can take
place. Many NPs of metals (Ag, Au, Pt, Pd, Ni), alloys, core–shell structures and
oxides (Fe3 O4 , NiO, TiO2 , MnFe2 O4 and ZrO2 ) can be prepared which can control
nucleation as well as the growth of NPs. Oxide thin films can be prepared from
amphiphiles and respective metal ions using the Langmuir Blodgett approach.
Microemulsions, developed by Hoar and Schulman in 1943, are clear homoge-
neous solutions in which two immiscible liquids (water and oil) coexist as a single
phase due to the presence of surfactants [62]. Typically, surfactants with a hydrophilic
head and a lipophilic tail are used. Two variants of microemulsions such as direct
emulsion (oil dispersion in water) and reversed emulsion (water dispersion in oil)
can be prepared for the synthesis of MNPs based on the hydrophilic–lipophilic
balance of surfactants as well as the ratio of oil–water. Cetyltrimethylammonium
bromide (CTAB) was used as a surfactant during the initial study by Schulman and
is still the commonly used surfactant for this method. In addition to this, sodium
bis(2-ethylhexyl)sulfosuccinate, pentaethylene glycol dodecyl ether (PEGDE) and
Triton-x have also been used as surfactants. Later, in 1970 Friberg investigated the
orientation of molecules through NMR and IR studies finding that the interfacial
tension between molecules is minimized in the microemulsion and is thermody-
namically stable [63]. For the synthesis of metal particles, a microemulsion solu-
tion consisting of dissolved metal salts is mixed with a second solution consisting
of the reducing agent to form metallic particles via reduction. A reducing agent
should be stable in an aqueous solution and non-reactive to other components in the
microemulsion as it plays a major role in this process. Commonly used reducing
agents for microemulsion methods are hydrazine dihydrochloride (N2 H4 ·2HCl) or
hydrazine hydrate (N2 H4 ·H2 O). For synthesizing metal oxide NPs, this technique
is similar to co-precipitation in which the hydroxides are precipitated by the addi-
tion of a microemulsion solution diluted with an oxidizing agent to the solution
of aqueous metal ions. Another way to prepare metal oxide NPs is the formula-
tion of 2 microemulsions in different beakers: the first microemusion contains metal
ions (Mn+ ) and the second one has oxidizing agent or anions such as OH− , VO2 +
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 669

and VO3 − (from NH4 OH, NaOH, KOH, NH4 VO3 ). When both microemulsions are
mixed, there is a fusion of two microemulsions leading to an interaction between
metal ions and anions. Finally, metal oxides or metal hydroxides or metal vanadate are
formed [64]. The obtained metal hydroxides are collected by centrifugation. Metal
ferrites (MFe2 O4 where M = Fe, Mn, Co, Zn) of 10–20 nm sized NPs have been
synthesized by this method. Zereffa et al. synthesized silica-coated Fe3 O4 NPs using
the water-in-oil microemulsion technique using ferric nitrate and ferrous sulfate as
iron salts [65]. Ammonia solution has been used as an oxidizing agent with Tween-
80 (surfactant),1-butanol (co-surfactant) and n-heptane as the oil phase. Solution I
constitutes iron salts dissolved in Tween-80/butan-1-ol/n-heptane. Solution II consti-
tutes a mixture of SiO2 solution with Tween-80/butan-1-ol/n-heptanes and ammonia.
Both the solutions were mixed and stirred for 150 min under 1000 rpm at various
temperatures of 30, 50 and 80 °C. Obtained Fe3 O4 @SiO2 was rinsed with a mixture
of DI water and acetone 2–3 times for removing excess ammonia and surfactants.
Here, reactants in the aqueous solution acted as dispersed phase and 16 nm sized
NPs were obtained. In another work by Singh et al., magnetite NPs were synthesized
by the microemulsion method with particle size < 10 nm confirmed by transmission
electron microscopy studies [66]. The metal salts of ferrous and ferric ammonium
sulfate dispersed in sulphuric acid were mixed with the solution containing sodium
hydroxide (reducing agent), CTAB and Triton- × 100 as surfactants. The mixed solu-
tion was thermally treated for 30 min duration at 80 °C to obtain magnetite phase NPs.
This method facilitated the production of nanostructures of narrow size distribution
with good reproducibility. Fe3 O4 /SiO2 core–shell nanostructures of varying sizes of
31, 33, 43 and 55 nm were prepared using the water-in-oil reverse microemulsion
method in the presence of Triton-X100 surfactant [67]. A cationic polymer layer was
further conjugated to the core–shell structure and hence proved to be used as a carrier
for anionic drug and nucleic acids. However, this synthesis method requires more
stabilization and several washing procedures of the synthesized NPs prior to bioap-
plications. A hypothetical phase diagram of the microemulsion method is shown in
Fig. 16.3 [68].
Depending on the water/oil ratio (reverse micelle route), different sizes and shapes
of particles can be prepared. In order to prepare pure compounds or metals, the
surfactants, oils and water, which are associated with particles, need to be removed.
There are many ways to remove these such as warming, dissolving with other solvents
and heating at higher temperatures (say above 500 °C).

16.2.1.5 Electrochemical Method

Electrochemical synthesis is a facile, cost-effective and efficient strategy for fabri-

cating MNPs with various nanostructures such as nanospheres, nanorods and
nanosheets in which fabrication is conducted in an electrochemical cell [69]. As
the name implies, electrochemical synthesis is carried out by passing an electric
current between electrodes in the electrolyte solution. Electrochemical synthesis
takes place at an electrode–electrolyte interface, and material gets deposited on the
670 A. Rajan et al.

Fig. 16.3 Phase regions of microemulsion system. Adapted and reprinted with permission from
Elsevier Publisher [68]

electrodes as thin films. It is one of the low-temperature synthesis methods, and the
kinetics of the reaction can be controlled easily by the applied current. The choice of
electrode, electrolyte, temperature, pH and composition of electrolyte affect the elec-
trochemical process. In a typical synthesis, the reactants dissolved in the electrolyte
will get deposited on the application of current. The experimental setup requires a
potentiostat or a galvanostat and an electrochemical cell with either two or three
electrode configurations, supporting electrolytes, solvents and precursor chemicals.
The transfer of electron(s) from the electrode to the electrolyte (metal ions in the
solution) or vice versa across the electrode/solution interface takes place to bring the
chemical changes. For the synthesis of IONPs in an electrochemical cell, a sacrificial
anode (iron) produces Fe3+ /Fe2+ ions whereas the cathode generates hydroxyl anions
via electrolysis of water. Reetz et al. were the first to synthesize powdered Pd metallic
NPs of size 4.8 nm by electrochemical synthesis [70]. Aghazadeh et al. synthesized
ultra-fine-sized PVA-coated IONPs of 10 nm by tuning the applied current density
through an electrochemical method using a two-electrode electrochemical cell [71].
The setup employs two graphite anodes which were placed in between a stainless-
steel cathode as electrodes. An aqueous solution of iron salts such as ferrous chloride
and ferric nitrate was used as electrolyte. After the addition of polymer (PVA) to the
electrolyte solution, PVA was deposited on an iron oxide surface at the cathode
with a current density of 10 mA/cm2 for 30 min duration and at a temperature of
40 °C. The steel cathodes were washed using ethanol several times and deposited
NPs were scraped from the cathode surface, dispersed in ethanol, centrifuged and
dried. Fajaroh et al. employed electro-oxidation of iron in the water for synthesizing
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 671

magnetite Fe3 O4 NPs [72]. Pure iron plate and PEG solution were used as the iron
source and electrolyte, respectively. The electro-oxidation of iron takes place in the
dilute solution of PEG under DC voltage for 4 h. Monodispersed spherical-shaped
particles with diameter 62.5 nm were obtained. It was found that the size of obtained
NPs could be regulated by varying the electrochemical cell parameters, and the
method seems to be promising for the synthesis of metal ferrites. However, it has
certain disadvantages associated with the poor structural properties of the material
formed and inability to produce uniform particle shapes or sizes and the inherent
limitation to only use conducting substrates. Figure 16.4 shows a depiction of the
electrochemical synthesis of IONPs [73].
Morphology of particles (size, shape and hollowness of particles) can be regulated
using the electrochemical route. One of the advantages of this route is homogenous
electroplating of any shape of materials. Other advantages of electrochemical route
over other synthesis methods include the following: (a) non-requirement of chemical
oxidants or reductants due to the presence of precursors. The chemicals such as ions
in solution undergo electron transfer directly on the electrode surface, (b) a large
redox potential range of several volts is easily accessible by selecting an appropriate
combination of electrode materials, solvents and supporting electrolytes. Such a
large potential range of several volts involves very high energy either comparable
or more than most of chemical bonds and activation energy involved in chemical
reactions, leading to a controlled generation of highly energetic intermediates under
mild experimental conditions and (c) a high selectivity and percentage yield can be
obtained because of very precise control over potential and current.

Fig. 16.4 Depiction of electrochemical fabrication of IONPs. Adapted and reprinted with
permission from RSC Publisher [73]
672 A. Rajan et al.

16.2.1.6 Sol–Gel Method

The sol–gel method also termed as chemical solution deposition is a wet chem-
ical route which involves the hydrolysis and polycondensation of metal alkoxide
precursors resulting in gel formation (dispersion of metal oxide particles) which is
then followed by drying and thermal treatment [74]. The sol–gel method proceeds
via a series of various phases: (i) Formation of metal alkoxide or metal precursor
solution, (ii) Gelation by polycondensation or polyesterification of the solution, (iii)
Aging of the gel, (iv) Drying to remove water from the gel (very slow evaporation)
in the temperature range of 50–100 °C and (v) Decomposition of gel by slow heat
treatment up to 500 °C. Here, simultaneous oxidation and reduction occur in the
temperature range 250–450 °C. Thus, a strain developed in particles is removed
and finally, non-agglomerated fine particles in a nanosized range of metal oxide can
be prepared. With a further increase of annealing temperature, particle size can be
increased uniformly. The density of metal oxide obtained by compaction of powder
and followed by sintering is higher than that of other synthesis methods. This is
an advantage of the sol–gel route as compared to other synthesis routes. Precur-
sors can be hydrolyzed with the aid of an acid or a base and the commonly used
solvent is water. The colloidal gel can be obtained if a base is used for hydrolyzing,
and polymeric gel can be obtained if an acid is used for hydrolyzing. The reaction
occurs at room temperature and subsequent thermal treatment is required for the final
crystalline formation. The reaction mechanism for the generation of Fe3 O4 NPs via
sol–gel using iron (III) aqueous solution occurs through different stages such as the
formation of iron (2Fe3+ , Fe2+ ) alkoxides, gelation in alkaline medium and decom-
position. The obtained NPs show a narrow size distribution and are hydrophilic.
Factors such as pH, precursor ratio, temperature, kinetics and gel properties influ-
ence the synthesis method. Instead of isopropyl alcohol, some precursors like citric
acid, ethylene glycol, polyvinyl alcohol, glycerol and polyethylene glycol have also
been used [75–77]. This can make cross-linking with metal ions to form a gel, which
is of amorphous and cross-linking polymeric type. Takai et al. synthesized magnetite
NPs using ferrous–ferric chloride salts via the sol–gel method [78]. The metal salts
were dissolved in ethylene glycol and continuously stirred at 45 ºC for 3 h to obtain
a sol. The obtained sol was heated at 45 ºC until a dark colored formation occurred.
Later the gel was aged for 72 h and dried at 140 °C for 5 h and annealed at temper-
atures ranging from 200 to 400 ºC. The obtained magnetite NPs were in sizes of
2.20, 5.58 and 8.35 nm for the decomposition temperatures of 200, 300 and 400 °C,
respectively. Jacintha et al. synthesized MnFe2 O4 NPs employing natural polymers
such as wheat flour and potato flour by the sol–gel method [79]. Manganese nitrate,
ferric nitrate and sodium hydroxide are dissolved in deionized water upon stirring
for 15 min to achieve a homogeneous solution. Subsequently, the polymer solution
was added and stirred continuously at 50 °C for the formation of sol. The sol was
then thermally treated to 90 °C to form a gel followed by aging for 2 days. It was then
annealed at 600 °C to obtain MnFe2 O4 nanoparticles. Crystallite sizes of 23.12 nm
and 16.87 nm were obtained with wheat flour and potato flour, respectively. Recently,
magnetic carbon dot-based heterostructures with 20–80 nm sizes synthesized using
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 673

the sol–gel technique have exhibited 37% cell death on tumor cells (human osteosar-
coma) [80]. Recently, Li-Zn-Co-ferrite of 12 nm spherical-shaped NPs synthesized
via the sol–gel method were taken in a CNT matrix for testing toward magnetic
hyperthermia [81]. The as-prepared NPs were proven to conjugate antitumor drugs
thereby exhibiting an enhanced therapeutic performance.

16.2.1.7 Solid State Reaction Method

In the solid-state reaction method, all precursors required for the formation of metal
oxides in the form of oxides, carbonates and acetates are mixed using a pestle mortar.
The mixture is heated at a higher temperature (800–900 °C) and subsequently cooled
to room temperature. Then the powder is grounded and pellets are prepared. These
pellets are then heated at a higher temperature at 1000 °C or above. Sometimes,
intermediate grinding and palletization are required to get a proper stoichiometry
and phase. Palletization helps in the diffusion of ions and direct contact between
particles [82]. For example, when a mixture of MgO and Fe2 O3 precursors are heated,
MgFe2 O4 compound can be formed, but in-homogeneities in phase may occur (partly,
MgFe2 O4 , Fe2 O3 and MgO). Intermediate grinding, palletization and heating help
in getting a proper stoichiometry without other impurities. In some cases, an oxygen
atmosphere is provided to get a proper stoichiometry and phase. In this way, many
magnetic oxides such A1-x Bx O3 (A = La, B = Ca, Sr, Ba) and A3-x Bx Mn2 O7 are
prepared [83].

16.2.1.8 Combustion Method

In the combustion method, metal ions in the form of nitrates or oxy-nitrates as

oxidants are treated with organic compounds such as urea, citric acid, ascorbic acid
and glycine as fuel in a large capacity of a borosilicate glass beaker, and then the
mixture is heated at 300–500 °C [84, 85]. The instantaneous reaction occurs due
to a huge amount of exothermic reactions. Voluminous or porous metal oxides are
observed inside the beaker and because of this, a large capacity of borosilicate glass
beaker (2–5 L) is preferable for the preparation of 2–10 g of metal oxides. Such
exothermic reaction produces a large evolution of gases such as CO, CO2 , N2 , H2 O
and NOx . It needs to take some precautions during preparation. The amount of heat
generation can be obtained by a ratio (φ) of the net oxidizing valency of oxidants to
the net reducing valency of fuel (O/F). This ratio is an important factor in getting a
high yield of the product. Generally, a ratio of 1:1 is used.
For attaining this, metal precursors are dissolved in HNO3 and glycine followed
by the addition of citric acids or polyvinyl alcohols according to the O/F ratio. The
solution is prepared by stirring which is kept for one day. Then it is heated very
slowly up to 300–500 °C. There is a decomposition of metal–glycine complex with
an exothermic reaction. This makes fine particles of metal oxides. Then it is further
heated at 600–1000 °C to get the different sizes of particles. In this way, many
674 A. Rajan et al.

magnetic compounds such as ferrites, garnets and hexa-ferrites and A1-x Bx O3 (A =

La, B = Ca, Sr, Ba) and A3-x Bx Mn2 O7 are prepared [86–99].

16.2.2 Non-aqueous/Organic Phase Synthesis Routes

Non-aqueous/organic routes for synthesizing hydrophobic NPs are based on chemical

reactions of metal precursors which are dissolved in high boiling point solvents at a
higher temperature. Major non-aqueous synthesis routes are briefly explained in the
following sections.

16.2.2.1 Thermal Decomposition Method

Thermal decomposition route is generally employed for synthesizing hydrophobic

NPs with controlled physico-chemical attributes such as size, shape, morphology,
chemical composition, crystallinity and magnetic properties. This method involves
the decomposition of organometallic precursors in the presence of surfactants in
high boiling point organic solvents at very high temperatures (240–350 °C) in
an inert atmosphere. However, there are reports on the synthesis of nanocrystals
in different atmospheres (reducing and oxidizing atmosphere). Such decomposi-
tion occurs owing to the chemical bond breakage in metal complex through an
exothermic or endothermic or simultaneous exothermic and endothermic reaction
in an inert atmosphere preventing undesirable phase formation. Commonly used
organic solvents possessing high boiling points are phenyl ether (bp = 258 °C),
benzyl ether (bp = 298 °C), octyl ether (bp = 292 °C), 1-eicosene (bp = 151 °C),
1-hexadecane (bp = 286 °C), 1-octadecene (bp = 315 °C), hexadecanodiol (bp =
72 °C) and trioctylamine (bp = 168 °C), and surfactants used are fatty acids, oleic
acid, oleylamine (bp = 364 °C), linoleic acid (bp = 230 °C), Trioctylphosphine (TOP,
bp = 408 °C), Trioctylphosphine oxide (TOPO, bp = 408 °C) and long-chain amines.
This method is proved as one of the most effective approaches to obtain high-quality
monodispersed NPs of various materials such as metals, alloys, metal oxides, metal
chalcogenides, composites and core–shell. Maity et al. reported enhanced magnetic
properties for thermally decomposed magnetite NPs with prolonged reaction duration
(4 h) and higher temperature (330 °C) [100]. In addition, the obtained narrow-size
particle distribution was attributed either to the selective binding of surfactant (oleic
acid) to core NPs’ surface or to the synthesis route involving a solvent-free reaction
[100]. The compounds prepared by thermal decomposition in an organic solvent are
highly crystalline.
Two types of synthesis approaches used in thermal decomposition are (a) rapid/hot
injection mode and (b) direct heating mode. Rapid injection mode comprises initial
heating of reaction solution consisting of surfactants and solvents to a certain temper-
ature. Following this, a metal precursor solution is injected into the hot reaction
system for facilitating a rapid nucleation process or short burst of nucleation at
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 675

the critical saturation. The size and shape of the crystalline phase depend on injec-
tion temperature, waiting time, metal to surfactant ratio, others such as reducing or
oxidizing environment, co-surfactant, catalysts and nucleation site used in the reac-
tion [101]. Hence, the growth process of NPs could be controlled in terms of reac-
tion temperature as well as reaction duration, thereby assuring uniform growth and
monodispersed NPs. Instantaneous supersaturation occurs in the case of the hot injec-
tion method compared to direct heating mode. Hyeon et al. prepared monodispersed
crystalline γ-Fe2 O3 NPs via rapid injection thermal decomposition of iron pentacar-
bonyl [Fe(CO)5 ] in the presence of surfactants [102]. Nucleation of NPs is attained by
the rapid injection of Fe(CO)5 into the hot reaction solution (mixture of surfactant and
solvent) heated above the precursor decomposition temperature. It has been proposed
that nucleation ensuing from the thermal decomposition of iron pentacarbonyl started
at a low temperature (100 °C). On the other hand, growth resulting from the decom-
position of the iron–oleate complex takes place at an elevated temperature (300 °C).
Distinctive nucleation and growth processes assist in obtaining extreme control over
particle size as well as distribution. Bawendi and group in 1993 introduced this
hot injection process to produce monodispersed highly crystalline cadmium chalco-
genides [103]. In their work, organometallic precursors such as dimethyl cadmium
and trioctyl phosphine selenide (TOPSe) have been injected into the reaction solution
at 360 °C which induced a burst of nucleation followed by subsequent growth for
the formation of monodispersed CdSe nanocrystals. It was inferred that precursors
as well as capping agents grafted on the nanocrystal surface control both nucleation
and growth rates thereby controlling the size and shape of NPs. Efficient exchange
coupled/core–shell nanostructures beneficial for biomedical applications can also be
prepared via the hot injection method. Here, the core will be synthesized initially
followed by the injection of shell precursors into the solution in which the core is
prepared. A major benefit of this method is that it allows the preparation of multiple
shells via successive injection of shell precursors in a single pot.
The direct heating strategy of thermal decomposition route (commonly known
as thermolysis) involves the complete mixing of metal precursors, surfactants and
solvents in a certain ratio followed by slow heating at 100–360 °C depending on
the required phase and morphology of crystalline compounds [104]. Under this
high temperature, decomposition of metal precursors occurs followed by rapid burst
nucleation leading to a steady growth process to form monodispersed NPs. Usually,
organic metal precursors such as metal acetate, carbonyl and acetylacetonates are
used. Lassenberger et al. studied the mixing of organometallic precursors such as
iron pentacarbonyl (Fe(CO)5 ) in the presence of oleic acid (capping agent) and dioctyl
ether (solvent) and heating at 290 °C to form mono-sized IONPs of 3–4 nm [105].
Size and morphology can be controlled by optimizing the heating process and heating
parameters. Long-chain surfactants such as oleic acid, oleylamine and octyl phos-
phonic acid significantly affect this type of synthesis routes. Owing to the strong
coordination ability and improved thermal stability, decomposition of the formed
intermediate products during this reaction could be difficult. At a specific reaction
temperature, slow decomposition of such intermediates occurs which can poten-
tially impact the size and morphology of NPs. This method is commonly employed
676 A. Rajan et al.

for the synthesis of ferrites such as manganese ferrite (MnFe2 O4 ), nickel ferrite
(NiFe2 O4 ), cobalt ferrite (CoFe2 O4 ), magnetite (Fe3 O4 ) and their composites. Sun
et al. have reported that monodispersed metal-ferrites such as MnFe2 O4 , CoFe2 O4
and Fe3 O4 with a narrow size distribution of 3–20 nm synthesized via the high-
temperature thermal decomposition method possess greater potentials to be explored
for prospective biomedical applications [106]. Corresponding metal acetylacetonate
salts as precursors with 1,2- hexadecanediol in the presence of oleic acid and oley-
lamine have been employed for this high-temperature solution phase reaction. A
diverse technique was adopted by Park et al. to synthesize monodispersed MNPs of
the narrow size distribution of 5–22 nm using metal–oleate complex as a precursor
in varying high boiling point solvents [107]. Even though the thermal decomposition
method is capable of synthesizing highly monodispersed IONPs, the prepared NPs
are hydrophobic in nature. Due to this hydrophobicity, subsequent phase transfer and
surface modification procedures with the aid of several ligand exchange methods are
required for their effective usage for biomedical applications.
Different shapes from spherical to cuboid Fe3 O4 particles can be prepared based on
Oswald repining methods. Here, smaller-sized particles got dissolved and deposited
over larger particles. Figure 16.5 shows TEM images of monodispersed particles of
Fe3 O4 and particle size increases after addition of scarifying material of small-sized
particles into already prepared particles by the concept of the core–shell model [104].
With the further addition of scarifying material of small-sized particles, particle size
distribution is broad and sometimes, bimodal distribution occurs. With a decrease of
particle size, there is a chance of occurrence of a mixed phase of Fe3 O4 and γ-Fe2 O3 .
This is confirmed by XANES and EXAFS [108].
MNPs of metallic Fe, Co, Ni, CoNi, FePd, FePt and their alloys have been prepared
by thermal decomposition of respective metal precursors [109–112]. Sometimes,
monodispersed particles (Co, Ni, CoNi (Fig. 16.6, [109]), Au, Ag, NaYF4 :RE (RE =
rare-earths)) are prepared from the metal precursors either by the process of digestion,
Oswald ripening or a combination during thermolysis. The formation of monodis-
persed particles may not be only due to the thermal decomposition of metal precursors
(acetate, carbonyl). The precursors of metal chlorides, nitrate and oxides are used to
prepare monodispersed particles. In the case of preparation of monodispersed parti-
cles NaYF4 :RE, the source of F is a mixture of NaF or NH4 F and NaOH in methanol
and metal precursor can be of metal chloride or oxide [113–115].

16.2.2.2 Microwave-Assisted Method

The microwave-assisted method is one of the methods that can prepare materials
within a short time [116]. When suitable frequency and power are applied to the reac-
tion vessel containing reactants/precursors and solvents for a few minutes, the mate-
rials such as metals, alloys, oxides, sulfides, composites, biomaterials and non-metals
(carbon allotropes, CNTs, graphene) can be prepared. Nanometre-sized regime parti-
cles can be synthesized. Heat generation in the reaction system under the microwave
cavity is due to dielectric polarization and ionic conduction. Solvents such as water
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 677

Fig. 16.5 Core Fe3 O4 particles (heating rate of 4 °C/min): (A) TEM image, (B) HRTREM image
and (C) SAED pattern. Core–shell Fe3 O4 @ Fe3 O4 particles after adding (D) 1 mL and (E) 5 mL
of ferric oleate (1 h heating duration) and (F) 5 mL of ferric oleate (8 h heating duration). (G) Core
Fe3 O4 particles synthesized with a heating rate of 1.3 °C per min. Graphical illustration of sphere to
cube shape transformation of particles in the core–shell model (Ostwald ripening mechanism): (H1)
slightly spherical oleate-coated particle along with magnetization axes of face-centered cube (Fe3 O4
unit cell), (H2) particles in ferric oleate medium, (H3) formation of Fe3 O4 small particles/cluster
which surrounds a larger particle, (H4) faster growth/deposition along < 111 > direction as compared
to < 100 > or < 220 > direction, (H5) cube-shaped particle formation. Reproduced with permission
from Springer Nature Publisher [104]

and ethylene glycol are used to get uniform heating. This is different from conven-
tional heating from heat sources. The role of solvents, reaction vessels, additives, MW
frequencies and powers to achieve microwave synthesis are important parameters.
In this method, uniform heating over particles can be obtained.
Compared to conventional heating techniques for NP synthesis, microwave-
assisted (MWA) synthesis has been extremely effective in terms of higher yield,
reduced particle size and dissolution enhancement. Here, microwaves (1 mm–1 m
range of wavelengths and frequency of 300 MHz–300 GHz) are used as heat sources
to stimulate the reaction for NP synthesis. Microwaves are capable of inducing
nucleation or growth of NPs. This method is generally executed in combination
with thermal decomposition method and hence this is considered as a non-aqueous
route. However, microwaves can also be employed to accelerate aqueous-based
678 A. Rajan et al.

Fig. 16.6 a Bright-field TEM image of Co50 Ni50 NPs and b its particle size distribution.
Reproduced with permission from Elsevier Publisher [109]

approaches such as hydro/solvothermal and sol–gel. MWA offers the advantages

of facileness, rapid heating, higher reaction rate, inexpensiveness, energy efficiency
and eco-friendliness. Due to higher heating rates and precise heating control, this
method produces highly crystalline uniform NPs with monodispersed size distribu-
tion. MWA uses a specially designed microwave synthesis reactor for controlling the
reaction temperature, stirring rate and pressure inside the reactor. MWA works on
the principle of exciting a material to induce dipole alignment by microwave electro-
magnetic waves. The heating effect of microwave occurs due to the interaction of the
electric field component of a microwave with charged particles in the material via
both conduction and polarization. Microwave irradiation directly activates molecules
possessing a dipole (dipolar polarization mechanism) or ionic (ionic conduction
mechanism) leading to a sudden upsurge in temperature. In general, microwaves
interact with material or solvent with polar molecules. Nature and polarity of solvents
play crucial roles in MWA for the formation of inorganic NPs. The polarity of the
solvent regulates the reaction rate. The higher the solvent polarity, the higher will be
the potentiality to couple with the microwaves for an increased temperature and reac-
tion rate. Water is a widely used solvent for MWA synthesis of inorganic NPs owing to
its polarity as well as the ability to absorb microwaves. Shorter reaction duration and
uniform heat distribution arising from instantaneous interaction of microwaves with
the material are major advantages over other methods. IONPs have been reported to
be effectively synthesized by the MWA method [117]. Hu et al. synthesized monodis-
persed Fe3 O4 NPs (∼6 nm) using Fe(acac)3 and 1,2-hexadecanediol in dibenzyl ether
in the presence of oleic acid and [bmim][BF4] via MWA heating instantaneously at
220 °C for 5 min followed by 250 °C for another 5 min [118]. Komarneri et al. synthe-
sized magnetite NPs with sizes ranging from 24 to 1000 nm exhibiting magnetization
in the range of 59–89 emu/g under MWA heating by varying temperature (80–150 °C)
and time (1–16 min). It was also inferred that the crystallinity of NPs was increased
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 679

as the temperature was raised by microwave heating [119]. In another study, simulta-
neous stirring and MWA heating reduced ferric chloride salt in the presence of dextran
(surfactant) and hydrazine (reducing agent) to generate FITC–dextran-coated IONPs.
Smaller-sized NPs of 21.5 nm size with excellent reproducibility were synthesized
which exhibited improved response for applications such as MRI positive contrast
agents and as optical probes (fluorescent imaging) [120]. In spite of the fact that
the penetration depth of the microwave is confined, MWA is capable of achieving a
higher yield with enhanced efficiency.

16.2.3 Biological Synthesis Routes

Biomineralization, in which biological systems produce finite size and shape-

controlled solid inorganic materials, has rectified several problems associated with
the conventional synthesis routes. Specific uptake of elements by the living organism
from the environment results in developing highly ordered inorganic materials in
the size regime of nanometeres to centimeters. Bio-reducing agents such as plant
extracts, algae and bacteria render biological routes facile, inexpensive and eco-
friendly. Among the different chemical synthesis routes, biological methods seem
to be superior due to the absence of the usage of virulent materials for any adverse
effects. Ferromagnetic materials have been reported to be biomineralized by a wide
range of organisms such as insects, algae and birds [121]. Various bio-inspired nano-
materials such as liposomes, lipid NPs, bio-synthesized metal NPs, viral NPs and
protein NPs have garnered immense attraction in cancer theranostics [122–127]. Bio-
inspired NP mimicking natural elements in the body can be employed as an alternative
biocompatible drug delivery system in cancer theranostics. Nanomaterial formation
by the living systems is usually carried out under mild conditions supplied from
the specific organelle which mediates the environment for nanomaterial growth. For
instance, magnetotactic bacteria produce magnetite NPs termed as magnetosomes in
a controlled manner with well-defined size and shapes. Magnetotactic bacteria use
Earth’s magnetic field for alignment and migration [128]. The bacteria derive the NPs
from a specially isolated protein present in their bodies via intra/extracellular miner-
alization processes. These naturally synthesized NPs are characterized by chain-like
structures possessing good crystallinity and better biocompatibility, advantageous
for homogeneous distribution in tumors capable of producing a large amount of heat
required for cancer therapies [129]. In addition to these applications, these types
of NPs are proved to be suitable for efficient drug delivery and imaging applica-
tions. Zhou et al. prepared 16 nm-sized mesoporous magnetite NPs using yeast cells
as templates [130]. Biologically synthesized multifunctional NPs with noble metal
centers functionalized with various therapeutic and imaging agents possess improved
theranostic activities against cancer [129]. Generally, the formation process of bio-
inspired theranostic agents involves (a) screening of plant extracts for the synthesis
of NPs, (b) optimization of physico-chemical parameters employed during biosyn-
thesis, (c) conjugating with theranostic agents and (d) finally characterization of
680 A. Rajan et al.

nanocarriers using various analytical methods. Though this method is eco-friendly, a

substantially slower rate of reaction kinetics limits the synthesis of iron oxide-based
NPs. However, a positive outlook for bio-synthesized NPs may open up new horizons
in the near future of cancer theranostics.
Recently, it is reported that MNPs of Fe3 O4 and γ-Fe2 O3 have been formed in
cancer cells [131]. It is due to the generation of reactive oxygen species (H2 O2 ) and the
involvement of the glycolytic pathway in the cancer cells as compared to the normal
cells. In vitro study confirms the significant increase of Fe and Zn concentrations in
cancer cells after treatment with FeCl2 and Zn gluconate. Under AC magnetic field,
hyperthermia temperature can be achieved.

16.3 Surface Modification and Ligand Exchange Method

Surface modification to make particles water-dispersible can be done for biomedical

applications. Two types of particles can be considered as follows.
• Bare particles.
• Particles having capping ligands.

In the case of bare particles, capping ligands (L) such as citric acids, oleic acid,
dextran, PEG-diacids, glutathiol and chitin can be added to the bare particles (NPs)
(mole ratio of L:NPs = 1:1, 2:1, 3:1,…) [64, 88, 91, 95, 132–139]. Water is used as a
solvent for proper interaction at different pH = 5, 7, 8. Mixing can be done for 10–36 h
under constant rotation. Then centrifugation will be done so that excess supernatant
is removed. In this way, bare NPs become properly surface-functionalized. Chemical
binding between the surface of particles and ligands can be investigated by many
techniques such FTIR and TG–DTA. The use of proper ligands having long-chain
hydrocarbons reduces agglomeration among particles.
In the case of particles having capping ligands, it needs to see whether particles
are water-dispersible as well as biocompatible or not up to 250 μg/ml or beyond.
In the case of hydrophobic ligands such as oleic acid, olylamine and linoleic acid,
particles will not be dispersible [104, 132]. To make water dispersible, the following
strategies can be done: (i) Ligand exchanges with hydrophilic ligands such as citric
acid, PEG diacids and glutathiol, (ii) Substitution reaction at long-chain hydrocarbon
molecule, (iii) Breaking of bonds at long-chain hydrocarbon molecule, (iv) Addition
reaction at double bond containing molecule, etc. In the case of hydrophilic ligands,
but not biocompatible, it needs to exchange with biocompatible ligands. For example,
CTAB-coated NPs are highly toxic, but by exchanging CTAB with biocompatible
ligands such as citric acid and PEG, particles become water-dispersible as well as
biocompatible. After proper surface functionalization, hydrodynamic radius needs
to be investigated using DLS and surface charge using zeta potentials. The hydrody-
namic size should not be more than 500 nm for biological applications. Zeta potential
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 681

should not be very high (< 5 mV). Otherwise, particles will affect other surrounding
environment in blood and cells.
To get efficient internalization of nanoparticles in cells, the surface of particles
should be partly hydrophobic as well as partly hydrophilic in nature, since layers of
cells have hydrophobic lipids. To make particles targeted to cells, other molecules
such as folic acids, iRGD peptides and glucose need to be added on the surface of the
particles [134]. Such molecules are overexpressed in such cells. To track nanopar-
ticles in the whole body, extra molecules or nanoparticles or radioisotopes need
to be added tover the surface of he nanoparticles. Sometimes, if drug molecules are
required to deliver to the target cells, it requires loading of drug molecules efficiently,
followed by the release of drug molecules by electrostatic forces or hyperthermia
temperature or pH response. Carrier nanoparticles such as mesoporous, liposomes,
micelles, hollow Au and carbon nanotubes have been used.
Bare NPs within the biological medium have a tendency to agglomerate for
reducing their large surface area to volume ratio and to get oxidized due to their
high chemical activity. Thus, the stability of NPs should be ensured during thera-
peutical applications for effective outcomes. Moreover, NPs when injected into the
bloodstream quickly follow opsonization (binding of plasma proteins) which dete-
riorates their functionality. Interactions with proteins in the biological media cover
the NP surface forming a protein corona which changes the transport as well as the
biodistribution properties of the particles. Hence to overcome these issues, surface
modifications are performed on NPs by either coating using biocompatibile poly-
meric or non-polymeric materials or conjugating using biomolecules. Coating with
effective surfactants not only prevents the NPs from aggregation but also modifies
the surface chemistry of NPs beneficial for interactions with proteins, cells or tissues
within the biological media. This coating layer can also provide colloidal stability
thereby acting as a pathway between particle and target site on cells and can mini-
mize direct exposure to the biological environment. Surface-modified NPs can further
assist in improving cell proliferation and viability, cellular uptake, target specificity
and preventing opsonization prior to in vitro/in vivo/clinical applications. In the
case of magnetic nanostructures, coatings minimize the exchange coupling effect
and short-range dipolar interactions between the particles. Biocompatible stabilizers
such as PEG and its derivatives are commonly used as effective coatings to form a
protective shield around the NPs [140, 141]. Moreover, surface modification with
suitable biocompatible materials is important in order to obtain monodispersed nano-
sized particles and stable ferro fluids advantageous for magnetic-based theranostics.
These coatings on the surface of NPs facilitate proper binding to the surface receptors
at the diseased area. Owing to their nanoscale size and physico-chemical properties,
surface-modified NPs can be employed as probes and magnetic delivery vectors
appropriate for theranostic applications [15, 142]. In order to prevent opsonization,
to increase the ability to evade the reticuloendothelial system and to favor biodis-
tribution and bioelimination, the suitable coating and its anchoring at its surface
have to be tailored and the average hydrodynamic size should be within 10–100 nm
size for high blood circulation times which is suitable for in vivo delivery. Poly-
mers such as polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyethylenimine
682 A. Rajan et al.

(PEI), polyvinylpyrrolidine (PVP), natural surfactants such as dextran, chitosan,

gelatin, ethyl cellulose, albumin, starch, lipids, proteins, dendrimers, polyacry-
lamide, polysaccharides, bisphosphonates and aminosilane have been used for
surface modification of NPs to target tumor cells [143–145]. Interaction of MNPs
with cells such as adhesion and internalization varies according to the coatings
applied. In addition, surfactants such as sodium oleate, cetyl trimethyl ammonium
bromide (CTAB), sodium carboxymethylcellulose and dodecylamine are also used
for aqueous synthesis routes to enhance the dispersibility of NPs [146, 147]. Surface
engineering using antibodies, aptamers, peptides and small molecules allows to
specifically target different receptors overexpressed on cells [148].
Surface modification can be accomplished during the synthesis or post-synthesis
of NPs through physical or chemical adsorption on the particle surface, chemical
grafting or ligand exchange. Surface modification along with nucleation and growth
processes during the synthesis (in situ) has a profound influence on NPs’ crystal struc-
ture and morphology. Post-synthesis surface modification can yield core–shell nanos-
tructures using inorganic materials such as gold, silica and organic dye molecules
[149]. These coatings render certain additional beneficial properties to the NPs such
as plasmonic features of gold and ensure protection from the biological medium. For
instance, a thin gold layer modified on the surface of IONPs dissipates more heat as
compared to bare IONPs, beneficial for thermal therapy applications [150].
The process of surface modification follows either non-covalent or covalent
approaches. The non-covalent approach refers to a physical absorption phenomenon
in which ligand adsorption occurs on NPs’ surface through non-covalent forces such
as electrostatic/hydrogen bonding/hydrophobic interactions. One of the examples of
this type of non-covalent surface modification is steric stabilization in which poly-
mers are used as capping agents/surfactants to produce monodispersed NPs. The
polymer layer bonded on to the NP surface acts as a diffusion barrier to the growing
species leading to diffusion-limited nuclei growth. This diffusion-limited growth
could suppress the size distribution of the initial nuclei resulting in monodispersed
NPs. Polymers not only stabilize individual NPs but also inhibit agglomeration due
to steric repulsive forces between particles maintaining the NP dispersion stable.
Moreover, polymers yield high-density functional groups which could be derivatized
afterwards with suitable ligands/biomolecules for bioconjugation.
Covalent approaches based on the formation of covalent bonds provide the advan-
tages of robust linkage and coating stability. In this approach, organic/inorganic
surfactants get attached to the surface of NPs via end functional groups either by
chemisorption or covalent bonding. This protective layer facilitates further function-
alization with specific binding agents or ligands or various drugs or functional groups.
For instance, surface functionalization performed on water-dispersible Fe3 O4 NPs
by conjugating with glycine and thereby cross-linking with carboxyl groups to form
carboxyl-decorated Fe3 O4 has shown to be used for thermal therapy as well as for
diagnostic applications [151]. Biocompatible coatings possessing varying end func-
tional groups such as –OH, –NH2 and –COOH have been exploited generally for
the covalent approach. Mahdavi et al. demonstrated that oleic acid gets coated on
magnetite via chemisorption, attributed to the carboxylic group (COO–) present in
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 683

the oleic acid molecules [152]. Suitable surfactants such as polymers/ligands to get
binded should be selected appropriately depending on core material characteristics.
Coating/surface functionalization of NPs is performed to ensure physical stability
and linkage to specific molecules prior to in vivo applications. A schematic represen-
tation of various precursor salts and coating materials/biological molecules used for
different synthesis and surface functionalization of MNP biomedical applications is
shown in Fig. 16.7 [153].
For the utilization of magnetic colloids for biological applications, MNPs need
to be water-dispersible. Otherwise, the MNPs must undergo a prior ligand exchange
process to make the MNPs water-dispersible. The ligand exchange method is an
effective surface engineering procedure based on the phase transfer of MNPs. The
selected ligand replaces the coating layer on the surface of NPs ensuring the colloidal
stability of MNPs achieved during surface functionalization. The ligand to be used
should possess equal or higher affinity compared to the coating material toward the
NPs for a full or partial replacement. Hydrophobic surfactants on the surface of NPs
(synthesized via non-aqueous approaches) could be replaced with hydrophilic ligands
of certain small molecules such as tetramethylammonium 11-aminoundecanoate to
form an aqueous phase before injecting into a biological medium. Ligand exchange
performed in a non-aqueous phase of a gold cluster containing triphenylphosphine
was initially reported by Schmid et al. [154]. Similarly, Yu et al. executed the
phase transfer of oleic acid-coated Fe3 O4 NPs via ligand exchange with the aid of
an amphiphilic co-polymer of poly(maleic anhydride-alt-1-octadecene) and PEG.
The co-polymer constitutes side chain each of hydrophobic C16 alkane as well
as hydrophilic PEG groups. The hydrophobic C16 side chain coordinates with the
alkane groups of oleic acid via hydrophobic–hydrophobic interactions whereas the
hydrophilic PEG chains being exposed outside make the NPs hydrophilic. Hence,
the free carboxylic groups present in PEG could be further used for bioconjugation
[155]. Later, Mao et al. reported aqueous phase transformation of co-polymer (poly-
lactide and PEG)-coated gold (Au) NPs via the hydrogen bond ligand exchange

Fig. 16.7 Schematic depicting synthesis and surface modification/functionalization of MNPs.

Adapted and reprinted with permission from MDPI, Basel, Switzerland [153]
684 A. Rajan et al.

selection process. During this process, NPs were treated with NaOH in the pres-
ence of citrate at 40 °C for the degradation of polylactide. During this treatment,
the hydrogen bond formed between PEG brushes and citrate drives the Au NPs to
cross the hydrophilic–hydrophobic interface after the complete degradation of the
polylactide brushes which transfers the NPs to the aqueous phase [156]. A two-step
ligand exchange process has been performed for strongly water-dispersed MNPs for
biomedical applications by Hatakeyama et al. Thiomalic acid (TMA) was selected
as a temporary ligand which is soluble in both oil and water to remove fatty acids.
Later, citric acids have been used as secondary ligands for TMA-exchanged MNPs
to remove TMA from the surface of MNPs to obtain highly water-dispersed MNPs
[157]. Grafting the NPs’ surface with active targeting ligands has been demon-
strated to improve tumor targeting and retention of the NPs. In a recent work, Hou
et al. employed a block co-polymer named poly (acrylic acid)-b-polystyrene (PAA-
b-PS) for surface grafting on oleic acid-coated Fe3 O4 NPs for ligand exchange.
The carboxyl group present in PAA polymer (hydrophilic) binds to the surface of
IONPs replacing monovalent oleic acid molecules through multivalent coordina-
tion whereas the PS units provide dispersibility in organic solvents. By adjusting
the pH of the aqueous phase, the oil/water interfacial interaction has changed and
resulted in the deformation of NPs readily to be used as T2 -weighted MRI [158]. The
ligand exchange process should ensure that the coating agents should be displaced
completely or should not interfere with the adsorption on the surface of NPs.
Monodispersed Fe3 O4 nanoparticles coated with oleic acids are hydrophobic
in nature. After proper surface functionalization, particles can become water
dispersible. A simple representation of surface functionalization to nanoparticles has
been carried out using methyl oleate as nanoparticles coated with oleate. Figure 16.8
shows the reaction pathways of (a) addition of thioglycolic acid to the double bond
of methyl oleate, (b) addition of aspartic acid to oxirane derivatives of methyl oleate
and (c) synthesis of aminophosphonate from aldehyde obtained from methyl oleate
[104]. These are characterized by FTIR and NMR spectroscopy.

16.4 Biomedical Applications of Nanomaterials

The potentiality of nanomaterials in invading the bloodstream for specific targeting

has undergone the most investigation recently in the field of cancer nanomedicine.
Nanomaterial-mediated biomedical applications for cancer are mostly oriented
toward imaging, sensing, drug delivery and thermal therapies. Figure 16.9 depicts
a schematic illustration of functional nanomaterials used for various biomedical
applications [159]. The concept of using multifunctional magnetic-based nanoma-
terials opens up improved therapeutic efficacy with minimal side effects ensuring
safe execution for clinical use. This section will explain the therapeutic and diag-
nostic nanomaterials capable of killing tumor cells and the possible mechanisms of
nanomaterial-mediated thermal therapy.
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 685

Fig. 16.8 The reaction pathways of (a) addition of thioglycolic acid to the double bond of methyl
oleate, (b) addition of aspartic acid to oxirane derivatives of methyl oleate and (c) synthesis of
aminophosphonate from aldehyde obtained from methyl oleate

16.4.1 Magnetic Nanomaterial-Based Thermal Therapy

Thermal therapy using nanomaterials as heat sources has paved the way for promising
trends in thermotherapeutical biomedical applications. These nanomaterials should
be (a) in the size regime of 10–100 nm for longer circulating times in the bloodstream
and effective nanoparticle incorporation into cells, (b) dispersible in biocompatible
liquids for easy penetration into the body, (c) with minimum side effects on the
normal behavior of the host biosystem in the absence of any external stimulus and
(d) dissipating heat in an efficient manner when externally excited [160, 161]. This
section provides an account of the nanomaterials used for thermal therapy empha-
sizing magnetic hyperthermia and photothermal therapy, both being a promising
therapeutic tool to combat cancer. Thermal therapy, termed as hyperthermia, exposes
cancer cells to a higher temperature of 41–46 °C for a specified time duration leading
to effective cellular destruction. Since cancer cells are highly susceptible to heat than
normal cells, this thermal therapy by elevating the temperature in the tumor area
686 A. Rajan et al.

Fig. 16.9 Functional nanomaterials used for various biomedical applications. Adapted and
reprinted with permission from Elsevier Publisher [159]

promotes cellular death via denaturation of intracellular protein and/or via disrup-
tion of the cell membrane. Generation of intracellular heat occurs within tumor sites
by the introduction of suitable NPs (magnetic/plasmonic particles) using either an
alternating magnetic field or electromagnetic wave (photon). The primary mecha-
nism of nanomaterial-mediated thermal therapy is based on the heat dissipation via
absorption of infrared light (photothermal therapy, PTT) or via magnetically induced
heating (magnetic hyperthermia). Both modes have exhibited improved therapeutic
efficiency in in vivo and a few clinical trials. Generally, thermal therapy possesses
trivial side effects in comparison with conventional chemo/radiotherapy.
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 687

16.4.1.1 Magnetic Hyperthermia (MHT)

Biocompatible MNP-mediated MHT is an innovative, efficient and safer thermother-

apeutic approach for cancer. MHT is an effective tool for therapeutic temperature
enhancement employing MNPs under an external AC magnetic field (ACMF). Such
NPs, also termed as tumor-specified nanoheaters, when subjected to ACMF, dissi-
pate heat to the specific tumor tissues for controlled homogeneous heating without
affecting normal cells which makes MHT distinct from other conventional cancer
modalities. This makes localized heating to tumor. The use of MNPs was initially
proposed by Gilchrist in 1957 [162]. Maghemite ferromagnetic particles of particle
sizes varying from 20 to 100 nm were utilized for heating cancer tissues exposed to
an external alternating current magnetic field with a frequency of 1.2 MHz. Applied
magnetic field parameters used for MHT to achieve the therapeutic limit should be
in the Brezovich limit (product of magnetic field amplitude and frequency < 5 × 10
9
Am−1 s−1 ) [163]. In the history of thermal therapies, MHT has gained spectacular
success due to its potential applications in medicine. MHT, assuring specificity to
the target area, improved colloidal stability of MNPs and minimal adverse effects
to the surrounding healthy tissues, has garnered recognition as a prospective cancer
therapy [160, 161]. MHT came out with successful results when experimented in
animal tumor models which led to the pathway for future clinical trials [164, 165].
Superparamagnetic NPs are highly exploited in MHT owing to their size as well as the
innate property of substantial magnetization value and magnetic susceptibility under
ACMF and nullifying its magnetization completely upon field removal. Such NPs
prevent aggregation and avoid detrimental conditions resulting in thrombus forma-
tion [166]. Moreover, these NPs are able to generate heat via relaxation processes at
physiologically relevant magnetic fields.
In general, heat generation occurs in magnetic materials under an ACMF that can
be categorized into (1) eddy current loss, (2) hysteresis loss and (3) susceptibility
loss (Nèel relaxation loss and Brownian relaxation loss). Eddy current loss can be
neglected in the MHT context since such losses occur in bulk magnetic materials.
Hysteresis loss results from the delay of a magnetic material where the magnetic
moment at some frequency fails to retrace its path instantaneously with an ACMF
resulting in hysteresis loops. Hysteresis loop due to this irreversible magnetization
process thus results in heat losses. Hysteresis heat loss is considered to be the basis
of heat dissipation for ferromagnetic particles. Optimal heat loss can be calculated
from the area of such hysteresis loops. Current research focuses on single domain
superparamagnetic NPs for MHT in which the heat dissipation is due to suscep-
tibility losses such as Nèel relaxation loss and Brownian relaxation loss as well
as hysteresis loss. Nèel relaxation (internal rotation) induced by an external ACMF
occurs due to the oscillations of the magnetic moments thereby changing the moment
direction keeping the physical orientation of particles fixed whereas Brownian relax-
ation (external rotation) is caused by the physical rotation of the particles itself in a
medium they are placed. The former mechanism primarily depends on the magnetic
anisotropy energy of MNPs whereas the latter is based on the local environment
such as viscosity of the medium in which MNPs are dispersed. These internal and
688 A. Rajan et al.

external rotations of particles can lead to a phase lag between the applied magnetic
field and the magnetic moment direction resulting in heat loss. Brownian relaxation
has a small contribution in a viscous medium. The amount of heat dissipated is eval-
uated in terms of specific absorption rate (SAR), and it is expressed in W g−1 of
MNPs. The larger the amount of heat generated by the MNPs, the larger will be the
SAR value. The power dissipation rate of MNPs is a function of MNP size, shape,
composition, magnetic interactions and applied magnetic field parameters. Eluci-
dating and optimizing these variables are vital for future clinical applications. The
success of MHT application underlies on developing biocompatible and superpara-
magnetic NPs with suitably functionalized surfaces exhibiting the highest saturation
magnetization thereby assuring effective heating under an oscillating magnetic field.
Generally, Nèel’s spin relaxation of superparamagnetic NPs takes 10–9 –10–10 s
[40, 160]. It is to be noted that a 200–300 kHz frequency is used in MHT. The experi-
mental time window will be 5–3 × 10–6 s. During the time window, the net magnetic
moment of superparamagnetic particles can be measured, and thus hysteresis loss is
associated in superparamagnetic particles under 200–300 kHz frequency and 100–
300 magnetic field or 100–400 A current. The experimental time window for VSM
or SQUID is 1 s–60 s that is not able to see a magnetic moment of superparamag-
netic particles. Only zero moment can be seen due to fast relaxation from + z to – z
direction within 10–9 –10–10 s.
Brownian relaxation (τB ) of particles in a fluid having the dynamic viscosity (η)
at absolute temperature (T) can be represented by Eq. (16.4).

4π ηrh 3
τB = (16.4)
kB T

rh is the hydrodynamic radius of the particle. τB varies from μs to ms and even to

hours depending on hydrodynamic radius and temperature.
Nèel relaxation (TN ) of superparamagnetic particles is represented by Eq. (16.5).

τ N = τo eE/k B T (16.5)

τo is 10–9 s, E is the anisotropic energy barrier (the product of anisotropic energy

constant (K) and volume (V) of particle = KV), k B is Boltzmann’s constant and T is
absolute temperature. Equation (16.2) suggests that Nèel’s relaxation is fast for the
smaller nanoparticles.
Hysteresis loss of magnetic particles in ACMF is represented by Eq. (16.6).

Area under curve = f Md H (16.6)

f is the frequency of the AC magnetic field, M is magnetization and H is the applied

magnetic field. The ratio of magnetization (M) to the applied magnetic field (H) gives
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 689

magnetic susceptibility (χ), which represents the type of magnetic materials (diamag-
netic, paramagnetic, antiferromagnetic and ferromagnetic particles). For diamagnetic
particles, χ has the negative value, where the other remaining particles have a positive
value. In the AC magnetic field, χ is represented by Eq. (16.7).

χ = χ  + iχ  (16.7)

where χ/ is a real part of susceptibility and χ// is an imaginary part of susceptibility,

which is represented by Eq. (16.8).
ωτ
χ  =   (16.8)
1 + ωτ 2

τ is the total relaxation contributed by Brownian (τ B ) and Nèel’s relaxations (τ N ).

According to Faraday’s and Lenz’s laws, eddy current loss (ED) from conducting
materials having μ (the permeability of a material), d (the diameter of the particle)
and ρ (resistivity of the material) is represented by Eq. (16.9).

(μπ d f H0 )2
ED = (16.9)
20ρ

Total heat/power dissipation from particles is represented by Eq. (16.10).

P = μ0 π χ  f H02 (16.10)

μ0 is the permeability of free space.

The specific absorption rate (SAR) in ACMF is represented by Eq. (16.11) and
its unit is W g−1 .

T 1
S AR = c (16.11)
t m magn

T/t is obtained from the slope of the time-dependent temperature curve at the
initial time, c is the specific heat capacity of combined superparamagnetic particles
and the solvent and mmagn is calculated by the ratio of the amount of MNPs or Fe per
total amount of MNPs or Fe and solvent.
In addition to magnetite (Fe3 O4 ), ferrites such as CoFe2 O4 , NiFe2 O4 , ZnFe2 O4 ,
CuFe2 O4 , MnFe2 O4 MgFe2 O4 and alloys such as FePt and NiCu have been used
for MHT [167–172]. In addition, anisotropic magnetic Janus nanostructures such as
Fe3 O4 –Pd and carbon-coated Fe–Co exhibited excellent magneto-thermal properties
[173, 174]. Pure metals (Fe, Co, Ni) are not suitable for MHT applications due to their
extreme sensitivity to oxidation and toxicity. However, iron oxides such as magnetite
690 A. Rajan et al.

and maghemite less prone to oxidation can provide a stable magnetic response and
are biocompatible being advantageous for MHT applications.
Studies reported that heat induction can be enhanced through proper synthesis
and surface modification strategy. The sol–gel route has been employed for reducing
Ni and Cu to produce Ni–Cu NPs for self-regulating MHT [175]. It has been
demonstrated that 50–87 nm sized spherical-shaped Ni–Cu NPs dissipate SAR in
the range of 6–80 W/g. Wang et al. PVP-functionalized Fe3 O4 nanotubes with an
outer diameter of 200 ± 20 nm and length of 400 ± 20 nm synthesized through
hydrothermal synthesis that exhibited highest SAR of 5050 W/g beneficial for
MHT [176]. Various superparamagnetic core–shell nanostructures have been synthe-
sized to achieve higher SAR values. For instance, Zn0.4 Co0.6 Fe2 O4 as core and
Zn0.4 Mn0.6 Fe2 O4 as shell to form a core–shell structure synthesized via thermal
decomposition method exhibited an enhanced SAR of 3866 W/g which is 1.7 times
greater than the SAR obtained from individual counterparts [177]. Xie et al. reported
IONPs synthesized via co-precipitation method followed by conjugating the surface
of NPs with polymers such as PMMA and PAA constituting novel Janus struc-
ture (PMMA/Fe3 O4 /PAA) [178]. These NPs were tested for in vitro MHT on 4T1
breast cancer cells under ACMF (445 kHz, 35A) and exhibited ~ 35% cell inhibi-
tion whereas DOX-loaded Janus NPs under ACMF showed a more pronounced cell
inhibition rate of ~ 78%. In addition, in vivo MHT demonstrated the improved anti-
tumor effect in DOX-loaded Janus NPs suggesting the effectiveness of synergistic
chemo-thermal therapy. Polycaprolactone-coated superparamagnetic IONPs synthe-
sized using a single precursor (ferrous chloride) have shown 60% cell death during
in vitro MHT when treated on HepG2 human cancer cells upon ACMF [179]. The
current research direction is focused toward MHT conjunction with other cancer ther-
apies such as photothermal therapy (PTT) or chemotherapy to achieve a synergistic
therapeutic effect.
SAR values of Fe3 O4 , PEG-coated Fe3 O4 and Oleic acid (OA)-coated Fe3 O4 are
estimated to be 40.52, 31.39 and 25.5 W/g, respectively [180]. Figure 16.10 shows the
heat generation from these particles at different applied currents [180]. The magnetic
field (H) at 100, 200, 300, 400, 500 and 600 A correspond to 83.8, 167.6, 251.4,
335.2, 419 and 502.8 Oe, respectively. With the increase of magnetic field, the heat
generation increases. This suggests that the role of hysteresis loss is important in
heat generation.
Fe3 O4 NPs coated with OA exhibit internalization with cancer cells (WEHI 164
cells), and more killing of cancer cells through apoptosis under ACMF is observed
and this could be seen from confocal microscopy images (Fig. 16.11) [132].
In vivo study provides the decrease of tumor size with respect to control in BALB/c
mice (Fig. 16.12) [181]. A decrease in tumor size can be seen from a decrease in
luminescent intensity of WEHI 164 cells expressing the luciferase gene as compared
to the control. Human trials have been reported using magnetic nanoparticles under
AC magnetic nanoparticles in Germany and Japan [182–184].
Using magnetic-luminescence magnetic nanoparticles (nanocomposite,
YVO4 :10Eu/Fe3 O4 ), localization or internalization of nanoparticles in cancer
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 691

Fig. 16.10 The heat

generated from Fe3 O4 MNPs
(bare MN), oleic acid
(OA)-coated MN and
PEG-coated MN at different
currents. Adapted and
reprinted with permission
from RSC Publisher [180]

cells as well as more killing of cancer cells are reported (Figs. 16.13 and 16.14)
[185].

16.4.1.2 Photothermal Therapy

Photothermal therapy (PTT) employing photo absorbers in the near-infrared (NIR)

region is an effective therapeutic tool for localized cancer therapy. Therapy makes
use of light-induced heating NPs as NIR photo absorbers which can convert light
energy into heat eventually elevating the temperature inside the tumor tissues to
induce thermal ablation beneficial for thermal therapy applications. NPs absorb the
light photons which then convert to heat sufficient for cell apoptosis. PTT ensures
the incorporation of NPs into the tumors for high heat dissipation at a lower laser
light intensity and minimal adverse effects to the surrounding healthy cells. PTT
treatment is primarily dependent on size, shape and optical properties of NPs as
well as the wavelength, energy, power density and diameter of laser beam deliv-
ered to the diseased tissue [186–190]. Though tissues and cells possess inherent
natural photothermal agents such as hemoglobin and cytochromes, their absorption
efficiency is very inferior. Therefore, NPs exhibiting strong absorption in the NIR
region are used as PTT photo absorbers for facilitating heat production and there-
fore, the optical absorption efficiency and biocompatibility of plasmonic NPs are of
prime importance. NPs should be selected depending upon the nature of the tumor
as well as the laser source. During the illumination of NPs with a laser beam, the
incident photons can be absorbed and scattered by the NPs. The absorbed incident
photons by the NPs cause either phonon emission or photon emission of different
frequencies. Phonon emission is responsible for heat production whereas photon
emission can lead to luminescence. The efficient utilization of NPs for PPT requires
692 A. Rajan et al.

Fig. 16.11 (A) Cell viability (%) of WEHI 164 cells treated with (0.22 or 0.44 mg) of MN-OA (0.5)
for 3 h with/without induction heating (400 A, 10 min.). Cells were also treated with corresponding
vehicle controls for which 4.4 μl of OA was dispersed in sodium carbonate and 50 μl (OA-1)
and 100 μl (OA-2) of the resultant stock was used for treatment. The viability of untreated control
(tumor cells not treated with MN-OA) was found to be 90 ± 2%. Error bars represent standard error,
n = 6 (B) The effect of different amounts of MN-OA(0.5) treatment on the morphological features
of WEHI 164 cells, with or without induction heating. (i–ii) Untreated controls, (iii–iv) cells treated
with 0.22 mg and (v–vi) 0.44 mg of MN-OA(0.5). The arrow in B (iv) indicates detached cells
and in B (vi) indicates cell rupture and debris. (C) The effect of MN-OA treatment with or without
induction heating on apoptotic cell death in tumor cells. The WEHI 164 cells were treated with
(0.22 mg or 0.44 mg) of MN-OA(0.5) and corresponding vehicle controls (OA-1 and OA-2) for 3 h
followed with or without induction heating. After 24 h, cells were harvested by trypsinization, and
apoptosis assay was performed using cell death detection ELISA PLUS kit. Relative apoptotic cell
death was expressed which is a ratio of absorbance in treated samples to untreated control. Error
bars represent standard error, n = 4. Adapted and reprinted with permission from Elsevier Publisher
[132]
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 693

Fig. 16.12 Tumor regression studies. (a) Tumors were subjected to MHT and tumor volume was
measured by digital Vernier caliper. Graph represents the increase in tumor volume measured
on different days after starting the therapy. (b) WEHI 164 cells expressing the luciferase gene
were transplanted in female BALB/c mice to obtain tumors and further subjected to MHT. The
luminescence intensity of tumors was measured on day 8 after treatment, using in vivo live animal
imaging system. Data is presented as Mean ± SD, N = 5 and * indicates that values are significant
at P < 0.05. (c) Images captured by live in vivo animal imaging system on day 8 after initiating the
treatment. Adapted and reprinted with permission from Taylor & Francis Group Publisher [181]
694 A. Rajan et al.

YVO4:10Eu NP
(a) (b) (c)

YVO4:10Eu/Fe3O4 hybrid
(d) (e) (f)

Fig. 16.13 Internalization of YVO4 :10Eu (a–c) and YVO4 :10Eu/Fe3 O4 (d–f) in WEHI 164 tumor
cells studied by confocal laser scanning microscopy. a and d correspond to luminescence measured
at 364 nm excitation wavelength and 575–615 nm emission wavelength. b and e correspond to bright-
field imaging and c and f correspond to merged images. Red color corresponds to the luminescence
from YVO4 @Eu. Adapted and reprinted with permission from RSC Publisher [185]

Fig. 16.14 Cell viability of

WEHI 164 tumor cells after
treatment with different
concentrations of
YVO4 :10Eu/Fe3 O4 in the
presence and absence of
induction heating (H).
*indicates that the values are
significant at P < 0.05.
Adapted and reprinted with
permission from RSC
Publisher [185]
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 695

Fig. 16.15 (a) FRET responsible spectral overlap of UC green band of UCNPs@SiO2 and absorp-
tion of AuNPs with their illustration inducing heat through FRET. (b) Temperature gain for 15 min
heating via 980 nm NIR laser radiation (power 600 mW). (c) Time-dependent temperature gain
under NIR laser excitation for different particle concentrations of AuNPs in hybrid NCC. Adapted
and reprinted with permission from ACS Publisher [113]

larger absorption efficiency (high heat dissipation) and lower luminescence quantum
yields. Absorption efficiency can be calculated as the ratio of the number of absorbed
photons to the total number of incident photons with the NPs. NPs should possess
a large absorption coefficient, minimal toxicity, ease of functionalization and better
solubility in biocompatible liquids. The synthesis methods for the formation of light-
induced nanostructures can be altered for fine-tuning the absorption band of NPs to
the desired wavelength range to enhance the specificity and response of PTT. NPs
such as noble metals, CuS, semiconductors, rare earth ion-doped NPs, carbon-based
NPs and organic NPs can be utilized for PTT. Though noble metals such as gold
(Au), copper (Cu), platinum (Pt) and silver (Ag) exhibit plasmonic resonances in
near-NIR region, Au is preferred as the primary choice for PTT applications. Au
is the single noble metal exhibiting localized surface plasmon resonance (LSPR)
in the NIR region beneficial for cancer therapy [191]. Au nanoshells were reported
for the tumor regression for in vivo PTT without any significant rate of increase in
the stem cells [192]. Hong et al. demonstrated PEGylated Au nanoclusters (AuNCs)
696 A. Rajan et al.

conjugated with AS1411 for achieving cancer-targeted PTT and anti-proliferation

activity [193]. Wang et al. explored different Au nanostructures such as nanorods,
nanocages and nanohexapods for photothermal therapy for cancer [194]. It has been
elucidated that Au nanohexapods are prospective materials for cancer theranostics
compared to others and exhibited the highest cell uptake with minimum cytotoxicity
in vitro. Further, incorporation of drug carrier into NIR photo absorbers has recently
been investigated for enhanced selectivity and therapeutic efficiency with minimizing
photothermal damage to normal tissues. Nanocage-like Au structures as a drug carrier
have proven to be potential for clinical PTT [195]. Phan et al. synthesized high NIR-
absorbed polypyrrole-coated FePt NPs via the thermal decomposition method and
performed in vitro PTT with breast cancer cells [196]. A laser of power density
1 W cm−2 for 5 min when exposed elevated the temperature from 39.3 °C to 71 °C
for varying concentrations of NPs. Liu et al. proved that PEG-modified graphene-iron
oxide-Au NPs combining the photothermal properties of graphene, magnetic prop-
erties of iron oxide and LSPR of Au NPs can enhance the therapeutic efficacy [197].
Moreover, the PTT is often combined with MHT for an enhanced synergistic cancer
therapy. For instance, Espinosa et al. synthesized Fe3 O4 nanocubes via the thermal
decomposition method and experimented for a combined MHT-PTT therapy in vivo.
Combined NIR laser exposure and ACMF exhibited an enhanced dual therapy when
treated on mice bearing solid tumors [198]. Recently, polydopamine (PDA)-coated
magnetite NPs synthesized via hydrothermal method have been exposed to laser
power of 2 W/cm2 for in vitro PTT on hepatocellular carcinoma HepG2 cells [199].
Reduced cell viability has been observed for the cells treated with increased NP
concentration after laser exposure to 5 min. Further drug conjugation on NPs has
been found to cause an enhanced cell death than bare NPs. This implies chemo-PTT
dual therapy is more effective compared to individual modalities.
Heating can be produced by florescent resonance energy transfer (FRET) by using
upconversion luminescence (UCNPs)—gold nanoparticles hybrid (NCC) [113].
Here, NaYF4 :Er-Yb (upconversion luminescence) nanoparticles absorb NIR light
at 980 nm and produce light at the visible range. This visible light is absorbed by
suitable Au nanoparticles through the SPR process (SPR = surface plasmon reso-
nance). Figure 16.15 shows heat generation of NCC by addition of Au NPs in a
fixed amount of UCNPs. With an increase of Au NPs, amount of the heat generation
increases.

16.4.2 Magnetic Nanomaterials for Drug Delivery

Nanocarrier-based drug delivery is attracting research interest due to the controlled

release of drugs, desired NPs size and its specificity toward the target site. Various
organic materials such as polymeric NPs, micelles and liposomes have previously
demonstrated to be beneficial for effectual clinical impacts [200]. However, magnetic
nanomaterial-based drug delivery system has significant advantages such as reducing
the problems associated with the usage of bare drugs and specifically targeting the
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 697

diseased areas sparing normal cells [201]. Intrinsic magnetic properties and the ability
to be guided with the aid of external ACMF in combination with their drug loading
ability enable the MNP drug delivery system to become a subject of intense research
[202]. Generally, the drug gets binded to the MNPs either via covalent attachment
or adsorption in case of porous structure or electrostatic interaction with functional
groups. Targeted delivery of MNPs can be of two types—passive and active targeting.
Passive targeting is achieved by the selective accumulation of NPs into the targeted
area via the leaky microvasculature of tumor as a result of the enhanced permeation
and retention (EPR) phenomena. In general, the majority of tumors have vascular
pore sizes around 380–780 nm, and this may differ depending on the growth and
type of tumor [203]. Thus, for targeted passive delivery, the particle size should be
below the capillary diameter of the tumor site. Clearance of NPs via healthy capil-
laries is another major concern. NPs < 6 nm can be rapidly cleared from kidneys
whereas larger NPs > 200 nm end up with phagocytic uptake [204]. In addition,
less accumulation of NPs for large tumors and short circulation times limits passive
targeting. Better protocols are required for a high concentration of nanocarriers to be
accumulated in tumor tissues with a minimal amount to be accumulated in the liver
and spleen for their effective clearance. Since passive targeting provides delivering
a wide range of nanocarriers, active targeting employs targeting ligands to facilitate
enhanced targeted delivery of the therapeutic agents to the specific surface recep-
tors at the tumor sites. Stimuli-responsive magnetic vectors have been employed
for conjugating drugs for active targeting. Active targeting is based on the conjuga-
tion of biochemical ligands such as proteins, peptides, folic acid, polysaccharides
(hyaluronic acid) and DNA to the magnetic vectors owing to their high specificity and
affinity toward specific surface receptors [205]. For drug delivery, magnetic vectors
are sensitive to external stimuli such as temperature, pH, light, electric field and
magnetic field for drug release.
Since the 1970s, the use of magnetic nanoparticles for chemotherapy has been
evolving. The first preclinical trial with MNPs has been conducted by Lübbe et al. in
1996 [206]. Since then, many researches have been conducted on magnetic vectors
for the potential use of drug delivery. MNP-conjugated drug carriers already commer-
cialized are TargetMAG-doxorubicin, FluidMAG and MagNaGel [207]. The main
advantages of the use of magnetic nanoparticles are they can be guided, visualized
(like in MRI) and heated (hyperthermia) with the help of a magnetic field. The major
factor for drug delivery is surface chemistry to increase the half-life in the blood-
stream by avoiding the immune system. Conjugation/coating with hydrophilic poly-
mers such as PEG on MNPs’ surface enhance longer circulation avoiding opsoniza-
tion [208]. IONPs are commonly employed as drug carriers owing to their ease of
preparation and superior magnetic properties. Kakwere et al. synthesized 20 nm
iron oxide nanocubes for conjugating an anticancer drug, doxorubicin (DOX) [209].
IONPs have been surface-functionalized with a thermoresponsive polymer shell
(poly(N-isopropylacrylamide)). DOX release as a result of heat dissipation with
the aid of external ACMF was observed and the release was more than 90%, when
the temperature was raised to 50 °C. Drugs can be released from the carrier through
pH response. Generally, cancer cells have lower pH (5–6) as compared to normal
698 A. Rajan et al.

cells (pH = 7.4). In another study by Zhang et al., iron oxide nanoflowers coated
with carbon shells were tested for loading acetaminophen drug [210]. The drugs
were trapped inside the pores of the carbon shell by hydrogen bond formation. The
drug loading efficiency was increased by the increase in pore volume of the material.
With a pore diameter of 65 nm, the loading percentage was around 30% and burst
release of 74% in 2 h and 80% after 4 h at 37 °C were obtained. Cheng et al. fabricated
porous hollow Fe3 O4 nanoparticles with a hydrodynamic diameter of 20 nm for DOX
release [211]. The release was studied in two different pH of 7.4 (physiological pH)
and 5 (cancerous cell pH). The DOX release % after 24 h was only 30% in pH 7.4
and 80% in pH 5 at 37 °C. Other ferrite NPs such as MFe2 O4 where M = Mn, Zi,
Ni and Co have also been investigated for drug delivery application. For example,
Ravichandran et al. fabricated a 25 nm size core–shell structure of MnFe2 O4 @Au
for the anticancer doxorubicin drug [212]. The nanoparticle has been coated with
folic acid for conjugation of DOX molecules on the surface. Loading efficiency of
97.5% and release of 79.6% at pH 5.4 were observed. MNP-based drug carriers are
expected to continue for specific targeting and safe image-guided delivery for the
future theranostic applications.

16.4.3 Magnetic Nanomaterials for Bioimaging

For the last several decades, MNPs have been studied for imaging purposes. Magnetic
resonance imaging (MRI) is one of the most widely used diagnostic imaging tech-
niques for clinical nanomedicine providing a cross-sectional view of the body. This
method is a non-invasive imaging tool commonly used for visualizing the structure
and function of tissues. MRI provides an enhanced image contrast of soft tissues
compared to other imaging modalities. MRI works on the basis of proton alignment
and its interactions in the presence of a high strength magnetic field. Under a very
strong magnetic field, protons present in the tissues get perturbed. Contrast agents
alter longitudinal (T1) or transverse (T2) relaxation times which are monitored by
MRI. Depending on T1 and T2 relaxation processes, contrast agents are named T1
and T2 contrast agents. T1 contrast agents shorten T1 relaxation time generating
bright images, whereas T2 contrast agents or negative contrast agents shorten T2
relaxation time generating dark images. In order to obtain an accurate interpretation,
positive and negative contrasts have to be used to obtain complementary informa-
tion. Recently, the use of superparamagnetic iron oxide nanoparticles (SPIONs) as an
MRI contrast agent has a significant advantage of differentiating the pathogenic cells
from the healthy cells [213]. SPIONs act as negative contrast agents showing a darker
image in MRI by shortening the transversal relaxation time (T2) of the surrounding
water protons. Increased relaxivity value results in enhanced image contrast even
at a lower concentration of SPIONs. Zhou et al. employed the thermal decomposi-
tion method for synthesizing small iron oxide nanocubes coated with DMSA with
varying sizes in the range from 7 to 21 nm and obtained transversal relaxivity (r2)
of 76 mM−1 s−1 –298 mM−1 s−1 [214]. In another work by Orza et al., PEI-coated
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 699

Fe3 O4 nanorods have been synthesized. NPs exhibited an improved MRI contrast
effect in terms of T2 relaxivity value enhancement from 670.6 to 905.5 mM−1 s−1 for
nanorods of size varying from 25 to 50 nm, respectively [215]. In addition to IONPs,
MNPs such as MnFe2 O4 [216, 217], CoFe2 O4 [216], NiFe2 O4 [216] and ZnFe2 O4
[218] have been used for MRI applications. In recent years, several studies revealed
the application of iron oxide as T1 contrast agents as a substitute to gadolinium-
based T1 contrast agents for reducing the associated toxicity [219]. Macher et al.
developed ultrathin iron oxide nanowhiskers (20 × 2 nm) and obtained longitudinal
relaxivity r1 of 6.13 mM−1 s−1 when used as a T1 contrast agent for MRI [220]. This
work suggests the potential of nanowhiskers to serve as T1 MRI contrast agents.
Zhou et al. developed magnetite hexagonal-shaped nanoplates as strong T1 and T2
contrast agents by tuning the size and composition [221]. In this case, morphology
and high magnetic moment of NPs led to the strong T2 effect and increased water
proton interaction in the [110] facet of iron oxide resulting in a strong T1 effect.
It was also found that T1–T2 dual-mode contrast agents can be controlled by the
thickness of the nanoplates.
Medical imaging techniques include positron emission tomography (PET),
computed tomography (CT), MRI and optical imaging. Since single imaging
modality cannot provide all the information, combining different techniques has been
recently under investigation. The PET-MRI multimodel image uses a combination
of radioactive metal ions with chelating ligands such as 1,4,7-triazacyclononane-
N,N ,N -triacetic acid (NOTA) and 1,4,7,10-tetraazacyclododecane-1,4,7,10-
tetraacetic acid (DOTA) for providing a high-resolution image [222]. For tumor
imaging, 64 Cu-NOTA and c RGD are coupled on the surface of multifunctional iron
oxide NPs. CT which is the most common imaging technique provides high temporal
resolution and low sensitivity when compared to MR imaging. CT uses iodine,
bismuth, gold, lanthanides and tantalum as contrast agents. Unlike PET-MRI, conju-
gating iodinate molecules onto the magnetic nanoparticle is complicated. Optical
imaging is used to verify biomarkers and its principle is based on the detection of
light. Deep tissue imaging is not possible in this technique since light has limited
penetration. This technique uses organic fluorescent dyes such as fluorescein isothio-
cyanate (FITC) and Cy 5.5. For a combined optical-MRI, these fluorescent dyes are
conjugated with MNPs [223]. Cy5.5 labeled IONPs have been used for brain tumor
imaging [224]. Some other magnetic probes for optical-MRI are the encapsulation
of dyes for enhancing the signal intensity [225] or the use of quantum dots instead
of dyes [226].

16.4.4 Magnetic Nanomaterials for Biosensors

A biosensor is a device which combines a biorecognition element to capture the

target molecules and a transducing element to transfer a measurable signal propor-
tional to the interaction between the target molecules. Based on the types of trans-
ducers, biosensors are classified as thermal, piezoelectric, optical and electrochemical
700 A. Rajan et al.

sensors. Owing to the prospective development brought about by nanotechnology in

the field of biosensing, MNPs have been utilized to enhance selectivity and sensi-
tivity. MNPs offer several advantages in sensing strategies such as low limit of detec-
tion (LOD), enhanced sensitivity, less analyzing time and high signal-to-noise ratio
compared to non-magnetic-based sensors [227]. MNPs are used either directly by
integrating MNPs into the transducer materials or/and dispersed in the samples to be
detected followed by attracting toward active detection surface of biosensor under
an external MF. Electrochemical (EC) biosensors measure EC signals originated
by the interaction of electrodes and analytes in the form of voltage or current or
impedance. The electrodes are coated with biochemical materials in order to improve
the signal intensity [228]. Due to their high sensitivity, easy operation and low cost,
EC biosensors are used in environmental, clinical, pharmaceutical and biological
fields [229]. Based on the working principle, electrochemical sensors can be clas-
sified as voltammetric, potentiometric, amperometric, capacitive and chemiresistive
[230]. MNPs have been used to improve the sensitivity due to their easy preparation,
biocompatible and superparamagnetic properties. The most commonly used mode
of detection is voltammetry. Surface-functionalized Fe3 O4 NPs are used commonly
in biosensor applications. In biosensors, core–shell structured MNPs are widely used
for the attachment of binding ligands and to improve stabilization in solution [231].
For example, Fe3 O4 @SiO2 is widely used to modify electrode surfaces owing to
its large surface area, good response in conductivity and increased electroactive
interaction sites [232, 233]. Carbon-based materials such as graphene oxide (GO)
and carbon nanotubes (CNTs) are also widely used to functionalize MNPs. Carbon-
coated MNPs have improved characteristics in terms of large surface area, thermal
and chemical stability, catalytic activity and electro-conductivity [234]. Recently,
Beitollahi et al. synthesized GO/Fe3 O4 @SiO2 core–shell nanocomposite sensors
for the detection of dopamine and uric acid [235]. For analysis, the concentration
ranges of dopamine and uric acid taken are 0.1–600.0 μM and 0.75–300.0 μM,
respectively. The detection limit obtained by GO/Fe3 O4 @SiO2 core–shell modified
electrode was 8.9 × 10−8 M for dopamine and 5.7 × 10−7 M for uric acid. The
sensor exhibited good analytical performance, and two different well-defined anodic
peaks were obtained for dopamine and uric acid. In another study by Arvand et al.,
multi-walled carbon nanotube (MWCNT)-decorated magnetic core–shell structure
Fe3 O4 @SiO2 /MWCNT-CPE was fabricated to determine uric acid [236]. The elec-
trochemical behavior of uric acid on an unmodified carbon electrode, an MWCNT-
electrode and Fe3 O4 @SiO2 /MWCNT-CPE modified electrode was investigated by
cyclic voltammetry. The anodic peak current of the magnetic nanoparticle-modified
electrode was found to be 4.6 times higher than that of the unmodified electrode and
2.7 times higher than the MWCNT-modified electrode. The increased sensitivity was
ascribed to a larger electroactive surface area and fast electron-transfer kinetics in
Fe3 O4 @SiO2 /MWCNT-CPE. Magnetic nanocomposites based on Au NPs are also
widely used as biosensor materials due to their easy preparation, strong absorption,
improved biocompatibility and good conductivity. Recently, Saljooqi et al. fabri-
cated a modified glassy carbon electrode by using the magnetic nanocomposite of
Fe3 O4 @SiO2 -PANI-Au for the detection of quercetin in food and biological fluids
16 Synthesis and Processing of Magnetic-Based Nanomaterials … 701

[237]. The modified electrode detected queretin in the range of 1.0 × 10−8 –1.5 ×
10−5 mol L−1 with the limitation of 3.8 × 10−9 mol L−1 . Furthermore, the sensor
was also studied on biological (human serum and urine) samples, apple juice, radish
leaves and teas with the detectable concentration range of 1.0 × 10–8 molL−1 or
5.0 × 10–6 molL−1 . In another study, Gan et al. use Fe3 O4 /Au magnetic nanoparti-
cles to modify a screen-printed carbon electrode to determine the organophosphorus
pesticides in Chinese cabbages, and its electrochemical properties were investigated
by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) [238]. The
sensor performance was comparable to gas chromatography, and it exhibited better
performance in terms of fast response and sensitivity for detecting organophosphorus
pesticides. The detectable concentration of dimethoate in cabbage is in the range of
1.0 × 10–3 –10 ng.mL−1 with a detection limit of 5.6 × 10–4 ng.mL−1 . Compared
with the other sensors, the recovery rate obtained is 88–105%. In addition, other
MNPs such as CoFe2 O4 NPs have also been utilized as electrochemical biosensors
like CoFe2 O4 NPs [239, 240].
Optical devices have also been employed as sensors for the detection of several
analytes due to their low manufacturing cost, reduced interferences and low signal-to-
noise ratio. Optical sensors can be used in food, environmental and clinical samples
[241–243]. Different principles of detection used in optical sensors are chemilu-
minescence (CL), reflectance, fluorescence spectroscopy, interferometry and light
scattering. CL-detection is the most commonly used technique, and for quantita-
tive analysis, the systems’ selectivity and emission intensity can be improved by
the use of MNPs as a catalyst in the reaction [244]. The surface plasmon reso-
nance (SPR)-based optical sensor is the most widely used to investigate the inter-
actions between two molecules, such as antibody-antigen, DNA/RNA and protein–
nucleic acid interactions. It has high assay sensitivity and can target analytes at a very
low nanomolar concentration range. Generally, Au and Ag nanoparticle-conjugated
MNPs at the size range of 10–15 nm are used for SPR sensors. Theoretically, by
increasing the particle size, the SPR effect can be increased but it may decrease the
colloidal stability of the nanoparticles. Sun et al. reported SPR biosensors based on
hollow polydopamine-Ag capped Fe3 O4 NPs reduced with graphene oxide to detect
rabbit IgG [245]. The comparative analysis with the conventional SPR biosensor
shows that Ag/Fe3 O4 biosensor showed detection at 132 times lower concentration
and 8 times lower than immuno-sandwich assay. In another study by Chen et al.,
core–shell structured Au/magnetic nanoparticle SPR-based biosensors were devel-
oped for the detection of thrombin with the LOD of 0.6 nM [246]. Piezoelectric
biosensors work on the principle of quartz-crystal microbalance (QCM). The QCM
has a quartz-crystal disk, and it vibrates under the influence of an electric field. The
frequency of vibration changes as molecules adsorb or desorb from the surface of
the crystal. The mass of the absorbed molecule on the surface is proportional to
the frequency. QCM sensors are inexpensive, small and capable of giving a rapid
response even at the change of 1 ng. MNPs with piezoelectric properties can increase
the active surface area and decrease the noise in conventional QCM sensors. Zhou
et al. developed Au NPs-coated SiO2 /Fe3 O4 nanoparticle-based immunosensors for
702 A. Rajan et al.

the detection of C-reactive protein (CRP) in serum [247]. The CRP detection of Au-
Fe3 O4 @SiO2 QCM is comparable with ELISA methodology, and the sensor surface
can be regenerated and used repeatedly. Still, more research is required on the use of
magnetic nanoparticle piezoelectric sensors to improve the sensitivity and stability
of the sensors.

16.5 Conclusions

Successful progress in the field of multifunctional magnetic nanoplatforms possesses

broad potential applications in cancer nanomedicine. Substantial improvements are
being incorporated into the synthesis methods to yield more stable monodispersed
NPs with controlled size, shape, chemical composition and surface functionaliza-
tion pertinent for biomedical applications. Various synthesis protocols to produce
magnetic-based nanomaterials, their surface functionalization along with the asso-
ciated challenges for distinctive biomedical applications have been summarized.
Further, the application of magnetic-based nanomaterials in distinctive biomedical
applications such as MHT, PTT, drug delivery, bioimaging and biosensing have been
discussed in detail.

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Chapter 17
Role of Synthesis in Evolution
of Catalyst: Bulk, Dispersed to Single
Atom

Mrinal R. Pai, Sushma. A. Rawool, Rajendra V. Singh,

Atindra Mohan Banerjee, and A. K. Tripathi

Abstract The quantity of information available on subject such as synthesis and

catalysis is vast. However, it is significant to integrate both subjects and present a
comprehensive article. The present chapter is a small contribution to acclaim the role
of synthesis in the development of catalysis industry and research. Three main cate-
gories of catalysts that evolved over the years are bulk, dispersed or supported and
single atom catalysts (SACs)—which is an ultimate possible form of the dispersed
catalysts. With the advancement in research on synthetic techniques, the dream of
dispersion of single atoms on support could be realized by managing the associated
high surface energy, which is a chief obstacle causing agglomeration and migration
of metal ions. SACs are promising catalysts with exceptionally high activity, selec-
tivity and turn over number. The catalyst industry is heavily dependent on bulk and
dispersed catalysts, while SAC is at research stage. This chapter aims to give a brief
account of all three classes and synthetic methods used to prepare industrial catalysts.
It also gives an overview of novel/modified methodologies used to prepare nanopar-
ticles of mixed metal bulk oxides and supported catalysts at large scale. Atomic layer
deposition, wet chemical co-precipitation route, photo-deposition and atom trapping
are four different approaches adopted to synthesize SACs are also discussed. Finally,
it emphasizes synthesis–activity correlations by using examples from our laboratory
on thermal reactions ranging from low-temperature CO oxidation, CO + N2 O to
high-temperature sulfuric acid decomposition catalytic reactions.

Keywords Synthesis · Bulk oxides · Dispersed · Single atom catalyst · CO +

N2 O · Sulfuric acid decomposition

M. R. Pai (B) · Sushma. A. Rawool · R. V. Singh · A. M. Banerjee · A. K. Tripathi

Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
Homi Bhabha National Institute, Mumbai 400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 715
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_17
716 M. R. Pai et al.

17.1 Introduction

Catalysis is a prominent realm of applied chemistry regulated by chemical engi-

neering principles leading to a significant contribution (30-40%) in the world’s
GDP [1–3]. The advent of catalysts has brought a revolution in chemical industry
by opening new possibilities for many important reactions, which were difficult to
realize under normal temperature and pressure conditions. In addition, catalysts have
immense applications in energy and environment sector. Catalysts are class of mate-
rials that improve the rate of forward and reverse reactions, or it can be said that they
allow the reactants to reach the equilibrium faster, without itself undergoing any
morphological or compositional change. However, this is an overrated statement.
After several cycles, the catalytic activity deteriorates; the surface characteristics
and bulk properties alter mainly due to the adsorption of reaction intermediates
and thermal shocks. Leaching of the active sites along with evolution of gaseous
products during a catalytic reaction is a very common drawback associated with
metal-supported catalysts. Thus, practically catalyst was defined as “a catalyst is a
substance that changes the rate of a chemical reaction without itself appearing in the
products” by Ostwald in 1895, almost 60 years after the standard definition given
by Berzelius of ideal catalyst. A more refined definition by IUPAC (1976) was, “a
catalyst is a substance that, being present in small proportions, increases the rate
of attainment of chemical equilibrium without itself undergoing chemical change”
[1–4].
The scope of the present article is limited to heterogeneous catalysis (gas or liquid
phase reactants and solid catalyst) in which reactions proceed at interface by adsorp-
tion of one or more reactant molecules on the catalyst surface. Adsorption on catalyst
surface concentrates and activates the reactant molecules, facilitates close interac-
tion leading to breaking and formation of new bonds. Conductors (metals, alloys),
semiconductors (oxides, chalcogenides) and insulators (metal oxides, solid acids or
bases, heteropolyacids, clays zeolites) are the three main categories of compounds,
which are employed as catalysts depending on the application. The reactive chem-
istry of these compounds guides their catalytic property. For instance, metals have
shown potential in catalyzing hydrogenation, dehydrogenation and hydrogenolysis
reactions. Semiconductors; metal oxides such as Fe2 O3 , NiO, CuO, etc. serve as
oxidation catalyst while sulfides carry out desulfurization reactions. Dehydration
and isomerization reactions can occur on insulator oxides such as Al2 O3 , MgO, SiO2
etc. Solid acids/bases catalyze organic reactions involving carbocation or anions as
intermediates. Thus, suggesting that all cannot catalyze all reactions. A compound is
qualified to catalyze a particular reaction, for which it has compatible chemistry with
reactant molecules. Mostly, catalysts have application in oil refining, automobiles,
bulk chemicals, fine chemicals, fertilizers, polymers, detergents, textiles, pharma-
ceuticals and energy and environment sectors. Many sections of these industries are
using one or more reactions in which catalysts are essential. It has been estimated
that at least 80% of chemical products are generated through the involvement of a
catalytic process at some stage or other. Catalytic converter installed in all modern
17 Role of Synthesis in Evolution of Catalyst: Bulk … 717

automobiles to control the exhaust emissions is one of the widely known applications
[5, 6]. Haber’s process catalyst brought revolution in fertilizer industry [7]. Electro-
catalysts coated on electrode surface play a vital role in fuel cells, where dissociation
and reaction of fuel molecules take place and that govern their overall functioning is
another example from innumerable applications [8].
Normally, performance of catalyst in a catalytic reaction is gauged by its activity,
selectivity and turn over number [9]. Catalytic activity is identified by percent conver-
sion (total number of moles of product formed per mole of reactant × 100) in a given
period. Conversion should reach theoretical thermodynamic yield possible under
given conditions of temperature and pressure. The faster the catalyst approaches
toward thermodynamic yield, better is the catalyst. Figure 17.1 compares the simu-
lated conversion calculated via thermochemical equilibrium modeling with experi-
mental results for catalytic methane decomposition (CMD) reactions over activated
char and biochar catalysts [10]. The experimental values are much lower than simu-
lated values and led researchers to investigate the plausible reasons hampering to
achieve the simulated thermodynamic yield. Industrialists search for catalysts enable
to attain the thermodynamic yield in minimum possible time under reduced temper-
ature and pressure conditions for an economically viable process. A complete under-
standing of a catalytic reaction involves a great deal of chemical kinetics, ther-
modynamics and surface chemistry explained in dedicated monographs and books
[11–16].
Designing a catalyst for a particular process is a mainstream research area and
innumerable laboratories in fact several institutes are dedicated to catalysis research
worldwide. A variety of tailor-made catalytic materials are required for specific

Simulation CH 4 :N2 1:9

Simulation CH 4 :N2 1:1
Simulation CH 4 :N2 9:1
Experiment (Biochar) CH 4 :N2 1:9
Experiment (AC) CH 4 :N2 1:9
Experiment (Biochar) CH 4 :N2 1:1
Experiment (AC) CH 4 :N2 1:1
Experiment (Biochar) CH 4 :N2 9:1
Experiment (AC) CH 4 :N2 9:1

Fig. 17.1 Percent conversion of methane observed experimentally and compared with simulated
equilibrium values as a function of temperature. Reprinted from Ref. [10] with permission from
Elsevier
718 M. R. Pai et al.

applications, which can perform the desired task selectively, efficiently and at the
same time during the long operational times In order to design such dedicated ratio-
nally designed catalysts, it is important to have a thorough understanding of their
physico-chemical properties. The first step in designing of catalyst is to screen the
potential candidate that fulfills the essential thermodynamic criteria necessary for the
required application. Next is to develop that candidate catalyst by pruning its bulk and
surface characteristics—using appropriate modification strategies—for enhancing its
catalytic properties. The modified developed catalyst is finally tested and evaluated
for catalytic activity and compared with the parent compound. Bulk and surface
properties play an important role in deciding the catalytic performance of a catalyst.
Adsorption of reactants takes place on surface of catalyst in heterogeneous reactions,
thus modification in surface area, porosity and distribution of active sites on surface
or surface composition results in considerable improvement of reaction kinetics by
lowering the activation energy. Surface of a catalyst may not adhere to the chemical
formula by which that compound is known. For instance, Cu0.02 Ti0.98 O2-δ may have
more than 0.02 mol percent Cu on surface [17]. Chemical composition on surface is
mainly governed by unsatisfied valence of metal ions and vice-versa. Particle size,
N2 -BET (based on van der Waal interactions) and metal (based on chemisorption)
surface area are other important characteristics of catalyst surface and are crucial for
its catalytic activity. The active sites for any catalytic reaction reside on surface and
depend on the above characteristics of surface. In case of thermal reactions catalyzed
by mixed or simple oxides, the crystal type, orientation of planes, flexibility of lattice,
non-stoichiometry and defects play an important role in determining the oxide O2−
ion mobility at high temperatures. Several mechanisms such as Mars van kreveleen,
Eley Rideal etc. are proposed [18–20] based on evidences from in situ experimental
probes to explain the participation of lattice oxygen during redox reactions at higher
temperatures. For photocatalytic processes, semiconductors mainly are employed to
harness the photon energy and thus referred as photocatalysts, are the core of photo-
catalytic process. The optical and electronic qualities of the photocatalyst control the
channeling and utilization of the absorbed solar photons into energy conversion reac-
tions. The valence orbitals of cations and anions forming crystal lattice combine and
based on this, band structure can be elucidated using first principles. At the same time,
the crystallite size and crystallinity are also very important for deciding the yield of
photocatalytic reactions as these have direct implications on path of photogenerated
photons from bulk to surface. The role of synthesis in designing and determining the
efficiency of photocatalysts will be dealt in details in the next chapter.
The basic chemistry of a catalyst is intrinsic to its chemical constitution and that
will not vary from one synthesis method to another. However, a synthesis method-
ology does control the surface and bulk properties to certain or may be large extent
in specific cases. Extensive understanding of a relationship between the structural
and morphological characteristics with the catalytic properties is extremely impor-
tant for developing a desired catalyst. Since, the advent of catalysts a constant
pursuit for improvisation has led researchers to invent newer technologies for the
synthesis of superior catalysts with desired control on composition, structure and
morphology. The synthesis of catalyst involves several steps where every step is
17 Role of Synthesis in Evolution of Catalyst: Bulk … 719

crucial in deciding its surface and bulk characteristics. Thus, catalysts must be
synthesized under accurate and carefully controlled conditions [21–23].
Aim and scope
The present chapter has two main aspects. First, it gives an account of existing
and emerging synthetic techniques adopted to modify the bulk and surface, of
potential catalyst candidates. Oxides (simple/mixed metal) and metal-supported are
two main catalyst categories that would be focus of the present article. This also
includes advancements in synthetic protocols for the preparation of catalyst in bulk
powder/granular, dispersed on support and dispersion of active component to the
extent of single atoms on support referred as single atom catalysts. The second
part will emphasize the role of synthesis in evolution of catalysts and catalytic
processes. Here, several catalytic thermal reactions investigated in our research group
will be discussed to exemplify how catalyst development is reliant on exploration
of synthesis methodologies. Our studies focus on how catalyst synthesis, plays a
crucial role in establishing the desired composition and structure of the catalytic
materials active for low to moderate temperature CO oxidation, CO + N2 O to
high-temperature sulfuric acid decomposition catalytic applications. This segment
illustrates synthesis–catalytic activity correlations.

17.2 Bulk Catalysts

A large number of simple oxides, mixed metal oxides, unsupported metals etc. are
used as heterogeneous catalysts in industries [24, 25] for the production of chemicals
(organic and inorganic), crude oil refining and petrochemistry, environmental protec-
tion, energy conversion process (Table 17.1). Simply, oxides can be classified into
stoichiometric and non-stoichiometric based on their thermal stability. Oxides such
as Al2 O3 , SiO2 , ZrO2 etc. are thermally stable, do not deviate from their stochiome-
tery on heating are called stoichiometric. While non-stoichiometric oxides tend to
loose or gain oxygen on heating, for example, ZnO, Fe2 O3 etc. Non-stochiometric
oxides can be either simple oxides or multi-metal also referred as mixed metal
oxides. The stability of simple oxides against melting (or sublimation) or disso-
ciation is of great importance in catalysis. Many transition metal oxides have rather
low melting points. These oxides can be stabilized thermally by the formation of
multicomponent mixed oxides systems. V2 O5 , contact process catalyst is known for
its high catalytic activity but its use is limited by its low melting at 695 °C. V2 O5
in combination with number of rare earth and other metal ions forms homophasic
new chemical identities, vanadates, such as lanthanum vanadate, LaVO4 , thorium
metavanadate, Th(VO3 )4, thorium pyrovanadate, ThV2 O7 and thorium orthovana-
date, Th3 (VO3 )4 . These compounds are thermally stable with very high melting
point (minimum 1000 °C) and have shown potential for catalyzing CO oxidation
reaction [26–30].
720 M. R. Pai et al.

Table 17.1 List of conventional synthesis methods used to prepare selected bulk and supported
catalysts employed in various industrial processes [12, 13, 24, 25, 36]
S. No Catalyst Processes Synthesis Operating
method conditions
Metal oxides
1 Fe3 O4 (K2 O, Al2 O3 ) Ammonia synthesis Fusion 450–500 °C,
250–400 bar
2 Pt/Rh nets Oxidation of NH3 to NO Fusion Around
(nitric acid) 900 °C
3 Bauxite, Al2 O3 Claus process (sulfur) Sol–gel 300–350 °C
2H2 S + SO2 → 3S +
2H2 O
4 CuCr2 O4 Esters to alcohols Precipitation 250–300 °C,
250–500 bar
5 Fe3 O4 (Cr, K oxide) Ethylbenzene to styrene Fusion 500–600 °C,
1.4 bar
6 Pt/Rh nets Methane to HCN Fusion 800–1400 °C,
1 bar
Mixed metal oxides
7 ZnO–Cr2 O3 Methanol synthesis Co-precipitation 250–400 °C,
200–300 bar
8 CuO–ZnO–Cr2 O3 CO + 2H2 → CH3 OH Co-precipitation 230–280 °C,
60 bar
9 Fe/Cr oxides CO conversion: CO + Co-precipitation 350–450 °C
H2 O  H2 + CO2
10 Cu/Zn oxides CO conversion: Co-precipitation 140–260 °C
CO + H2 O  H2 + CO2
11 Bi/Mo oxides Propene to acrolein Co-precipitation 350–450 °C,
1.5 bar
12 Al2 O3 /SiO2 ; zeolites Cracking of kerosene Hydrothermal 500–550 °C,
1–20 bar
13 V2 O5 –K2 S2 O7 SO2 oxidation Fusion 400–500 °C
Supported catalysts
14 V2 O5 /support Oxidation of SO2 to SO3 Impregnation 400–500 °C
15 V2 O5 /support Benzene or butene to Impregnation 400–450 °C,
maleic anhydride 1–2 bar
16 MoO3 /Al2 O3 Demethylation of toluene Impregnation 500–600 °C,
to benzene 20–40 bar
17 Ni/Al2 O3 Steam reforming of Precipitation 750–950 °C,
methane 30–35 bar
H2 O + CH4 → 3H2 +
CO
(continued)
17 Role of Synthesis in Evolution of Catalyst: Bulk … 721

Table 17.1 (continued)

S. No Catalyst Processes Synthesis Operating
method conditions
18 Ni/Al2 O3 Methanization Precipitation 500–700 °C,
CO + 3H2 → CH4 + 20–40 bar
H2 O
19 Co or Ni on Al2 O3 Nitriles to amines Impregnation 100–200 °C,
200–400 bar
20 Cr2 O3 /SiO2 Polymerization of ethene Impregnation 50–150 °C,
to polyethylene 20–80 bar
21 H3 PO4 /SiO2 Alkylation: Ethylbenzene Impregnation 300 °C,
from benzene and 40–60 bar
ethylene
22 H3 PO4 /kieselguhr Oligomerization of Impregnation 200–240 °C,
olefins to prepare 20–60 bar
gasoline
23 V2 O5 –K2 S2 O7 /SiO2 o-Xylene or naphthalene Impregnation 400–450 °C,
to phthalic anhydride 1.2 bar
formation
24 V2 O5 /TiO2 o-Xylene or naphthalene Impregnation 400–450 °C,
to phthalic anhydride 1.2 bar
formation
25 H3 PO4 /activated Oligomerization of Impregnation 200–240 °C,
carbon olefins to form gasoline 20–60 bar

Perovskites, scheelites, pyrochlores, spinels etc. are of considerable interest not

only form stable oxyions but also perform better than constituent oxides. The crystal
structure, lattice distortion, defects, multi-valence, oxygen non-stochiometry help in
enhancing the oxygen ion mobility makes it more labile at lower temperatures. Elec-
tronic transfers may lead to valence exchange between two metal ions, for example,
iron cobaltite may contain Co2+ and Fe3+ , instead of Co3+ and Fe2+ . This leads to vari-
ation in the oxygen content over a small range, close to stoichiometry corresponding
to the given spinel phase. Mixed oxides either as solid solution or as poly phases have
been used extensively as complete oxidation and partial oxidation catalysts [20, 31,
32]. For example, molybdates are used as catalysts for a number of selective oxida-
tion reactions. Bismuth molybdate catalyzes the oxidation of olefins whereas iron
molybdate catalyzes the oxidation of alcohol to aldehydes [33]. In complex mixed
oxides such as Fe–Mo–O system, bulk oxygen is very mobile as compared with
constituent oxides. The mobility of bulk oxygen depends upon the ease of desorp-
tion of surface oxygen, and gets enhanced, if metal—surface oxygen bond strength
(qs ) is low. When constituent components of a complex oxide catalyst give a new
chemical compound, the later has a value of qs , which is not the sum of the values
of qs for the components. Thus complex mixed oxides generally have a lower qs
and higher mobility of oxygen, as compared with constituent metal oxides [11, 34].
For instance, when potassium sulfate is added to V2 O5 , it results in loosening of the
722 M. R. Pai et al.

V–O bond. Similarly, high mobility of the bulk oxygen in V–Mo–O system [35] is
attributed to a lowering in value of qs for V–Mo–O mixed oxide as compared with that
of corresponding constituent oxides. Thus, by virtue of improved thermal stability
and lattice mobility, mixed metal oxides are preferred and more recommended over
simple oxides as catalysts.

17.2.1 Preparation of Bulk Catalysts

For industrial applications, tons of catalysts per day are required to be produced. From
Table 17.1, bulk oxides such as Fe/Cr oxide are used for CO oxidation, ZnO–Cr2 O3
and Cu–Cr–Zn–O for methanol synthesis, spinel CuCr2 O4 for ester to alcohol conver-
sion, Bi–Mo–O, MoO3 , V2 O5 , Fe3 O4 and Cr2 O3 are also used as active component
for many catalytic reactions, Al2 O3 , TiO2 , SiO2 and are used as supports [12, 13,
24, 25, 36]. These oxides are synthesized in bulk as these are inexpensive. Precip-
itation is one of the most common methods used to prepare the oxides and also
pure support materials. Stoichiometric amounts of one or more metal salts solutions
are mixed and the co-precipitated under specific conditions to yield hydroxides or
carbonates, which are further, dried, shaped, calcined in air to yield oxide powders.
The precipitation conditions can affect the crystallinity, particle size, porosity and
composition. Iron-chromium oxide used as catalyst for high-temperature CO oxida-
tion is produced by co-precipitation, Fe3 O4 required for styrene production, and
CuO–ZnO–Al2 O3 from their respective nitrates is prepared by co-precipitation for
methanol synthesis. However, each compound precipitates at different rates that
cause microscopic inhomogeneity.
Unsupported metals were also used as bulk catalysts such as Pt–Rh gauge
catalyzed oxidation of ammonia. Pt–Rh gauge was prepared by fusion of pre-molten
precursors. The famous Fe2 O3 catalyst of Haber’s process for ammonia synthesis
(Table 17.1) was also prepared by fusion methodology in which iron ore was melted
in an electric furnace at 1600 °C in the presence of process promoters such as alumina
and silica. While other promoters viz; CaO and KNO3 or K2 CO3 are added later
during oxidation step at 1600–2000 °C. The melt is then cooled, crushed and sieved
into several size fractions. Fine particles are discarded and again fed to melt for
recycling. Molten V2 O5 is fused with K2 S2 O7 to yield V2 O5 –K2 S2 O7 catalyst for
SO2 oxidation reaction. Fusion catalysts generally have low surface area in range
of 1–2 m2 /g. Among bulk non-supported metal catalysts, Raney nickel is the most
established for hydrogenation and dehydrogenation reactions. It is also referred as
skeletal metal ore sponge catalysts. These are having metal crystallites anchored on
skeletal metal sponge. The metal sponges are prepared by leaching the alloys using
caustic soda. In 1921, Murray Raney performed independent research, prepared an
alloy of Ni/Si in 1:1 ratio and treated it with sodium hydroxide, which was found to be
five times more active than the best catalyst used in the hydrogenation of cottonseed
oil. Subsequently, Raney produced a 1:1 Ni/Al alloy following a procedure similar
to the one used for the nickel–silicon catalyst, leached it by concentrated NaOH and
17 Role of Synthesis in Evolution of Catalyst: Bulk … 723

most of the aluminum dissolved, leading to a porous sponge-like metal with very high
surface area (30–120 m2 /g) and catalytic activity. 2–15 nm sized microcrystallites
agglomerated to form macropores of sponges. In the porous network of the spongy
metal, black Ni crystallites are supported on Ni–Al cores. The choice of Ni–Al ratio
was accidental without much scientific basis. However, this is the preferred alloy
composition for the production of Raney nickel catalysts currently in use. Raney
catalysts are often referred as skeletal catalysts or active base metal catalysts too.
There are many other Raney catalysts used commercially, such as Raney Cu–Zn
catalysts for methanol synthesis and water–gas shift reactions, Raney Cu–Zn–Cd
catalysts for selective hydrogenation of α, β-unsaturated aldehydes and ketones and
Raney Cu for methyl formate production. Due to spongy nature, these are highly
reactive and catch fire in air (pyrophoric), thus stored as wet catalysts.
Melting procedures show limitations for the preparation of high-temperature
refractory materials. Wet chemistry, however, provided a new approach to synthe-
size homogeneous ceramic materials called sol–gel method. It is a versatile method
widely used in industry for the preparation of amorphous high surface area catalysts
and carriers such as SiO2 , TiO2, etc. also offer nanocrystalline homophasic refractory
materials such as spinel, MgAl2 O4 . There are several parameters in each step, which
influences and controls the morphology of the final product. It involves hydrolysis
of the metal precursor in the acidic or basic mediums, followed by polycondensa-
tion of the hydrolyzed products. In this way, hydrogel—a metastable open structure
polymer—is formed in which metal nanoparticles are retained. The gel is aged, dried
and calcined for the final product. Depending on the drying and preparation proce-
dure, pore size and porosity of the products can be tailored. Supercritical drying
results in mesoporous aerogel (pore size 2–10 nm) with large surface area, while
slow drying at ambient conditions results in microporous xerogel with a narrow
pore size distribution, which is comparable to that of zeolites. During heat treat-
ment, different product forms can be acquired such as powder, monoliths, thin films
or membranes. For practical application, the catalyst powder is cast into different
shapes by kneading or by extrusion or by pressing into tablets with help of additives.
An overview of different shapes in which commercial catalysts are functional [37]
is given in Fig. 17.2.
Flame hydrolysis method is used for the preparation of dense non-porous supports
with high thermal stability and surface area such as fumed silica, alumina, TiO2 . The
precursors, hydrogen and air are fed into flame, where the precursor is hydrolyzed to
hydroxide formation. P25 TiO2 is synthesized using aerosol flame pyrolysis process
having a particle size of 21 nm and 50 m2 /g surface area [38]. The hydroxides are
later recovered, calcined to oxides. Alumino silicates are prepared by hydrothermal
route.
724 M. R. Pai et al.

Fig. 17.2 Various shapes of catalysts for practical applications. a Granules b Extrudates c Pellets
d Cylinders e Spheres f Monolith g Rings. Reproduced with permission from Ref. [37] Copyright
2018 MDPI

17.2.2 Preparation of Mixed Metal Oxides (MMO)

Nanoparticles

With increasing demand for catalysts and catalytic reactions, continuous advance-
ment in synthetic procedures was made. Researchers have investigated and devel-
oped both physical and chemical methods for the preparation of MMO nanoparticles
[39–49]. Figure 17.3 presents a flowchart summarizing all possible methods for the
preparation of MMO nanoparticles. The details of most of the chemical methods
adopted for the preparation of nanomaterials are dealt with other chapters of the
present book.
Physical methods for the preparation of MMO mainly are based on aerosols
that include gas condensation techniques, [39–41] spray pyrolysis, [42, 43] ther-
mochemical decomposition of metal–organic precursors in flame reactors [44, 45].
Among physical methods, perhaps flame spray pyrolysis (FSP) was found to be
most useful and extensively used for the preparation of MMO nanoparticles. This
method was developed and patented by University of Michigan [50]. Tal materials
Inc. adopted flame spray pyrolysis method for commercial production of inexpen-
sive MMO nanopowders. FSP is collective term for preparation techniques such
as aerosol thermolysis, evaporative decomposition of solutions, plasma vaporiza-
tion of solutions, aerosol decomposition, flame pyrolysis, etc. Here, the appropriate
salts or precursors in form of sol, solution or suspension can be used, whichever is
17 Role of Synthesis in Evolution of Catalyst: Bulk … 725

Fig. 17.3 Flowchart showing the methods for the preparation of MMO nanoparticles

conveniently available. These precursors can be automized by various methods such

as including pressure, two-fluid, electrostatic and ultrasonic atomizers resulting in
2–15 μm droplets depending on atomization rate and droplet velocities. Pramanik
et al. [51] reported a new polymer matrix-based precursor solution for the synthesis
of a variety of nanosized MMO such as Spinels MgAl2 O4 , CuFe2 O4 , NiFe2 O4 ,
CoFe2 O4 , ZnFe2 O4 , also orthoferrites such as LaFeO3 , NdFeO3 , GdFeO3 powders
using thermolysis/flame pyrolysis.
Other physical methods such a mechanical milling and laser ablation follow top-
down approaches are single step, easy to execute and does not require toxic/hazardous
chemicals or solvents. The fundamental principle is energy imparted to material
through either collisions among reactants and metal balls or laser energy to break
the larger particles into smaller ones. The mechanical milling or say ball milling
methods cannot be employed for reduction in particle size infinitely. Shin et al. [52]
reported an investigation on wet ball milling of Al2 O3 powders using zirconia balls
with varying speed and ball sizes. They revealed that for a given speed, there is an
optimum size of balls, which can yield minimum particle size. The optimum ball
diameter deceases as the rotation speed of ball milling increases. This is obvious also
as the speed increases, the kinetic energy increases which shift the ball size toward
smaller size. Also for a given rotation speed and optimum ball diameter, with an
increase in amount of sample from 1 to 35 g, the milling efficiency decreases. Thus,
mechanical procedure by ball milling will not reduce the particle size infinitely; in
fact, it is limited by sample amount, particle size, rotation speed and ball diameter.
726 M. R. Pai et al.

17.3 Dispersed Catalysts

Table 17.1 shows another category of catalysts called dispersed or supported catalysts
used in industry, where active component is dispersed over support such as supported
V2 O5 for SO2 oxidation used in contact process, MoO3 supported on Al2 O3 for
demethylation, hydrocracking processes, Ni/Al2 O3 for steam reforming and so on
so forth. Here, the active component is carried by most often less reactive oxides
such as stoichiometric oxides, Al2 O3 , SiO2 etc. In a heterogeneous catalytic reac-
tion, adsorption/desorption of reactants/intermediates/product species takes place
on surface of the catalyst. Thus, efficiency of a process is largely determined by the
surface properties such as surface area, crystallite size, porosity of a catalyst. To
increase the surface area, crystallite size has to be sacrificed. A correlation between
the specific surface area and crystallite size of nickel metal shows that for preparation
of reasonably high surface area Ni catalyst, particle size has to be decreased below
10 nm [53]. To carry such small nanoparticles, a support is required.
Porous supports are preferred in order to allow high loading of highly dispersed
metal particles. Supported catalysts fulfill the following two requirements: i. Reduces
cost of catalyst, the amount of active component dispersed is much less as compared
with bulk catalysts, more economical in case of precious metal (Pt, Au, Ag, Rh,
Ru) supported catalysts, ii. Improves the quality of catalyst. Supported catalysts also
propose to immobilize the organometallic complex or enzyme on an inert support
thus, allowing easy recovery of active phase after reaction and solves one of the major
issues of homogeneous catalysis. The invention of supported catalysts, advance-
ment in field of heterogeneous catalysis has rendered affordable and superior noble
metal catalysts to industry for various applications. Actual credit goes to researchers
who have invested serious efforts and interest in preparation procedures of catalyst
and have investigated the influence of preparation parameters in detail on catalyst
properties and eventually activity [54, 55].
Impregnation and precipitation are two very successful methodologies to disperse
active component on a support. However, both are extremely different in their
approach. One is impregnation in which active component is dispersed by ion
exchange on an already selected optimal design support with well-defined surface
area and porosity. After interaction with metal precursor, the samples are dried,
calcined and undergo reduction step. Other is precipitation route in which support
particles allows nucleation or crystallization of active component into fine particles
from its precursor. Precipitation can be carried out by co-precipitation, homoge-
neous deposition precipitation and precipitation at constant pH techniques [53]. The
supported catalysts can take a powder or granular form or the form of a pre-shaped
support (Fig. 17.2).
Impregnation route is more advantageous as compared with precipitation as this
route provides choice for support with desired pore structure, surface area, shape,
size and mechanical strength. Thus, impregnation route offers tailor-made catalysts
with respect to support such that it can manipulate mass transport properties. For
example, in automobile industry, the catalytic converters (to catalytically convert
17 Role of Synthesis in Evolution of Catalyst: Bulk … 727

harmful gases of automobile exhaust into harmless products) utilize monoliths as

carriers for the active noble metals using impregnation route. These monolith supports
are specifically designed to overcome mass transfer and mechanical stability issues
and, therefore, have unique pore as well as geometrical structure. The develop-
ment of impregnation route facilitated the anchoring of active components on such
supports. Impregnation method as the name suggests, precursor of the active compo-
nent containing thermally unstable anions (nitrates, acetates, hydroxides, carbon-
ates, chlorides) or cations (ammonium) is allowed to interact with the pre-shaped
or powder support, either by exchanging with surface OH or gets adsorbed over it.
For reaction, the concentration of hydroxyl groups on surface of support matters,
which can be controlled by pretreating the support under different conditions. While
in case of interaction through adsorption, surface charge is very crucial. The pH
value at which surface is electrically neutral is called point of zero charge (PZC). For
pH more than PZC, the surface is negatively charged, and for pH values <PZC, the
surface acquires positive charge. Depending on the cation or anion of the precursor
to be adsorbed, the pH is maintained for maximum adsorption. PZC for alumina
and silica is 8–9 and 3, respectively. For the synthesis of dispersed alumina or silica
catalysts, one has to select appropriate pH for modifying the surface charge of carrier
depending on the cationic or anionic precursors. It is important to mention that the
exact PZC values of carrier depend on its chemical nature also on its source and
method of preparation. Also, it may happen that the carrier may not be stable and
dissolve at some inappropriate pH value say >12 for alumina. If the adsorption of
[Pt(NH3 )4 ]2+ on silica gel and alumina supports with increasing pH is compared,
then it was observed clearly that silica gel adsorbs Pt ions more than alumina. Since,
PZC of silica is 3, so as soon as pH 3 is crossed, its surface charge becomes nega-
tive and Pt adsorption takes place upto pH of 9. In case of alumina PZC is much
higher (8–9) than silica and could not adsorb Pt species unless pH was raised more
than 8. On similar lines, it is predictable that adsorption of anionic Pt species such
as [Pt(Cl)6 ]2− would follow reverse, will be more for alumina than silica. Thus, to
prepare Pt/alumina catalysts, by ion exchange, [Pt(Cl)6 ]2− and for Pt/silica-supported
catalysts, [Pt(NH3 )4 ]2+ precursor should be preferred.
Another main highlight of impregnated catalysts is distribution profiles of active
phase on support. The distribution of active phase may or may not be uniform and it
may acquire different forms. Figure 17.4 shows different distribution profiles possible
by impregnation. These are termed as uniform, egg-shell, egg-white and egg-yolk.
Each profile is beneficial for specific reactions. By modifying the parameters of
drying step or pretreatment step of support during synthesis, the distribution profile
of supported impregnated catalysts can be tailored [56–58]. For reactions, where
catalyst is susceptible to pore-mouth poisoning, it is advisable to anchor the active
sites in the interior of catalysts as in egg-yolk profile. Similarly, to prevent leaching
of precious metals during reaction, it can be placed in the interior of catalysts.
Under normal conditions, adsorption of H2 PtCl6 over alumina will yield egg shell
type of profile, however, in the presence of some poison such as citric acid, it will
be adsorbed preferably on the outer surface, and H2 PtCl6 will then be adsorbed
on inside ring leading to egg-yolk profile (Fig. 17.4d). Drying after adsorption is
728 M. R. Pai et al.

(a) (b) (c) (d)

Acve Phase Support

Fig. 17.4 Shapes of distribution profiles of active phase over support obtained in impregnated
catalysts

very critical in determining the homogeneous dispersion of active phase. In drying

step, the solution inside pores will be dried and precipitation of active phase will take
place. Fast drying may lead to fast evaporation of the precursor, with inhomogeneous
distribution. Slow drying with well-crystallizing precursors will result in egg-shell
profile. The use of more viscous, less crystallizing precursor and slow drying leads to
homogeneous dispersion [56]. In case of structured monoliths, microwave or freeze-
drying is applied for homogeneous distribution [57, 58]. However, conventional
stationary air drying resulted in increased concentration of Ni ions at the entry and
exit of monoliths, which was not suitable for the application.
Impregnation technique is well established and recommended for lower metal
loadings with high dispersion of small crystallites. However, for higher loadings and
high dispersions, the procedure has to be repeated many times till required loading is
achieved. Precipitation method has this advantage; in this method, the metal precursor
solution is supersaturated to induce nucleation and crystal growth of metal particles.
If both support and metal precursors are taken together and allowed to co-precipitate,
it is referred as co-precipitation. In case metal precursor solution is allowed to super-
saturate on existing support, it is called homogeneous deposition precipitation (HDP)
[53, 59]. Both co-precipitation and HDP techniques offer advantage of higher load-
ings with high dispersion. The HDP can be carried out either under influence of
increasing pH or constant pH conditions [59–61]. The details of these methods are
given in several review articles as well as books [62–64].
Besides these methods, there are more recent and advanced methodologies to
prepare supported catalysts such as melt filtration, colloidal route and vapor depo-
sition [65–67]. Mehrabadi et al. [67] have provided a thorough survey of different
methods for preparation of most popular and extensively applied Pt catalysts on
four different supports, TiO2 , Al2 O3 , SiO2 and carbon. A histogram presentation
was prepared after survey of around 1500 studies published during the period from
2015 to 2017. Since particle size achieved of the metal particles is one of the criteria
predicting the efficacy of the catalyst, so particle size obtained from different prepa-
ration routes of these four different catalysts from 1500 studies is presented. It
17 Role of Synthesis in Evolution of Catalyst: Bulk … 729

compares the different emerging routes with traditional routes. Strong electrostatic
attractions (SEA) and charge enhanced dry impregnation are newer approaches to
modify conventional impregnation route [67].

17.4 Single Atom Catalysts (SAC)

Supported metal catalysts are widely used in industry for various heterogeneous
catalytic processes. The particle size of metal ions is a key aspect that influences the
catalyticperformance. Figure 17.5 shows the effect of particle size on conversion and
surface energy of supported catalysts.
Downsizing the metal ions increases the number of active sites on surface and
offers more active sites for a catalytic reaction. Decrease in particle size increases
the specific activity of catalyst by providing low coordination unsaturated envi-
ronment, quantum size effects and associative metal support interactions [68–70].
Progress through numerous modifications in synthetic procedures and optimiza-
tion of synthetic parameters to the finest resolution created supported catalysts with
nanosize as well as sub-nanosized metal particles/clusters. Despite nanosized, the
supported catalysts still suffer with existence of range of nanosized metals dispersed,
instead of uniform sized particles. This brings heterogeneity on the catalyst surface as

Fig. 17.5 A schematic depicting the effect of particle size of active phase on catalytic conversion
and surface energy
730 M. R. Pai et al.

active sites contain multiple active centers that may set aside undesired side reactions,
and thus deteriorates the catalyst performance.
In view of above considerations, the ideal scenario would be uniform distribution
of single atoms of metal on the support. This is the ultimate goal of fine disper-
sion for supported catalysts, also referred as single atom catalysts (SACs) [71–74].
SACs have huge potential due to their superior catalytic properties and, therefore,
are new frontier area in catalysis research. The advantages of single atom cata-
lysts are; drastic improvement in catalytic performance, facilitates understanding
of catalytic mechanisms, and have huge potential in bringing down the cost of
commercial noble metal catalysts in industry. The first and foremost challenge in
the development of SAC is their synthesis, and the second is development of tools
to characterize them. Recent studies [74–77] have shown technological advance-
ments toward the synthesis of SACs with indubitable characterization. The very first
synthesis of single atom catalysts was reported by Qiao et al. [73]. Single Pt atoms
were successfully anchored on FeOx support using co-precipitation method under
carefully optimized pH and temperature conditions also reported exceptionally high
catalytic activity and stability for CO oxidation reaction. It was simulated using
density functional theory and revealed that partially vacant 5d orbital of Pt plays role
in decreasing the activation barrier for CO oxidation reaction. The morphology and
distribution of single atoms/metal clusters are characterized using subangstrom reso-
lution, aberration-corrected scanning transmission electron microscopy (STEM) in
the catalysts. High-angle annular dark-field (HAADF) helps in identifying the heavy
atoms at atomic resolution.
Chief obstacle in preparation of SAC is the high surface energy associated with
single atom, which causes migration and agglomeration of the atoms. Therefore,
role of support is very important to achieve dispersion and stabilization of single
atom. Support that has defect sites or other specified sites where metal particles
can be anchored are preferred. Some of the strategies for the synthesis of SACs are
summarized below.

17.4.1 Atomic Layer Deposition (ALD) Method

Atomic layer deposition (ALD) method is a sophisticated technique used for the depo-
sition of a catalyst in the nanometer and subnanometer range in a controlled manner
by changing the number of deposition cycles [78]. However, long processing time and
relatively high cost are the demerits of this method. ALD has been used for the depo-
sition of the SACs. This method offers the control over the size, morphology, density
and the amount of deposited metal. ALD is divided into four steps: (i) exposure of
the metal precursors, (ii) precursor or by-product removal from the chamber by evac-
uation or purging, (iii) exposure of reactant species and (iv) removal of the reactants
and by-product from chamber by evacuation or purging [79]. Sun and coworkers
[80] implemented the ALD method for the deposition of the Pt single metal atom on
the surface of the graphene used as a support. Deposition was carried out by using
17 Role of Synthesis in Evolution of Catalyst: Bulk … 731

(methylcyclopentadienyl)-trimethylplatinum (MeCpPtMe3 ) and oxygen as precur-

sors, and nitrogen as purge gas. Figure 17.6 shows the schematic representation of
the reactions expressed by Eqs. 17.1 and 17.2:
Equation 17.1:

Fig. 17.6 Schematic representation of the ALD process for Pt deposition on graphene nanosheets
(GNS), a existence of the monolayer of functional groups possessing oxygen ions on the surface of
the graphene nanosheets, b during exposure of the MeCpPtMe3 , some of the ligands reacts with the
adsorbed oxygen on the surface leading to the generation of Pt containing monolayer, c exposure
of oxygen leading to the formation of the adsorbed oxygen layer on the surface. Process b and
c constitute a complete ALD cycle. By varying the ALD cycles, d a Pt deposition in a controlled
way can be achieved. (* and Pt-O* represent an active surface species and oxygen molecules or
dissociated oxygen ions adsorbed on the Pt surface). Reproduced with permission from Ref. [80],
with the permission from Springer Nature
732 M. R. Pai et al.

Equation 17.2:

where, * and Pt-O* correspond to the active surface species, and oxygen molecules
adsorbed on the Pt surface, respectively. The ALD cycle composed of two processes.
First is exposure of the MeCpPtMe3 , where precursor ligands reacted with the
adsorbed oxygen to form CO2 , H2 O and hydrocarbon fragments as shown in Fig. 17.6
and Eq. 17.1. The limited oxygen supply prevented the oxidation of all ligands and
helps to form Pt monolayer. In the second process, a new layer of the adsorbed
oxygen formed on the surface of Pt on the exposure of the oxygen. The amount of
Pt was accurately controlled by the number of ALD cycles. The catalytic activity
for methanol oxidation reaction using Pt SACs was found to be 10 times higher than
that of commercial Pt/C catalyst.

17.4.2 Wet-Chemical Route

The surface defects present on the surface of the support offer the site for the attach-
ment of the single atom. The metal–support interaction prevents the aggregation of
the single atoms. Co-precipitation method is the most commonly employed method.
The temperature and pH are the important parameters during synthesis of SACs by
this method. Qiao et al. [73] synthesized the atomically dispersed Pt over FeOx by
co-precipitation method. Here, simple strategy of dispersion of lower metal loadings
leads to better dispersion on high surface area nanocrystalline support (290 m2 g−1 )
was adopted to successfully anchor the Pt ions on to the defects sites of the FeOx
support. 0.17 wt% of Pt with Pt/Fe ratio of 1/1430 was dispersed to prepare Pt1 /FeOx
SAC using co-precipitation method. SACs were compared with conventional cata-
lysts with similar loading (Pt loading of 2.5 wt% with a Pt/Fe atomic ratio of 1/95)
to establish and affirm their superiority catalytic activity. These methods are widely
used for the synthesis of the SACs as it is easy to operate and no requirement of any
special equipment. Moses-De Busk et al. [81] have dispersed single atom of Pt over
the support by wet impregnation method. In this method, Θ-Al2 O3 dispersed in an
aqueous solution of the chloroplatinic acid and then the water was evaporated to get a
powder, which was calcined at 450 °C. With the help of computational studies, it was
deciphered that Pt was situated between two oxygen atoms of support. Characteri-
zation using STEM, IR and EXAFS data show that the samples are supported single
Pt atoms. Based on their investigations, they concluded that the conventional Lang-
muir–Hinshelwood mechanism is not applicable for CO oxidation on single atom
and proposed a variation of L–H mechanism for CO oxidation reaction on SACs.
17 Role of Synthesis in Evolution of Catalyst: Bulk … 733

17.4.3 Photodeposition Method

This method involves the utilization of light energy for the deposition of the metal
atom. This method is better than the conventional calcination methods as it prevents
the agglomeration of atoms to give cost-effective nanoparticles. Liu et al. [82]
dispersed Pd atomically over ultrathin TiO2 nanosheets up to 1.5 wt% (referred
as Pd1 /TiO2 ) under UV light photodeposition. Ultrathin nanosheets of TiO2 were
synthesized using TiCl4 and ethylene glycol (EG) as the precursors. It was observed
that the TiO2 nanosheets were coated with ethylene glycolate. The ethylene glycol
radicals were generated during UV irradiation that helped in removal of the Cl− ions
from the Pd precursor. To load Pd atom, H2 PdCl4 dispersed in water and then irradi-
ated under UV source. As a result of this Pd atom was stabilized by forming Pd–O
bonds over TiO2 nanosheets. Pd1 /TiO2 exhibited high catalytic activity and stability
for styrene hydrogenation reaction as compared the commercial Pd/C catalyst.

17.4.4 Atom Trapping Strategy

Pt nanoparticles agglomerate into large particles undergoing aging treatment at high

temperature in air. This process is called as Ostwald ripening. Carrillo et al. [83]
found that the PdO could trap mobile PtO2 to form Pt–Pd alloy, thus, prohibiting the
sintering of the Pt nanoparticles. By taking inspiration from this work, Jones et al.
[84] synthesized the atomically dispersed Pt over CeO2 . For this, 1 wt% Pt/La-Al2 O3
and CeO2 was physically mixed in 2:1 weight ratio and then subjected to the aging
treatment at 800°C in air flow. During aging treatment, the vapor of mobile PtO2 was
emitted from alumina and got deposited over surface of ceria to form the atomically
dispersed Pt/CeO2 catalysts.

17.5 Thermal Reactions

Mixed metal oxides are suitable catalyst systems for oxidation or reduction processes.
In our laboratory, we continually prepared and improvised oxide-based catalysts for
CO oxidation, CO + N2 O reactions and SO2 oxidation reactions. Here, in this section,
highlights of our work are presented to emphasize the role of synthesis in improvising
the catalyst performance and stability.
734 M. R. Pai et al.

17.5.1 CO Oxidation

First example is about strategy to improve the thermal stability of active bulk cata-
lyst, V2 O5 . It is known to be a good catalyst [85] for many inorganic and organic
reactions but it melts at 658 °C whereas lower valent oxides like VO2 and V2 O3 melt
at 1640 °C and 1970 °C, respectively, but they were catalytically inactive. Therefore,
a way of stabilizing such low melting oxide can be in the form of oxy anions. As
vanadium exhibits multiple oxidation states right from 2 to 5, its mixed oxides can
exist as varied anionic species like VO− 3 (metavanadate with perovskite structure),
V2 O7 4− (pyrovanadate with pyrochlore structure) and VO4 3− (orthovanadate with
scheelite structure). ThO2 is thermally stable. Thus, combination of catalytically
active, V2 O5 and thermally stable, ThO2 in different stoichiometric ratios resulted
in ternary compounds, viz; thorium metavanadate, Th(VO3 )4 and thorium pyrovana-
date, ThV2 O7 and thorium orthovanadate, Th3 (VO3 )4 where vanadium is in +5 and
Th exists in +4 valence state. Both Th(VO3 )4 and ThV2 O7 are stable up to 1000 °C
and have stable structure. The structural aspects of these three oxides systems were
available in literature but as far as catalytic properties are concerned almost nil or
scanty information was available. In our laboratory, we, thus, entered into a totally
unexplored area of research on thorium vanadates, synthesized, characterized and
evaluated temperature-dependent catalytic activities of these oxides for CO oxida-
tion. These multi-metal oxides were found to exhibit the improved thermal stability
as well as catalytic activity [26–30]. Several nominal compositions of La/Mn substi-
tuted non-stoichiometric Th3 (VO3 )4 and pyrovanadates were found to be active in
temperature window of 300–400 °C. Since, catalytic activity in case of oxides is
determined by the crystal structure of the phase obtained and also mixed phase
composition, our studies on La and Mn substituted Thorium vanadates could estab-
lish the structure–activity correlations. The thorium vanadates in our studies were
prepared by ceramic route, which has drawback of insufficient homogeneous mixing.
For enhancing the catalytic activity, synthetic procedures were modified allowing
mixing of metal ions at atomic level by mixing nitrate solutions of metal ions in appro-
priate stoichiometry. Solution route fabricated pure phase mixed oxides, prevented
the segregation of secondary phases due to homogeneous mixing and reactions.
A new series of perovskites with Fe substitution at B site, La0.8 Sr0.2 Mn1-x Fex O3-δ
(LSMF) samples with x values from 0 to 1.0 were also synthesized by solution route
using nitrate precursors and compared with their solid-state analogues, and finally
calcining at 900 °C and 1400 °C, respectively [86, 87]. Since the metal ions come
in close contact in solution route, their diffusivity during lattice reorganization is
enhanced, leading to single phase formation at lower calcination temperatures. Thus,
samples prepared by nitrate route yield the pure phase orthorhombic Fe substituted,
LSMF samples at 900 °C while solid state route required 1400 °C. As expected,
the solution route LSMF (x = 0.2–0.4) samples produced 15–16 nm crystallites as
compared with 49–50 nm through solid state route [86]. LSMF2 sample exhibited
100% conversion at 400 °C as compared with ~60% conversion when prepared by
ceramic route. This was also augmented by increased reducibility of the sample at
17 Role of Synthesis in Evolution of Catalyst: Bulk … 735

lower temperature shown in their temperature programmed reduction (TPR) profiles.

The results of comparative study of same compositions prepared by different routes,
revealed that the particle morphology is a crucial factor in determining the catalytic
performance. The substitution-induced micro-structural defects and the synergistic
effects due to presence of multivalent Fe and Mn ions at b-site, play an important role
in determining and uplifting the catalytic behavior of the substituted perovskites.

17.5.2 N2 O Reduction

Nitrous oxide (N2 O) poses threat to environment as it contributes to global warming

causing stratospheric ozone destruction. N2 O emissions can be converted to harmless
gases catalytically by supported metals, zeolites, pure or mixed oxides [88]. Here, we
present the sequence of adaptations in our approach to enhance the catalytic activity
for CO + N2 O reaction. To begin with bulk layered perovskite, lanthanum titanate,
La2 Ti2 O7 with Fe substitution at B-site were prepared by citrate gel combustion (GC)
route using metal nitrate precursors and compared with conventional solid-state (SS)
synthesis [89, 90]. Among complete series of La2 Ti2(1-x) Fe2x O7-δ , nominal composi-
tion of La2 Ti1.2 Fe0.8 O7-δ (LF4) was found to be most active for CO + N2 O reaction,
where activity was credited to substitution induced non-stoichiometry defects and
short-range crystallographic shears, which increased the lability of lattice oxygen
at lower temperatures, thus improving the catalyst activity [89]. Gel combustion
synthesis lowered the reaction temperature considerably . 100% conversion was
achieved at 325 °C with onset at 200 °C while with solid-state samples, conversion
initiated at 275 °C and a temperature of 550 °C was required for 100% conversion
using 40–60% Fe substituted samples. Thus, lowering of particle size and increased
surface area by GC route improved the reaction kinetics. The role of Fe substitu-
tion was further investigated by monitoring the CO + N2 O reaction insitu using
FTIR as probe. As a result of aliovalent, Fe3+ substitution, additional active sites in
form of anionic vacancies/defects or pores are created, where CO and N2 O gases
are chemisorbed. Insitu IR shows a band of 1337 cm−1 at 200 °C over LF4 sample,
and 1230 cm−1 over unsubstituted LTO surface attributed to carbonate formation.
Normally, the adsorption at defect site such as anionic vacancy or pores in LF4
leads to more stronger adsorption at higher wave number (1337 cm−1 ), as compared
with normal terrace sites as in LTO (1230 cm−1 ) [90]. The intensity of band due to
gaseous phase CO2 at 2342 cm−1 correlates well with the carbonate formation. The
presence of easily reducible Fe3+ ions and highly mobile lattice oxygen assists the
binding of CO with two surface oxygen, thus forming carbonate (CO3 2− ) species
over iron-substituted sample. The carbonate formation facilitates the reduction of
pre-adsorbed N2 O on LF4 surface. However, the unsubstituted, parent lanthanum
titanate, La2 Ti2 O7 , are stoichiometric oxide and, therefore, deficient in such reactive
sites on the surface. Thus, reactants were physisorbed not chemisorbed as suggested
by the absence of insitu carbonate formation. Based on insitu FTIR investigations and
catalytic activity results, following mechanism over Fe-substituted LF4 sample was
736 M. R. Pai et al.

proposed. It follows a redox mechanism here, where the surface is initially reduced
by CO, and then, the reduced surface is oxidized by dissociative N2 O chemisorp-
tions (Scheme 1). While, in case of unsubstituted lanthanum titanate, La2 Ti2 O7 , an
associative mechanism was observed.
Dispersed catalysts
With an objective to further decrease the temperature required for the 100% conver-
sion, for CO + N2 O reaction, fine powders of metal ions (Ni, Co and Pt) were
dispersed on Fe substituted/unsubstituted lanthanum titanate, La2 Ti2(1-x) Fe2x O7-δ
oxides as supports. Two compositions of La2 Ti2(1-x) Fe2x O7-δ oxides in which x =
0 and 0.4 (LTO and most active LF4 from previous section) were chosen to act as
support for dispersion of Ni, Co and Pt metal ions. Lanthanum titanate, La2 Ti2 O7, or
modified Fe substituted, La2 Ti1.6 Fe0.4 O7-δ are layered perovskites with several advan-
tages as support as compared to alumina or other traditional supports. La2 Ti2 O7 is
stable toward reduction and oxidation atmosphere up to 1000 °C. La2 Ti2 O7 is a
monoclinic layered perovskite, which is capable of compensating for small fluctu-
ations in the oxygen content of automobile exhaust by virtue of the mobile lattice
oxygen and reducible B-site cations. Thus, metal dispersed on perovskite surface can
migrate between the B-site in the perovskite structure and the metal particle lattice
site in the real catalyst when exposed to fluctuation of the oxygen content of the
emission exhaust. Perovskite surface offers stability to dispersed metal ions during
prolonged use and prevents the aging, agglomeration and subsequent deterioration
of catalyst performance [88] unlike the conventional catalysts, Pt/Al2 O3 , Pd/Al2 O3 .
Thus, here some important observations and findings are given that are obtained after
dispersing metals (Pt, Ni, Co) on unconventional layered perovskites as supports.
Support samples La2 Ti2 O7 (LT) and La2 Ti1.2 Fe0.8 O7-δ (LF4) were synthesized by
gel combustion route (GC) followed by dispersion of metal using wet impregnation
method resulting in M-La2 Ti2(1-x) Fe2x O7-δ oxides (M = Ni, Pt and Co; x = 0 and 0.4)
compositions characterized by XRD, SEM, TEM, XPS, TPDRO and AAS. Reduction
behavior of these supported perovskite catalysts was monitored by recording multiple
TPR-TPO cycles and further analyzed for CO + N2 O as well as N2 O decomposition
catalytic reactions. The course of adsorption of CO, N2 O and CO + N2 O, formation
of intermediate species on the surface of self-supported catalyst pellets during the

CO (g) + * CO*
*-CO + O* + O2- *-CO3 2- + * CO2 + *-O + 2e
N2O (g)+ * N2 + *-O
CO (g)/*-CO + O* CO2 + *
Scheme 1. Reactive sites on catalyst surface facilitated carbonate formation and N2 O decompo-
sition as shown in above mechanism proposed for CO + N2 O reaction proceeding via CO3 2−
formation over Fe-substituted Lanthanum Titanate, LF(0.6)GC, sample
17 Role of Synthesis in Evolution of Catalyst: Bulk … 737

catalytic reaction was monitored by insitu FTIR to provide insights about the reaction
mechanism involved. XRD patterns of Ni, CO and Pt dispersed on La2 Ti1.2 Fe0.8 O7-δ
sample revealed the formation of single phase of rhombohedral LaFeO3 (JC-PDS No.
37–1493) with unit cell parameters a = 5.566 Å, b = 7.854 Å, and c = 5.56 Å, Vol
= 242.81 Å3 . No additional XRD reflections due to metal ions were observed for M-
LTO/LF4 samples suggesting that metal ions are finely dispersed on surface and were
left undetected by XRD. Oxygen excess layered perovskite, A2 B2 O7 support was
subjected to consecutive four to five reduction-oxidation cycles. Each temperature
programmed reduction (TPR) cycle was followed by a temperature programmed
oxidation (TPO cycle). It was found that A2 B2 O7 support reorganizes to ABO3
type perovskite lattice on reduction (TPR) and reverse was observed for TPO cycle.
This shows that support lattice facilitates easy removal and uptake of oxygen, due
to its capability of reorganizing within same composition. After metal dispersion,
additional low-temperature peaks at ~ 150 °C and 280 °C were also observed in first
and second TPR cycles of Pt-LFGC and Ni-LFGC samples attributed to reduction
of Pt and Ni, respectively (Fig. 17.7). TPR profiles suggest strong metal–support
interactions. During first cycle, due to strong interactions and linkages of M–O–LT

Fig. 17.7 Metal support interactions are evident by multiple TPR/TPO profiles of
Pt/La2 Ti1.2 Fe0.8 O7-δ and Ni/La2 Ti1.2 Fe0.8 O7-δ supported catalysts
738 M. R. Pai et al.

type, a sluggish profile with poor reduction kinetics was observed. However, during
second cycle, metal ion bonds with support weakened and show distinct reduction
peaks (Fig. 17.7). All these samples were found to be active and the decreasing
order of catalytic activity was NiO-LT (PT-LT) > NiO-LF4 > PtO-LT > Ni-LF4 >
Ni-LT > CoO-LT > Co-LT (Fig. 17.8). For the CO + N2 O → CO2 + N2 reaction,
the maximum conversion was observed with NiO dispersed on LT support where
sample showed activity at 250 °C and attained 100% conversion at 300 °C. Metal
dispersed LT/LF4 samples have exhibited considerably enhanced activity, as against
support alone. Negligible conversion was observed for LTO at 300 °C. In case of
LF4, conversion was initiated at 300 °C and 100% was reached at 400–410 °C. TEM
image of NiO/LT sample (Fig. 17.9) confirmed uniform dispersion of amorphous
NiO particles with average size of ~10–12 nm on crystalline La2 Ti2 O7 support.
Electron diffraction images (inset of Fig. 17.9) show two different patterns, one is

Fig. 17.8 The temperature-dependent catalytic activity of M-La2 Ti2(1-x) Fe2x O7-δ oxides for CO +
N2 O reaction
17 Role of Synthesis in Evolution of Catalyst: Bulk … 739

NiO (220)

NiO (111)

100 nm LT- Support

Fig. 17.9 TEM/ED image of NiO dispersed on lanthanum titanate support (white spots correspond
to the NiO nanoparticles). Inset shows electron diffraction patterns corresponding to nanocrystalline
NiO and lanthanum titanate crystalline support

showing diffused rings due to 220 and 111 planes of amorphous NiO dispersed
on support, other consists of well-defined dots attributed to crystalline monoclinic
lanthanum titanate support. Highly dispersed NiO nanoparticles are responsible for
the considerable rise in activity over NiO/LT sample as compared with other samples.
Pt-LTGC exhibited considerable enhancement in catalytic activity for CO oxidation
reaction with onset at 75 °C and complete 100% conversion at 275 °C (Fig. 17.8).
Temperature-dependent insitu IR results show the adsorption and conversion of CO
to CO2 via carbonate formation evident at 1585 cm−1 in temperature range of
250–300 °C (Fig. 17.10). Metal dispersed samples also facilitated the adsorption and
decomposition of N2 O alone considerably at 300° as observed on NiO-LTGC surface
(Fig. 17.11), in contrast to support samples, LT and LF4 where no decomposition was
observed even at 350 °C. Overall, conclusion is that dispersion of Ni and Pt metal
ions by impregnation on La2 Ti2 O7 and LF4 support modifies the characteristics
of bulk LT/LF4 catalysts considerably and makes them superior catalysts for N2 O
decomposition reaction.
740 M. R. Pai et al.

CO2
573K

2-
523K
M-CO
3
Intensity (a.u.)

1585

473K

373K

Gaseous CO
RT

1500 2000 2500

-1
Wavelength (cm )

Fig. 17.10 To monitor the adsorption of CO as a function of temperature on surface of NiO-LTGC

catalyst using insitu FTIR spectroscopy

17.5.3 H2 SO4 Decomposition

Another very useful thermal reaction for which we have developed catalysts
is sulfuric acid decomposition reaction. It is one of the most challenging and
endothermic steps of sulfur-based thermochemical cycles [91, 92]. Thermochem-
ical water splitting cycles are designed based on Hess’s law of chemical thermody-
namics. Water splitting into hydrogen and oxygen is achieved via chemical reactions
using intermediate elements and compounds, which are recycled. The sum of all
the reactions is equivalent to the dissociation of the water molecule. Sulfuric acid
decomposition takes place in following two steps:

H2 SO4 (l) → H2 O(l) + SO3 (g)(450◦ C) (17.3)


SO3 (g) → SO2 (g) + 1 2O2 (g) (800 − 900◦ C) (17.4)
17 Role of Synthesis in Evolution of Catalyst: Bulk … 741

Fig. 17.11 To monitor the adsorption of N2 O as a function of temperature on surface of NiO-LTGC

catalyst using insitu FTIR spectroscopy

First is simple thermal decomposition of sulfuric acid into its anhydride by loss
of water at ~450 °C, while second is the reduction of SO3 to SO2 , with evolution
of oxygen is a catalytic reaction. Figure 17.12 shows the calculated thermodynamic
yield and experimental yield in the absence of catalyst obtained at different tempera-
tures [93]. Without catalyst, almost negligible yield is obtained around 1073 K. It has
slow kinetics in the absence of catalyst. Some of the reported noble metal-based cata-
lysts employed for sulfuric acid decomposition include supported platinum catalysts
such as (Pt/ Al2 O3 , Pt/ TiO2 and Pt/ ZrO2 ) [94], (Pt/TiO2 (rutile) [95], (Pt/BaSO4 )
[96] and theoretical studies on supported metal particles (Pd, Pt, Rh, Ir and Ru
supported on titania) [97]. Metal oxide catalysts are active and can be a substitute for
noble metal catalysts as they fulfill the essential requirement of materials with better
chemical, thermal stability and modified catalytic properties. Long back in 1977,
742 M. R. Pai et al.

Fig. 17.12 Comparison of thermodynamic yield and experimental yield in the absence of catalyst
as a function of temperature obtained in H2 SO4 decomposition reaction. Reprinted from Ref. [93],
with permission from Elsevier

Dokiya et al. [98] first reported the use of several metal oxide catalysts for sulfuric
acid decomposition, where Fe2 O3 was found to be the most active catalyst. Thus, to
explore the potential of cheap Fe-based catalysts, development of Fe-based catalysts
started at our end. To begin with, studies on Cr doped Fe2 O3 -based powder catalysts
were undertaken [99–105].
Bulk catalysts: A series of iron-chromium binary mixed oxides (Fe2(1-x) Cr2x O3 :
0 ≤ x ≤ 1.0) Fe2x Cr1-x O3 were synthesized using ceramic route. Highly crystalline
powders are obtained by this method and if proper intermittent grinding and heating
are done, the product obtained is also homogeneous. One of the disadvantages of this
method is that the powders obtained are in micron range as high-temperature heating
causes sintering and grain growth. The catalytic activity of Cr substituted sample
during prolonged duration was found to be better than unsubstituted iron oxide [101].
This was also further established by reproducible TPR/TPO cycles. The maximum
conversion was obtained at 800 °C with the onset of formation of SO2 at 600 °C. Solid
solution of 20% Cr substitution in Fe2 O3 lattice has not only enhanced reproducibility
toward repeated reduction–oxidation cycles but also prevented the deactivation of the
catalyst during use in sulfuric acid decomposition reaction. Fe1.8 Cr0.2 O3 was found
to be promising active and stable mixed oxide catalyst for the above reaction. For,
further improvement in catalytic and mass transfer properties considering fixed bed
reactor, granular Fe1.8 Cr0.2 O3 and Fe2 O3 catalysts were prepared by co-precipitation
route as described in Scheme 2. The main difference in the two routes is the proximity
of the reacting species. Several parameters, such as pH, mixing rates, temperature and
concentration have to be controlled to produce satisfactory results. The composition
17 Role of Synthesis in Evolution of Catalyst: Bulk … 743

Scheme 2. Synthesis Aqueous Fe(III)/Cr(III) nitrate

methodology followed to
prepare granular Fe2 O3 and
Cr doped iron oxide catalysts

Fe(III)/Cr(III) Hydroxides

Oxides

1. Granulation using PVA

2. Calcination at 750 for 12 h

Granular Catalyst (4-6 mm dia)

Fe2O3 Fe1.8Cr0.2O3

control, purity and morphology of the resulting product are good. However, different
rates of precipitation of each individual compound may lead to microscopic inhomo-
geneity. Co-precipitated granular catalysts, Fe1.8 Cr0.2 O3 and Fe2 O3 , were tested for
their efficacy in actual reactor conditions where inert gas will not be used to facilitate
the elution of product gases. The activity was evaluated in an indigenously designed
and fabricated dual-tube quartz catalytic reactor [101, 103], which served as an inte-
grated boiler, preheater and decomposer having no high-temperature connections at
larger scale of ~20 g. The concept of this dual-tube type of catalytic reactor can also
be enhanced to an engineering scale for pilot plants.
The SO2 yield as measured with chemical titrimetric method increased with rise
in temperature with a maximum activity of 76% and 82% for Fe2 O3 and Fe1.8 Cr0.2 O3
at ~825 °C. However, the SO2 yield was higher for the Cr-doped samples than the
pristine Fe2 O3 throughout the 100 h run [101].
Fe2 O3 and 10% Cr-doped Fe2 O3 catalyst pellets or granules were tested as catalyst
for sulfuric acid decomposition reaction for 100 h at 800 °C and a sulfuric acid flux of
0.63 ml/min (WHSV of 3.4 g acid g−1 catalyst h−1 ), in an indigenously constructed
quartz dual tube catalytic reactor, which served as an integrated boiler, preheater
and decomposer [102]. No decrease in catalytic activity was observed during this
long-term experiment, although the doped sample exhibited slightly higher catalytic
activity throughout. However, in the temperature-dependent catalytic runs, the Cr-
doped sample showed much higher intrinsic activity at lower temperatures (<775 °C).
Both the catalysts exhibited a loss in catalytic activity when subjected to very high
744 M. R. Pai et al.

flow of sulfuric acid of 2–10 ml/min. Bulk Fe2 O3 -based catalysts both in powder
and granular form suffer limitations of limited mass transfer.
Dispersed Fe2 O3 -based catalysts
One of the challenges in supported catalyst is to rationally design the catalysts such
that it possesses essential activity, selectivity and stability. For this, selection of
support is very critical. Jin et al. [106] reported an excellent example of rational
catalyst design of bimetallic CuPd-graphene nanocatalysts in which a deliberate
attempt to match the lattice of active metals with support phase (graphene) was
done. It resulted in exceptionally improved catalytic properties for facile conversion
of biomass-derived polyols to lactic acid, owing to electron density overlap of the
support and dispersed phase. We in our laboratory with an objective to further improve
the prowess of sulfuric acid decomposition catalyst-dispersed Fe2 O3 nanoparticles on
a support [103–105]. With an aim to investigate the metal–support interactions; Fe2 O3
was dispersed on different supports such as TiO2 , CeO2 , ZrO2 and SiO2 using equi-
librium–adsorption method [104]. Basically, support lowers the associated surface
energy and prevents agglomeration and migration of metal nanoparticles. The role
of suitable carrier here is to immobilize the iron oxide particles in the maximum
possible dispersed state and preserve the nanostructured morphology of catalyst
during long operational conditions of high temperature and corrosive exposure by
sulfuric acid. Figure 17.13 shows the catalytic activities of Fe2 O3 supported catalysts.
Role of different synthetic route supports and mesh size in development of sulfuric
acid decomposition catalyst is highlighted. CeO2 and ZrO2 underwent sintering
during calcination step at 1000 °C and yielded low surface area supported catalysts.
Anatase TiO2 formed a solid solution at 1000 °C resulted in pseudo-brookite Fe2 TiO5
dispersed over TiO2 . Among all supports, silica-supported Fe2 O3 was found to be
most active (Fig. 17.13). Silica owing to its high surface area (~249 m2 /g) facilitated
homogeneous distribution of nanosized iron oxide (~2–3 nm) as evident by TEM
mages. Surface area of SiO2 decreased to ~149 m2 /g after dispersion indicating that
Fe2 O3 has diffused inside the pores. Other supports such as ZrO2 , CeO2 resulted into
heterogeneous distribution, evident by mapping along line distribution of Fe2 O3 in
TEM images. Although same synthesis methodology was adopted, different supports
produced catalysts with varied characteristics and catalytic activity. Among different
loadings, 15 wt % was found to be most optimum with ~74% conversion at 850 °C
as shown in Fig. 17.13. The amorphous SiO2 stabilized crystalline Fe2 O3 through
Fe–O–Si linkages evident by XPS and TPR studies. In XPS, the presence of peaks at
~712.8 eV can be attributed to Fe3+ bound to the SiO2 support. A lower intensity peak
of O 2p at the highest BE value of ~533.5 eV assigned to chemisorbed surface oxygen
or surface adsorbed water or hydroxyl moieties, which progressively increased with
increase in Fe2 O3 loadings indicated that the peak could be assigned to O2− present in
dispersed Fe2 O3 . TPR profile characteristics provided evidence for reduction of Fe 3+
to Fe0 present in Fe–O–Si linkages. The amount of Fe3+ species reduced in first TPR
cycle, increased in 2, 3 and 4th TPR cycles during multiple TPR/TPO runs. Increase
in intensity of Fe3+ is possible only if we consider metal support interactions. During
17 Role of Synthesis in Evolution of Catalyst: Bulk … 745

1- (5wt %)Fe2O3/SiO2 (80-45 mesh)Eq.Adsorption method

2-(10wt %)Fe2O3/SiO2 (80-45 mesh)Eq.Adsorption method
3-(15wt %)Fe2O3/SiO2(80-45 mesh)Eq.Adsorption method
4-(20wt %)Fe2O3/SiO2 (80-45 mesh)Eq.Adsorption method
5-(15wt %)Fe2O3/SiO2(45-20 mesh) Eq.Adsorption method
6-(15wt %)Fe2O3/SiO2(45-20 mesh) Polyol
7-(15wt %)Fe2O3/SiO2(45-20 mesh) Solvothermal
8-(15wt %)Fe2O3/SiO2(45-20 mesh) Wet impregnation
9-(15wt %)Fe2O3/TiO2(45-20mesh)Eq.Adsorption method
10-(15wt %)Fe2O3/ZrO2(45-20 mesh)Eq.Adsorption method
11-(15wt %)Fe2O3/CeO2(45-20 mesh)Eq.Adsorption method

Fig. 17.13 Effect of synthesis, mesh size, loading and support on catalytic activity of Fe2 O3
dispersed catalysts for sulfuric acid decomposition reaction at 800 °C

first cycle, SiO2 inhibits the reduction of Fe3+ species anchored over it, and a slug-
gish reduction profile of Fe3+ to Fe0 was observed. Subsequently, more and more free
Fe2 O3 segregated on surface and intensity of reduction peak increased. The presence
of peaks due to Fe2 SiO4 in the XRD of spent TPR sample confirms the participa-
tion of support in reduction of active iron oxide nanophase. These metal–support
interactions facilitated sulfation of support and its facile decomposition. Although,
SiO2 could not prevent completely the agglomeration of Fe2 O3 particles, but enabled
Fe2 O3 to sustain through the corrosive environment during the long operational times
746 M. R. Pai et al.

(~100 h). A feature specific to SiO2 was that it was immune to sulfation under exper-
imental conditions in sharp contrast to what was observed for other supports such as
ZrO2 , TiO2 and CeO2 [104].
To study the role of synthesis on catalytic activity and stability, the most active
Fe2 O3 (15wt%)/SiO2 combination was synthesized by other methods also such
as polyol (P), solvothermal (ST) and wet-impregnation (WI) methods in addition
to equilibrium–adsorption method and evaluated for sulfuric acid decomposition
(Fig. 17.13). The different procedures yielded catalysts with varying crystal struc-
ture, porosity, morphology and redox properties. These were examined by XRD,
Mössbauer spectroscopy, N2 -BET surface area, SAXS, ED-XRF, HR-TEM, TPR/O
and XPS techniques. Due to their varying effect, on bulk and surface properties,
catalytic activities were also affected. Figure 17.13 exhibits that the catalytic activity
was maximum by polyol > wet impregnation ~solvothermal at 800 °C. Polyol and WI
yielded surface area of 125 m2 /g, while ST was lower of ~75 m2 /g. Pore confinement
and high calcination temperature are two main reasons for reduction in surface area.
SAXS profiles of all samples show that maximum fraction of Fe2 O3 has aggregated
inside mesopores using polyol method. The mesopores with pore radius of 12.9 nm
existing on SiO2 were filled by Fe2 O3 to a maximum extent using polyol method-
ology and that has favorable effect on its catalytic properties. Interestingly, different
methods yielded different morphology, polyol yielded rod-shaped α phase of Fe2 O3
and that goes well with filling up of mesopores observation from SAXS results too,
WI yielded elliptical shape and ST method resulted in spherical Fe2 O3 probably
due to high pressures in autoclave. TPR shows maximum hydrogen consumption
by polyol > WI > ST, thus suggesting more reducible species on surface and better
catalyst for redox reactions. Ethylene glycol is a high boiling solvent used in polyol
method, allows formation of highly crystalline nanomaterials [105] and is one of the
major advantages of synthesis by polyol method. Dispersion of highly crystalline and
stable phases is suitable for high temperature catalytic applications as in the present
case of sulfuric acid decomposition reaction. Thus, through polyol method, most
active and stable supported catalyst was fabricated. It has facilitated homogeneous
distribution of nano-crystalline rod-shaped α-Fe2 O3 over mesoporous SiO2 with Fe–
O–Si linkages, which is favorable for high temperature sulfuric acid decomposition
reaction. Mesh size is important from the back pressure exerted by particulate cata-
lyst in fixed bed reactor. Lower the mesh size, bigger is the particle size and will have
lower contact time with reactant gases, thus 45-mesh yield poor activity as compared
with 80–90 mesh (Fig. 17.13).

17.6 Conclusions

In this chapter, we have described three main categories of catalysts that devel-
oped over the years in search of improvisation: bulk, dispersed and single atom.
The general features of the three categories are described. An overview of prepara-
tion methods that developed for the synthesis of both bulk and supported industrial
17 Role of Synthesis in Evolution of Catalyst: Bulk … 747

catalysts is given above. Novel methods to prepare nanosized mixed metal oxides
at large scale are also described. The above article highlights how advancement in
synthesis practices helped in addressing optimum usage of active phase, active site
engineering, morphology and cost of active component (precious metals). Single
atom catalyst (SAC) is an emerging and promising science. It is ultimate form of
dispersed catalyst with exceptionally high catalytic activity, selectivity and turn over
number. Sophisticated atomic layer deposition, wet chemical co-precipitation tech-
nique based on carefully tuning the pH, temperature and loading amount in order to
lower the associated surface energy and prevent agglomeration and other approaches
such as photo-deposition and atom trapping are presently adopted to prepare SACs.
Thermal reactions such as CO oxidation, CO + N2 O and sulfuric acid decomposition
performed in our research group are discussed to illustrate that mobility of lattice
oxygen, adsorption on surface-active sites, extent of crystallinity, pore confinement,
dispersed phase–support interactions, shape and size of dispersed phase—all can be
tailored by adopting suitable method of preparation. By using selected examples,
we attempted to correlate synthesis-induced modifications with catalytic properties.
Finally, based on above, it can be concluded that catalysis science is an artwork and
most workable catalytic formulations can be created by the finest synthesis process.

Acknowledgements Authors sincerely thank Dr. A. K. Tyagi, Outstanding Scientist, Director,

Chemistry Group and Head, Chemistry Division, BARC for his keen interest, support and encour-
agement. MRP sincerely thank her mentor and PhD guide, Dr. N. M. Gupta, former Head, Applied
Chemistry Division, BARC for introducing to the exciting field of heterogeneous catalysis.

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Chapter 18
Synthesis—Activity Correlations
Established for TiO2 Based
Photocatalysts

Sushma A. Rawool, Mrinal R. Pai, Rajendra V. Singh,

Atindra Mohan Banerjee, and Arvind K. Tripathi

Abstract Photocatalysis is one of the promising technologies that can harvest solar
energy for various applications: production of solar fuels, removal of pollutants, water
purification, etc. The success of process is primarily dependent on the performance
of the photocatalyst. Conventionally, bulk titanium dioxide (TiO2 ) was considered
as a robust, cheap, and UV light active photocatalyst. In last few decades, newer
synthesis methodologies helped in evolution of TiO2 as a photocatalyst. The photo-
catalytic properties of nano (0D, 1D, 2D), single atom, defected TiO2 are unique.
Present chapter deals with the photocatalytic reactions and impact of the synthesis
methodologies on photocatalytic properties of the TiO2 . It is mainly divided in three
parts. First part of chapter introduces the general scheme of processes involved, ther-
modynamic selection criteria and suitability of a photocatalyst. A brief overview
of selected promising photocatalytic systems from literature is given. Second part
provides synthetic protocols to prepare bulk, nano titania of different dimensions, and
single atom dispersed photocatalysts. It discusses variation of the electric, optical,
and surface properties based on the dimensionality and nature of the catalyst. The
synthesis method—physicochemical property—photocatalytic activity correlations
for TiO2 based photocatalysts involved in different applications are established.
Finally, the developments in our laboratory towards improving the sunlight driven
photocatalytic hydrogen yield by introducing various modifications in TiO2 are
discussed.

Keywords Photocatalysis · Nano TiO2 · Single atom · Hydrogen · Synthesis

S. A. Rawool · M. R. Pai (B) · R. V. Singh · A. M. Banerjee · A. K. Tripathi

Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
Homi Bhabha National Institute, Anushaktinagar, Mumbai 400094, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 753
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_18
754 S. A. Rawool et al.

18.1 Introduction

Energy requirements of world’s population are majorly fulfilled by the non-renewable

fossil fuels. The world’s energy demand is growing continuously due to ever
increasing urbanization and industrialization. The use of fossil fuels is limited by
its scarcity and emissions of greenhouse gases (GHG) on combustion. Thus, exten-
sive research is going on to replace fossil fuels with sustainable, environment friendly
fuels [1].
Solar energy is one of the most abundant sources of renewable energy with 1.73
× 105 terawatts (TW) power irradiating earth continuously. This amounts to four
orders of magnitude higher than the current global human energy consumption (18.5
TW) and therefore can easily suffice the global demands. However, the variance in
solar flux with season, time, and geographical location is a major limitation in its
application. Intermittency issues can be resolved either by storage or conversion into
another form. Photovoltaic cells convert solar energy directly into useful electrical
output. Photovoltaic cells though efficient, but costlier than the fossil fuels and also
its transportation to the remote places is challenging [2].
Another approach found suitable to harvest solar energy is to store it in form of
solar fuels; hydrogen from water and hydrocarbons from CO2 reduction. Among
fuels, hydrogen has very high calorific value, yields 141.8 kJg−1 (three times that
of gasoline ~40 kJg−1 ) on combustion accompanied with water vapor and devoid of
any GHG emissions. Photocatalytic water splitting is a process in which solar energy
is utilized to split water molecules and produce hydrogen as energy carrier. Absorp-
tion and conversion of solar energy with the help of a photocatalyst is an effective
technique for the generation of sustainable fuels at room temperature. Thermally, the
water splitting is not feasible as it requires temperature more than 2500 K. Conversion
of CO2 into hydrocarbons photocatalytically is another thrust area as it offers a prac-
tical solution to tackle the adverse climatic change occurred due to rising levels of
CO2 in atmosphere [3]. These CO2 derived hydrocarbons can be utilized further as a
fuel in a closed cycle [4]. Dye degradation, abatement of volatile organic compounds
(VOCs) present in atmosphere to harmless products, and water purification are some
other important applications of photocatalysis.

18.1.1 Background

Photocatalytic water splitting is a chemical reaction driven by solar energy used to

dissociate water molecules into H2 and O2 in presence of a photocatalyst. It mimics
photosynthesis by green plants hence referred as artificial photosynthesis. Verne, in
1874 predicted that hydrogen will be futuristic fuel and would be produced from
water and solar energy, therefore termed water as ‘future coal’ [5]. Ciamicin, in
1912 [6], suggested the application of sunlight for photochemical reactions involving
generation of O2 and CH4 from water and CO2 , respectively. Bard, [7] referred
18 Synthesis—Activity Correlations Established for TiO2 … 755

water splitting by sunlight as “holy grail”. During 1972, Fujishima and Honda [8]
performed an historical experiment in which photoelectrochemical water splitting
was demonstrated over n- type TiO2 (rutile) electrode under light illumination. When
light shines on TiO2 electrode, electrons and holes are produced, the electrons travel
to the platinum counter electrode and reduce water to produce H2 . The holes on the
TiO2 electrode oxidize water to give O2 . At the same time in 1978, first report on
photoelectrochemical CO2 conversion to formic acid, formaldehyde, and methane
under UV–visible light illumination using single crystal gallium phosphide were
reported by Halmann et al. [9]. Inoue et al. [10] in 1979 reported the photocatalytic
CO2 conversion using different metal oxides/non-oxides like WO3 , TiO2 , CdS, GaP,
SiC, and ZnO under UV–visible light illumination. Subsequently, large number of
investigations was carried out in the field of photocatalytic hydrogen generation and
CO2 conversion, using different metal oxide and non-oxide semiconductors.

18.1.2 Processes Involved

Photocatalytic reactions can be homogeneous as well as heterogeneous in nature.

Till date several kinds of homogeneous catalysts [11–13] such as Pt, Ni, Fe, and Co
complexes as well as heterogeneous catalysts [14–16] such as metal oxide, nitride,
sulfide, and oxysulfide are well studied for photocatalytic reactions. In order to scale
up the reaction and for efficient utilization of the solar energy heterogeneous catalysis
is more advantageous as compared to homogeneous catalysis. The scope of present
chapter is limited to heterogeneous photocatalysis. In heterogeneous photocatalysis,
sequence of processes that take place during light illumination is described here and
pictorially shown in Fig. 18.1. (i) Absorption of light and generation of charge carriers
e− and h+ . When a semiconductor is illuminated with a light source (energy equal
or more than band gap) it absorbs photons and charge carriers are generated. (ii)
Separation of charges takes place by transfer of electron from valence band (VB) to
conduction band (CB) leaving behind hole in the VB, (iii) transfer of electron and
hole to the surface of the semiconductor, and (iv) utilization of electron and hole to
carry out the reduction and oxidation reactions, respectively.
The electron and hole thus generated can be used to drive reduction and oxidation
of the reactant molecules. These reactions are similar to an electrolysis where reduc-
tion and oxidation occurs at different electrodes. Thus in powdered photocatalyst
each particle behaves as a small electrochemical cell.

18.1.3 Thermodynamic Criterion for Selection

Reduction potential (E0 V vs. Normal hydrogen electrode (NHE) at pH 7) required

to form various compounds are given below:
756 S. A. Rawool et al.

Fig. 18.1 Schematic representation of photocatalytic reaction using TiO2 (CB: conduction band,
VB: valence band, R: chemical undergoing reduction reaction, and O: chemical undergoing
oxidation reaction, Eg: band gap of semiconductor)

CO2 + e− → CO−
2 E = −1.90 V
0
(18.1)

CO2 + 2H+ + 2e− → HCOOH E0 = −0.61 V (18.2)

CO2 + 2H+ + 2e− → CO + H2 O E0 = −0.53 V (18.3)

CO2 + 4H+ + 4e− → HCHO + H2 O E0 = −0.48 V (18.4)

CO2 + 6H+ + 6e− → CH3 OH + H2 O E0 = −0.38 V (18.5)

CO2 + 8H+ + 8e− → CH4 + 2H2 O E0 = −0.24 V (18.6)

2H+ + 2e− → H2 E0 = −0.41 V (18.7)

2H2 O → O2 + 4H+ + 4e− E0 = +0.81 V (18.8)

Based on the above reduction potentials and the band potentials (VB and CB) a
semiconductor possess, it is selected to be a photocatalyst for a CO2 reduction and
hydrogen generation. For example, for water splitting, a photocatalyst should fulfill
following minimum thermodynamic requirements.
18 Synthesis—Activity Correlations Established for TiO2 … 757

(i) The conduction band minima must be more negative than the reduction poten-
tial of water, i.e., 0 V vs. NHE at pH = 0 and maxima of the valence band must
be more positive than the oxidation potential of water, i.e., 1.23 V vs. NHE
at pH = 0. Therefore, the minimum band gap required to bring the overall
water splitting is 1.23 eV which corresponds to the wavelength ~1100 nm.
However, there is a barrier that the electron needs to overcome during the
charge transfer process between photocatalyst and water molecules. Hence,
energy greater than 1.23 eV is needed to drive the reaction. A photocatalyst
having a band gap around 2 eV is preferred. This energy corresponds to wave-
length in visible region thus making it possible to carry out reaction using
solar energy.
(ii) The photogenerated e− -h+ pair transfer rate must be faster than their
recombination rate.
(iii) A photocatalyst should not undergo corrosion during reaction, and it must be
stable at least up to ten years of use.
(iv) The intermediates and the product formed during evolution of H2 and O2 may
recombine back to give reactants. Photocatalyst should not promote such kind
of back reactions.

18.1.4 Evaluation of Photocatalytic Activity

Photocatalytic activity generally expressed as number of moles of hydrogen produced

per gram of photocatalyst per unit time. Amount of hydrogen evolved depends on
many factors such as flux of light, reaction time, reactor geometry, and illumination
area. If experimental parameters such as type of light source and reaction cell are
different, then it is difficult to compare the H2 yield from lab to lab. Hence, determi-
nation of quantum efficiency (ratio of number of electrons produced to the number of
photons absorbed by the system) is important. It is difficult to determine the number
of photons absorbed by the photocatalyst, but it is possible to determine the number
of photons incident on it by a luxmeter. Hence, the determined quantum efficiency is
the apparent quantum efficiency (AQE, η). AQE is expected to be lower than the
real QE because it takes into account only the incident photons which are higher in
number than the absorbed photons. AQE is calculated by using following equation:

2 × Number of H2 molecules evolved

η(%) × 100 (18.9)
N

where N is number of photons incident on the reactor.

Solar to fuel efficiency (SFE): The other parameter to evaluate the efficiency of
the catalyst is solar to fuel efficiency (SFE). It is given as follows:

r H2 × H
SFE = × 100 (18.10)
Psun × S
758 S. A. Rawool et al.

where rH 2 is the hydrogen production rate (mol/h), Psun is the solar light energy flux
(W/m2 ), H is enthalpy of water splitting reaction and S is the illumination area of
the reactor (m2 ).

18.1.5 Overview of the Literature Reports for Photocatalytic

Hydrogen Generation

Researchers have put tremendous efforts in finding a photocatalyst formulation that

can demonstrate water splitting with required AQE and can sustain hydrogen yield
for long durations. In search of low cost, active semiconductor materials with opti-
mized properties, such as minimized overpotentials for catalysis, narrow band levels
for visible-light absorption, and stability, various metal oxide and non-oxides, are
extensively investigated and reported in last few decades. Out of which few systems
have shown promising results as listed in Table 18.1.
There are innumerable semiconductors of different classes such as metal oxides,
sulfides, nitrides, and oxynitrides developed for various photocatalytic applications.
Among all types, TiO2 has gained tremendous attention as it is chemically stable,
environmentally friendly, non-toxic, and inexpensive. The valence band of TiO2
is comprised of O 2p states, while conduction band is composed of titanium 3d
states. The band edge potentials, crystal structure, electronic, and optical properties
of TiO2 are such that it can carry out different photocatalytic reactions and makes it
a promising photocatalyst [15].

18.1.6 Aim and Scope

TiO2 is considered to be cheap, robust, nontoxic, and stable conventional photocata-

lyst. Over the decades it has been evolved into nano titania of different dimensions and
as a support for single atom dispersed catalysts with unique photocatalytic properties.
The present chapter illustrates the role of synthesis in development of TiO2 photo-
catalysts for various applications. It is mainly divided in three segments. First part
of chapter introduces general features of photocatalytic reactions and emphasizes its
importance in harvesting solar energy for various applications. Second part discusses
the impact of synthesis methods for the generation of nano TiO2 with different dimen-
sion and effect of different morphology and shape of nanoparticles on the photocat-
alytic activity of TiO2 . It also discusses different synthesis strategies employed with
examples to overcome the disadvantages of TiO2 —such as poor light absorption
in visible region of sunlight and inefficient separation of charge carriers—leading
to improved photocatalytic properties. It also establishes synthesis—photocatalytic
activity correlations in nano and single atom TiO2 based photocatalysts. Third and
Table 18.1 Photocatalyst systems, hydrogen yield obtained, light source, and other experimental conditions are listed below [17–28]
Sr. no Photocatalyst Co-catalyst Light source Reaction conditions H2 yield AQE/SFE Reference
1 (Ga(1−x) Znx ) Rh2-y Cry O3 High pressure Hg 300 mg photocatalyst H2 : 927 μmol/h AQE 5.9% at [17]
(N(1−x) Ox ) [17] lamp (450 W) with aq dispersed in 370 ml O2 : 460 μmol/h 420–440 nm
NaNO2 as filter (λ > of aqueous H2 SO4 ,
400 nm) pH adjusted to 4.5
2 CdS [18] Pt-PdS Xe-lamp (300 W, λ > 300 mg of 8.77 mmol/h AQE 93% [18]
420 nm) photocatalysts
powder suspended in
200 mL of 0.5 M
Na2 S-0.5 M Na2 SO3
solution
3 Black TiO2 [19] Pt Solar simulator 20 mg photocatalyst 10 mmol/h/g SFE 24% [19]
dispersed in 1:1
water: methanol
solution
4 CoO [20] No cocatalyst Solar simulator 25 mg photocatalyst 20 ml in 30 min SFE 5% [20]
dispersed in water
5 Carbon/TiO2 /Carbon Pt Solar simulator (AM 10 mg photocatalyst 37.6 mmol/h/g AQE = 95% at λ < [21]
18 Synthesis—Activity Correlations Established for TiO2 …

nanotube [21] 1.5G filter) dispersed in 120 ml 340 nm& 1.5% at

of 1:1 water: ethanol 430 nm
solution
6 Carbon dots/g-C3 N4 No cocatalyst Xe-lamp (300 W, λ > 80 mg photocatalyst H2 : 45.3 μmol/h SFE 2% [22]
[22] 420 nm) dispersed in 150 ml O2 : 22.7 μmol/h AQE 16%
water
7 La/NaTaO3 [23] NiO High pressure Hg 1 g of catalyst H2 : 19.8 mmol/h AQE 56% (at [23]
lamp (400 W) dispersed in 390 ml O2 : 9.66 mmol/h 270 nm)
of pure water
(continued)
759
Table 18.1 (continued)
760

Sr. no Photocatalyst Co-catalyst Light source Reaction conditions H2 yield AQE/SFE Reference
8 Hf doped (Na, No cocatalyst High pressure Hg 0.1 g dispersed in H2 : 4.96 mmol/h Not given [24]
K)TaO3 [24] lamp (350 W) 350 ml pure water O2 : 2.46 mmol/h
No cocatalyst High pressure Hg 0.1 g dispersed in 25.6 mmol/h Not given
lamp (350 W) 300 ml pure water
and 50 ml of
methanol
9 ZrO2 –TaON and Pt Xe lamp, (300 W, 420 100 mg of Pt/WO3 H2 : 32.6 μmol/h AQE 6.3% at [25]
WO3 [25] < λ < 800 nm) and 50 mg of O2 : 15.6 μmol/h 420.5 nm
Pt/ZrO2 /TaON; (420 < λ < 800 nm)
100 ml NaI
10 BiVO4 :In, Mo [26] RuO2 Hg arc lamp (500 W) 0.3 g of photocatalyst H2 : 17 μmol/h AQE 3.2% (at [26]
in 100 ml of water 420–800 nm)
11 GaN:Mg/InGaN:Mg Rh/Cr2 O3 Xe lamp (300 W, AM 0.48 mg sample H2 : 3.46 mol/h/g AQE: 12.3% [27]
[27] 1.5G, 26 suns) deposited over 3 cm2 O2 : 1.69 mol/h/g (400–475 nm),
glass plate and SFE: 1.8%
immersed in water
12 SrTiO3 :Al [28] Rh/CrOx, CoOOH Xe lamp (300 W) 0.1 g sample H2 : 3.54 mmol/h/g AQE = 96% at [28]
dispersed in 100 ml O2 : 1.78 mmol/h/g (350–360 nm),
of water SFE: 0.65%
S. A. Rawool et al.
18 Synthesis—Activity Correlations Established for TiO2 … 761

last part briefly presents the synthesis strategies and modifications adopted in our
laboratory to enhance the solar hydrogen yield using TiO2 based photocatalysts.

18.2 Bulk TiO2 as a Photocatalyst

Anatase, rutile, and brookite phase are three polymorphs of TiO2 which occurs natu-
rally [29, 30]. Both anatase and rutile phases of TiO2 show tetragonal crystal system
consist of chains of distorted TiO6 octahedral structure. Along with these poly-
morphs, TiO2 can exist in α-PbO2 -type structure (orthorhombic structure) at high
pressure around 0.8 to 10 GPa [31]. At pressure higher than 20 GPa, formation of
baddelleyite with ZrO2 structure and cotunnite with PbCl2 structure has been reported
[32, 33]. In addition, TiO2 (I) ramsdellite, [34] TiO2 (B) monoclinic [35], and TiO2
(H) hollandite [36] are also reported. TiO2 (I) ramsdellite was synthesized by soft
chemical method in which lithium ions extracted and oxidized from Li0.5 TiO2 using
1 M HCl. Hydrothermal method has been reported for the synthesis of TiO2 (B)
(monoclinic) [35]. TiO2 (H) hollandite was synthesized by oxidation–ion extraction
process using hollandite K0.21 TiO2 [36]. Table 18.2 lists the synthetic procedures
adopted to prepare polymorphs of TiO2 and their typical structure.
Rutile is thermodynamically stable phase among the three naturally occurring
polymorphs of TiO2 , whereas the other two phases, i.e., anatase and brookite are the
metastable states. Anatase phase gets transformed into rutile phase above 600 °C
[37]. TiO6 octahedra is more distorted in anatase phase in comparison to the rutile
phase. Structural difference in anatase and rutile results in different electronic band
alignment. Anatase and rutile possess the band gap of 3.2 and 3.0 eV, respectively.
Pristine Brookite form is difficult to synthesize hence scarcely reported [38]. Forma-
tion of different phases depends on the synthesis conditions as shown in Table 18.1.
In ancient times TiO2 were used as a white pigment [39]. Before knowing the photo-
catalytic properties of TiO2 , it was reported for dye bleaching in vacuum as well
as in oxygen atmosphere in 1938 [40]. In this report, TiO2 was referred as photo-
sensitizer. It remains unaltered during UV light irradiation and produces the active
oxygen species that causes bleaching of dye [40]. Also, in 1956 the photooxidation
properties of TiO2 were invaded [41], and it was concluded that the anatase phase
was more photocatalytically active as compared to the rutile phase of TiO2 . The
photocatalytic properties of TiO2 came into light after the historical experiment by
Fujishima and Honda in 1972 [8]. In which photon assisted splitting of water was
demonstrated using a photoanode made up of single crystal wafer of n-type rutile
phase of TiO2 under UV light illumination. Since then, many modifications were
done to further improvise the photocatalytic properties of TiO2 .
Bulk materials with micrometer sized particles show the low surface area, and
photogenerated electron–hole pair needs to travel larger distance, thus limits the
photocatalytic activity. Downsize of the micron particle to the nanometer scale opens
up new avenue for exploring the different physico-chemical properties of the mate-
rial. The electronic, surface, and optical properties of the material affected while
762 S. A. Rawool et al.

Table 18.2 Synthesis methods, crystal structure, space group, and band gap of different polymorphs
of TiO2 are listed below
Phase of TiO2 Synthesis method Crystal system Space group Band References
gap
(eV)
Anatase Sol gel, Tetragonal I41 /amd 3.2 [16, 29, 30]
Hydrothermal
method
Rutile Sol gel, Tetragonal P42 /mnm 3.0 [16, 29, 30]
Hydrothermal
method
Brookite Hydrothermal Orthorhombic Pbca 3.3 [16, 30]
method
α-PbO2 -type High pressure Orthorhombic Pbcn NA [31]
phase around
0.8–10 Gpa
Baddelleyite At pressure Monoclinic with P21 /c NA [32]
higher than ZrO2 structure
20 Gpa
Cotunnite At pressure With PbCl2 Pnma NA [33]
higher than structure
20 GPa
TiO2 (R) Li ion extraction Orthorhombic Pbnm 3.34 [34]
(ramsdellite) and oxidation
from the
ramsdellite-type
Li0.5 TiO2 by 1 M
HCl treatment
TiO2 (B) Hydrothermal Monoclinic C2/m NA [35]
(monoclinic) synthesis
TiO2 (H) Oxidation–ion Tetragonal I4/m NA [36]
(hollandite) extraction process
using hollandite
K0.21 TiO2
* NA: the data on band gap value was not found for pure phase to the best of our knowledge

moving from micron size bulk particle to the nano size dimension to the single atom.
As TiO2 is evolved from bulk to nanoparticles to nanoclusters, its absorption charac-
teristic (λmax) also decreased from 400 to 250–300 nm [42]. Anpo et al. [43] in 1987
first time reported the impact of the particle size on photocatalytic properties. Along
with increase in particle size with calcination temperature, significant change in the
absorption and photoluminescence spectra was also observed. It was found that the
quantum yield for photocatalytic hydrogenation reaction of unsaturated hydrocar-
bons with H2 O increased significantly for small particles having particle size below
10 nm.
18 Synthesis—Activity Correlations Established for TiO2 … 763

In case of small particle size, the photogenerated charge carriers have to travel
shorter distance from bulk to the surface active sites. This resulted in decrease in
recombination probability of the charge carriers and thus improved photocatalytic
performance. Along with particle size, crystallinity and surface area are the impor-
tant factors which govern the photocatalytic properties of the photocatalyst. During
synthesis of nanoparticles, defects in addition to grain boundaries form which can
act as a recombination centers for photogenerated e− -h+ pair. Generally, calcination
at high temperature is needed to eliminate the grain boundaries and annihilate the
defects. With increase in calcination temperature particle size increases and also the
crystallinity of the material, but it leads to decrease in surface area of the material
as a result of agglomeration of the nanoparticles at high calcination temperature.
Therefore, optimization of the surface area, particle size along with crystallinity
of the nanoparticles is necessary to improve the photocatalytic conversion. In our
earlier study, we synthesized indium titanate by solvothermal method at 220 °C using
titanium isopropoxide and indium acetate as titanium and indium precursors, respec-
tively [44]. The correlation between photocatalytic activity for hydrogen generation
and surface area and crystallinity of nanoparticles of the indium titanate were estab-
lished. It was found that with increase in calcination temperature the photocatalytic
activity increased and reached maximum for nanoparticles calcined at 800 °C having
a surface area of ∼38 m2 g−1 with optimum crystallinity. While on further increase
in calcination temperature beyond 800 °C, photocatalytic activity deteriorated.

18.3 Nano TiO2

Nanomaterial is defined as the material possessing at least one of the dimensions

in the 1–100 nm range. Pokropivny and Skorokhod classified the nanomaterials as
0D, 1D, 2D and 3D [45]. Nanomaterials are classified as zero dimensional (0D), one
dimensional (1D), two dimensional (2D), and three dimensional (3D) on the basis of
dimensions. Zero dimensional nanomaterials (0D) include spherical nanoparticles.
One dimensional nanomaterials (1D) include nanowires, nanotubes, nanorods, and
nanobelts. Two dimensional nanomaterials (2D) include nanosheets, whereas three
dimensional nanomaterials (3D) includes bulk powders, bundles of nanowires and
nanotubes, and multi-nanolayers and porous nanostructure.
TiO2 nanoparticles were synthesized in different forms. Synthesis methods have
significant influence on the dimension of the nanomaterials. Also, the electrical,
optical, and surface properties of the nanomaterials can be altered by adopting
different synthesis methods. As explained in the previous chapter, the synthesis
methods of nanomaterials are divided into two parts: chemical methods and physical
methods. Chemical methods include bottom-up approach and the physical methods
deals with the top-down approach. As explained in the previous chapter, physical
methods include gas condensation techniques, spray pyrolysis, ball milling, and
aerosol processes, and flame decomposition of metal-organic precursor and chemical
methods include sol–gel method, reverse microemulsion/micelle method, and wet
764 S. A. Rawool et al.

chemical synthesis methods. Physical methods are preferred over chemical methods
as the material can be synthesized in a large quantity. However, the demerit of phys-
ical methods is that one can generate particles of sizes in tens of nanometers only.
Whereas using chemical methods the particle size can be tuned to even less than 10 nm
and can approach atomic scale [46]. However, the demerit of chemical methods is
that it produces nanoparticles in small quantities. Physical vapor synthesis, laser
pyrolysis, mechanical milling, spray pyrolysis, and sol–gel methods are some of
the synthesis methods adopted to industrially scale up the nanoparticle production
[47]. Most researchers compare the photocatalytic activity of their photocatalysts
with commercially available Degussa P25 as a benchmark and have reported the
compared activities. Degussa (Evonik) P25 is a commercially available TiO2 photo-
catalyst containing crystalline phases of anatase, rutile and amorphous phase in the
proportion of 78:14:8, respectively and this formulation was found to be possessing
very high photocatalytic activity for many reactions [48]. P25 is white color titania
powder, in which both high temperature (rutile) and a low temperature phase (anatase)
coexists. Moreover, it is not a mechanical mixture of both the phases, then curiosity
arises to know about the synthetic method which has resulted in both high and low
temperature phases at the same time. P25 is synthesized using aerosol flame pyrolysis
process having particle size of 21 nm and 50 m2 g−1 surface areas [49].
Among all the methods, chemical methods are well suited for the synthesis of
nanoparticles for photocatalytic application as the control over size, phase, and
surface area is easy to achieve [46]. The synthesis of TiO2 nanoparticles with different
dimensions by using chemical methods and the role of synthesis methods in altering
the physico-chemical and photocatalytic properties of TiO2 is explained in next
sections of this chapter.

18.3.1 Zero Dimensional TiO2

Chemical methods, like sol gel, hydrothermal, and solvothermal methods are gener-
ally used for the synthesis of nano and microspheres of TiO2 . Cargnello et al. [46]
summarized the synthesis methods used to prepare quasi-zero-dimensional TiO2
nanocrystals.
We also attempted to synthesize 0D TiO2 nanoparticles and observed that photo-
catalytic activity dramatically changes on varying the synthesis conditions. Here,
sol–gel method was selected for the synthesis of 0D TiO2 nanoparticles. Synthesis
of TiO2 nanoparticles was done under acidic condition and in presence of non-
ionic ligand like ethylene glycol. TiO2 -E was synthesized using tetrabutyl titanate as
titanium precursor and ethylene glycol as non-ionic ligand. In similar way, TiO2 -1
and TiO2 -2 were synthesized using same protocol as TiO2 -E but without ethylene
glycol for comparison. Unlike TiO2 -1, TiO2 -2 was synthesized under acidic condi-
tions. Faceted nanoparticles were formed and seen in TEM images of TiO2 -E sample
synthesized using ethylene glycol. While in case of TiO2 -1 sample, irregular shaped
particle was observed. Extended X-ray absorption fine structure (EXAFS) studies
18 Synthesis—Activity Correlations Established for TiO2 … 765

revealed that the Ti–O and Ti–Ti bond lengths were higher with lower disorder in
TiO2 -E as compared to other TiO2 samples. All the samples were evaluated for photo-
catalytic H2 generation. TiO2 -E showed highest activity for H2 generation at the rate
of 476 μmol h−1 g−1 under sunlight illumination achieving 2.2% AQE (Fig. 18.2).
Dispersal of 1 w/w% Pt as cocatalyst over surface of TiO2 -E, rate of H2 genera-
tion further enhanced to 3382 μmol h−1 g−1 under sunlight illumination with AQE
15.9%. The improvement in the photocatalytic activity of TiO2 -E was attributed to
the presence of crystalline anatase phase with increased surface area and porosity
and modified local structure (increased bond length and reduction in lattice disorder
as revealed by EXAFS) of TiO2 .
During 2013, Pan et al. [50] synthesized the defect free TiO2 nanosheets decorated
with 0D quantum dots of anatase TiO2 using hydrothermal route. In this work, a
solution of tetrabutyl titanate and hydrofluoric acid (HF) solution was hydrothermally
treated at 180 °C by varying the reaction time (t = 24, 72 and 168 h). It was found
that the 24 h of hydrothermal treatment produces nanosheets and 72 and 168 h

Fig. 18.2 Comparison of photocatalytic hydrogen yield evolved over different TiO2 samples
766 S. A. Rawool et al.

treatment produces nanosheets decorated with the nanodots of 1.5–3 nm size and
with further increase in hydrothermal treatment time, concentration of nanodots
increased. Band gap of 72 and 168 h treated samples was blue shifted in comparison to
the clean nanosheets (24 h). The photocatalytic performance for Rhodamine B (RhB)
dye degradation was evaluated for different samples. It was found that the catalytic
activity was highest for 168 h sample having more number of TiO2 quantum dots. In
order to get rid of surface defects, the sample was hydrothermally treated in water at
100 °C for 24 h or calcined at 500 °C. Improvement in photoactivity for Rhodamine
B dye degradation after hydrothermal as well as calcination treatment was observed.
The nanosheets decorated with quantum dots provided a new charge transfer pathway
as compared to the pure nanosheets. The transfer of the photogenerated electron
occurred from {001} facets of nanosheets to the quantum dots, thus reduced the
recombination of charges and improved the photocatalytic activity. This suggested
that tailoring of local surface structure is an effective synthetic strategy to improve
the activity.
Inducing surface/sub-surface defects improved the light absorption as well as
charge separation properties of quantum dots of rutile TiO2 as reported by Li et al.
[51]. 10 nm sized rutile particles were synthesized by direct hydrolysis of TiCl4
solution and calcination at 473 and 673 K. Rapid hydrolysis and evaporation steps
in the presence of high concentration of chloride ions resulted into formation of
nanoparticles instead of nanorods and also generated defects in the nanoparticles.
The presence of defects improved the visible light absorption as compared to other
rutile synthesized by hydrothermal route. Among all samples, 473 K calcined sample
exhibited highest photocatalytic hydrogen generation at 1954 μmol h−1 g−1 under
simulated solar light using 1 wt% Pt as cocatalyst. An upward shift of 0.3 eV in the
valence band edge was observed in the sample calcined at 473 K thus, enhancing
photoresponse in visible region. The improved photocatalytic activity of 10 nm rutile
TiO2 synthesized by hydrolysis route was attributed to the existence of the surface
defects, i.e., hydroxyl group on the surface which resulted into narrowing of band
gap and improved charge carrier separation.

18.3.2 One Dimensional TiO2

1D TiO2 nanomaterials include nanorods, nanowires, nanotubes, and nanobelts. Sol–

gel template method, hydrothermal method, solvothermal method, and electrochem-
ical oxidation are used for the synthesis of nanorods, nanowires, and nanotubes.
Wang et al. [52] reviewed the synthesis and growth mechanism of 1D nanomaterials
and also includes the morphology assisted properties and application of the 1D TiO2
nanomaterials. For the synthesis of 1D structure, hydrothermal method is the most
commonly used. Hydrothermal synthesis of TiO2 nanorods offers several advan-
tages such as i. formation of product at relatively lower temperature thus preventing
agglomeration of the nanorods, ii. high purity of the product due to recrystallization
18 Synthesis—Activity Correlations Established for TiO2 … 767

in the hydrothermal solution, and iii. TiO2 with different morphology and structure
can be easily synthesized by changing the reaction conditions [53].
1D nanorods with different exposed crystal facets have gained tremendous atten-
tion, as the electron and hole can be driven to the different facets to carry out the
reduction and oxidation reaction, respectively. This occurs because of the different
atomic arrangement at the exposed facets which resulted into different surface energy
levels of the conduction bands and valence bands. Yang et al. [53] synthesized the
nanorods of TiO2 having rutile, anatase, and brookite phase with different facets by
hydrothermal synthesis using peroxide titanic acid (PTA). It was found that pH of
the solution plays a critical role in deciding the crystal phase of TiO2 . The amount
of hydroxyl group and their position in the complex decides the formation of the
different phases at different pH. Rutile phase TiO2 nanorods formed when the pH
of PTA was lower than 10, due to the presence of neutral Ti2 O5 (OH)2 (H2 O)4 or
cationic Ti2 O5 (H2 O)6 2+ condensing complexes. At lower pH, number of hydroxyl
group were less and thus corner shared bonding was preferred, thus rutile phase was
dominant. At pH higher than 10, anatase phase was formed due to the presence of
anionic Ti2 O5 (OH)4 (H2 O)2 2– condensing species. The anionic species contained a
greater number of hydroxyl groups which enhanced the probability of edge sharing
and crystallization of anatase phase. Whereas, at pH 10 the presence of neutral
species facilitated both edge sharing and corner sharing leading to crystallization of
brookite phase. Figure 18.3 shows the TEM images of the nanorods synthesized at
different pH conditions. Rutile TiO2 nanorods efficient in photocatalytic oxidation of
methylene blue dye while brookite phase was active for chromium ion reduction. The
improved oxidation ability of rutile phase was attributed to the better spatial sepa-
ration of charge carriers on different facets, while the shift of the conduction band
towards cathodic potential improved the reduction ability of brookite nanorods.
Alkaline hydrothermal method is a simple and easily scalable method for the
production of the 1D TiO2 nanotubes. Peng et al. [54] synthesized the 1D TiO2 by
alkaline hydrothermal method using TiO2 nanoparticles (P25 TiO2 ) as Ti precursor
and reported the impact of the synthesis conditions such as NaOH concentration,
temperature, and amount of TiO2 precursor on photocatalytic hydrogen generation
using 3-factor 3-level Box Behnken design (BBD). In this synthesis method, P25
TiO2 nanoparticles were added to NaOH solution and subjected to the hydrothermal

Fig. 18.3 TEM images of TiO2 nanorods synthesized at pH equal to a 4, b 10, and c 11. Inset shows
the HR-TEM images and SAED pattern. Reproduced with permission from Ref. [53]. Copyright
2015 American Chemical Society
768 S. A. Rawool et al.

treatment for 48 h. The BDD model illustrated that the reaction temperature and
NaOH concentration during synthesis has substantial effect on the TiO2 phase,
crystallite size, specific surface area, band gap, and thus on photocatalytic activity.
It was observed that maximum hydrogen generation was produced at the rate of
475 μmol h−1 under UV irradiation using 10 mg of 1D TiO2 having anatase phase
with crystallite size of around 20 nm.

18.3.3 Two Dimensional TiO2

Exposed {001} faceted anatase TiO2 nanosheets have attracted tremendous attention
in the field of photocatalysis. The sequence of average surface energies of anatase
TiO2 is 0.90 J m−2 for {001} > 0.53 J m−2 for {100} > 0.44 J m−2 for {101} [55,
56]. Nanosheets can be synthesized using hydrothermal, solvothermal, chemical
vapor deposition (CVD) and sol gel method [57]. Most commonly used method
for synthesis of 2D TiO2 is hydrothermal as it is simple and easy to scale up. Han
et al. [58] synthesized the single crystal of anatase TiO2 nanosheets by hydrothermal
treatment using tetrabutyl titanate [Ti(OBu)4 ] as titanium precursor and HF as a
capping agent. It was revealed that the F− ions played crucial role in formation of
exposed {001} facets and also the temperature of the reaction determined the size as
well as thickness of the TiO2 nanosheets. Figure 18.4 shows the TEM images of the
TiO2 nanosheets having 77% average percentage of (001) facets. Under optimum
conditions such as reaction temperature 200 °C, 5 ml of Ti(OBu)4 , and 0.8 ml of HF,
the TiO2 nanosheets with average percentage of 89% of (001) facets having average
size of 130 nm and thickness of nearly 8 nm could be synthesized. The as synthesized

Fig. 18.4 a TEM image (inset shows selected area electron diffraction, SAED pattern) and b HR-
TEM image of vertical nanosheets of TiO2 synthesized by hydrothermal method at temperature
180 °C using 5 mL of Ti(OBu)4 and 0.6 mL of HF, having 77% of average percentage of (001)
facets. Reproduced with permission from Ref. [58]. Copyright, 2009 American Chemical Society
18 Synthesis—Activity Correlations Established for TiO2 … 769

nanosheets with 89% exposed (001) facets showed improved photocatalytic activity
for the methyl orange degradation.
Another strategy adapted was the synthesis of porous 2D nanomaterials with
copious in-plane pores. The well-defined microstructural porous 2D nanomaterials
offer benefits that are obtained by combining the property of both 2D nanomaterials
and porous materials and thus improved photocatalytic properties. Song et al. [59]
synthesized the 2D hollow nanoplates of anatase phase of TiO2 by hard template
method. In this case, α-Fe2 O3 was used as a template. The ratio of anatase and
rutile phase was adjusted by changing the calcination temperature. 2D hollow TiO2
nanoplates showed improved catalytic activity for rhodamine B dye degradation, and
it was attributed to the high specific surface area of 59 m2 g−1 and increased number
of active centers.

18.3.4 Three Dimensional TiO2

Three dimensional TiO2 nanomaterials (3D) include bulk powders, bundles of

nanowires and nanotubes, and multi-nanolayers and porous nanostructure. Meso-
porous TiO2 structure has received tremendous interest because of the high surface
area, large pore volume, tunable pore structure, and nano-confined effects [60]. These
properties are advantageous in the field of catalysis as the high surface area provides,
more number of surface active sites for better adsorption of reactant or intermediate
formed during the process and porous structure further helps in the enhancement of
reactants and products diffusion, thus facilitate the reaction kinetics.
Polshettiwar and co-workers [61] reported a solution deposition method for depo-
sition of TiO2 over the fibers of nanosilica (KCC-1 as a support). This synthesis
protocol was developed as an alternative to the costly and complex atomic layer
deposition technique. In this method, KCC-1 was used as a support and the titanium
butoxide as a titanium precursor. The hydrolysis of the titanium salt was brought
over the surface of the KCC-1 in the solution deposition technique. It was revealed
that the high surface area, accessible active sites, and formation of Si–O–Ti increased
hydrogen yield to 26.4 mmol h−1 per g of TiO2 under UV light irradiation. Polshet-
tiwar and co-workers [62] also probed the formation mechanism of TiO2 coated
fibrous nanosilica using solid-state 1 H, 47,49 Ti and 29 Si NMR, and insitu FTIR studies.
The proposed mechanism included following steps: a. silanols present on the surface
of silica deprotonated in the presence of ammonia and titanium butoxide hydrol-
ysed to titanium hydroxide, b. lone pair of ammonia donated to Ti4+ ion of titanium
hydroxide, c. hydroxide ions released and subsequently Si–O-Ti oxo-bridges gener-
ated by condensation of dehydroxylated titanium ions with the deprotonated silanols,
d. oxy-anion of titanols formed and Ti–O-Ti generated by the reaction of oxy-anion
of tiatanols with ammonia-activated titanium hydroxide molecules, and the continu-
ation of above steps till titanium hydroxide was utilized to form titanium hydroxide
coating over silica. At the time of calcination, titanols get converted into TiO2 over
the silica support.
770 S. A. Rawool et al.

TiO2 hollow shells with well-defined inner cavity offer advantages such as
improved diffusion of the reactants to the surface-active sites and enhanced light
absorption due to multiple reflections of light within inner cavity. Eskanderloo
et al. [63] reported a synthesis of hollow shell using a droplet-based microfluidic
approach. In this, a single emulsion technique was used for the emulsification of oil
phase having titanium butoxide (TBT), UV-curable resin ethoxylated trimethylol-
propane triacrylate (ETPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP),
and aqueous phase containing 1 wt.% triblock copolymer Pluronic F108. The emul-
sion droplets formed undergo a phase separation, and hydrolysis of TBT takes place
at the interface of the emulsion which leads to the formation of the TiO2 shell. This
shell gets ruptured and released ETPTA core and formed hollow shell of anatase TiO2
after the post-treatments with UV, washing with isopropanol and thermal treatment.
Schematic representation of different steps during the synthesis of hollow sphere of
TiO2 along with their optical microscopic images recorded at different time interval
is given in Fig. 18.5a. This leads to the formation of the TiO2 hollow shell with
uniform size about 50 μm and well-defined inner cavity of around 18–20 μm. The
hollow shell showed better light absorption efficiency as compared to the hollow
sphere because of the multiple light reflections within inner cavity. Also, the hollow
shell of TiO2 provides high surface area and improved contact between the photo-
catalyst and reactant molecules. Also, Pt deposition within and outside the hollow
shell showed better photocatalytic activity for methylene blue degradation than the
hollow sphere or hollow shell decorated with Pt only on outer surface.

Fig. 18.5 a Schematic illustration of different steps during the synthesis of hollow sphere of
TiO2 b optical microscopic images recorded at different time intervals and steps. Reproduced with
permission from Ref. [63]. Copyright 2018 Elsevier
18 Synthesis—Activity Correlations Established for TiO2 … 771

Mesocrystals signifies the new class of nanostructured solids. A mesocrystal is

defined as a superstructure of crystalline nanoparticles with external crystal faces on
the scale of some hundred nanometers to micrometers [64]. Jiao et al. [65] devel-
oped a protocol for one-pot synthesis of the mesocrystals of TiO2 with exposed
{101} facets and hollow single crystal of TiO2 . In this work, hydrothermal synthesis
was performed using titanium sulfate as precursor of Ti and Na3 PO4 and HF as a
morphology controlling co-mediators. The solid and hollow crystal was obtained by
varying the concentration of HF used during synthesis. To understand the factors
affecting the formation of hollow and mesocrystal, different additives were added
systematically during hydrothermal synthesis. The presence of F− and PO3 4− ions
leads to the formation of micron meter sized crystals and 10 nm sized nanoparticles,
respectively. From this, it was concluded that the presence of both F− and PO3 4−
is necessary for the growth of the hollow crystals with exposed {101} facets. The
SEM and TEM images of the solid anatase TiO2 single crystals, hollow anatase TiO2
single crystal, and hollow anatase TiO2 mesocrystals with exposed {101} facets are
given in Fig. 18.6. Specific surface area of the solid single crystals, hollow single
crystals, and hollow mesocrystals synthesized in this work were found to be 17,
35, and 42 m2 g−1 , respectively. It was revealed that the hollow TiO2 structure and
the mesocrystal showed highest H2 generation and CO2 conversion to methane as
compared to the solid single crystal TiO2 . The position of the CB and VB band edges
were derived from UV–vis DRS spectra and valence band XPS spectra (Fig. 18.6g).
It was found that the CB and VB edges of hollow mesocrystals were higher as
compared to the hollow and solid single crystal. Hence the photogenerated electrons
in the CB of mesocrystals possess the higher reduction ability as compared to the
solid and hollow single crystals, thus improved photocatalytic activity. The author
attributed the improvement in activity to the presence of surface terminated PO3 4−
species which resulted into increase in the band gap and the co-existence of major
{101} and minor high-index facets on the hollow single crystals and mesocrystals
which could improve the transfer of charges on different facets.

18.4 Modifications in TiO2

Application of TiO2 as photocatalyst is limited by its inability to absorb visible light

wavelengths of sunlight and high rate of recombination reaction [16, 29, 37]. Metal
loading, cationic and anionic doping, composite formation and dye sensitization are
most commonly used strategies to improve the photoresponse of TiO2 towards visible
wavelengths as discussed below.
772 S. A. Rawool et al.

Fig. 18.6 SEM and TEM images of (a) and (d) solid anatase TiO2 single crystals synthesized
using 500 mM HF concentration, (b) and (e) hollow anatase TiO2 single crystal synthesized using
400 mM HF concentration and (c) and (f) hollow anatase TiO2 mesocrystals with exposed {101}
facets synthesized using 300 mM HF concentration, and g. schematic of band structure derived
from the valence band XPS spectra and the DRS data. Reproduced with permission from Ref. [65].
Copyright 2012 American Chemical Society

18.4.1 Cationic Doping

Dopant is a foreign element which replaces the crystal lattice point of the host material
[37]. Doping of cation creates impurity levels within the band gap by changing the
electronic structure of semiconductor. These levels may be donor level above the
valence band or the acceptor level below the conduction band [66], thus helps in
overall reduction of band gap. Along with improvement in light absorption in visible
region, the presence of dopant in the TiO2 lattice also helps to improve the electrical
conductivity.
18 Synthesis—Activity Correlations Established for TiO2 … 773

The effect of doping of higher valent ion (W6+ , Ta5+ ), undoped and doping with
(Ge4+ ), and doping with lower valent ion (Mg2+ ) on the electrical conductivity of 0.5%
Pt/TiO2 was studied by Akubuiro et al. [67]. Figure 18.7 shows the influence of high
and low valent doping and undoped 0.5% Pt/TiO2 on electrical conductivity under
different gas environment. It was revealed that incorporation of higher valent cations
into TiO2 lattice improved the electrical conductivity as compared lower valent ions.
However, electrical conductivity was unaffected by doping with isovalent ions such
as Ge4+ . The doping with higher valence cations introduced excess electrons to

Fig. 18.7 Effect of gas cycles of sequences on electrical conductivity of 0.5% Pt/TiO2 , doped with
A W6+ , B Ta5+ , C undoped and D Mg2+ . Reproduced with permission from Ref. [67] Copyright
1989 Elsevier
774 S. A. Rawool et al.

Fig. 18.8 a Schematic illustration of synthesis of OMBT, TEM images along b [100] and c [110]
planes, d and e HR-TEM images of the OMBT. Reproduced with permission from Ref. [70].
Copyright 2014 American Chemical Society

TiO2 , thus resulting in increased n-type semiconductivity whereas doping with lower
valence cations resulted in introduction of positive holes in TiO2 lattice resulting in
decreased n-type semiconductivity, while electronic structure of TiO2 was retained
on isovalent doping.
Also, the presence of point defects in TiO2 plays an important role in deciding
the electrical conductivity of TiO2 [29]. Point defects in TiO2 can be generated
by different reduction methods. Reduction methods include use of H2 gas, treat-
ment with inert gases like Ar, N2 , and He, reducing agents such as NaBH4 , metal-
lothermic reduction involving metals for reduction viz; Al, Mg, Zn etc., bombardment
with high energy particle (such as electron beam, proton beam, hydrogen plasma),
electrochemical reduction, etc. More details are available in literature [68, 69].
Self doping with Ti3+ is also an effective way to improve visible light absorption
of TiO2 . Zhou et al. [70] reported facile synthesis of the ordered mesoporous black
TiO2 (referred as OMBT). An evaporation-induced self-assembly method in combi-
nation with an ethylenediamine encircling process followed by hydrogenation was
employed for synthesis of OMBT (Fig. 18.8a). In order to understand the role of
ethylenediamine encircling process, synthesis was carried out by alternate routes 2
and 3 (Fig. 18.8a). During direct calcination at 500 °C (route 2), the ordered porous
structure was collapsed. After hydrogenation, porous structure further collapsed also
some of anatase transformed to rutile phase. The ordered mesoporous structure was
collapsed due to intrinsic crystal growth and sintering at high calcination tempera-
ture, while in route 3, as synthesized product was directly calcined in presence of H2
at 500 °C. It resulted in formation of mixed phase product with reduced surface area
(62 m2 g−1 ). From this, it was concluded that ethylenediamine encircling process,
allows the formation of the highly crystalline ordered mesoporous TiO2 with anatase
phase, high surface area, and large pore size. Because of the presence of large pore size
and high surface area, hydrogen diffusion and its interaction with surface was facili-
tated. And also, the transformation of anatase to rutile phase and crystal growth during
hydrogenation process at 500 °C was prevented. Specific surface area of OMBT was
18 Synthesis—Activity Correlations Established for TiO2 … 775

124 m2 g−1 . The OMBT showed highest photocatalytic hydrogen generation at the
rate of 136.2 μmol h−1 using 100 mg of photocatalyst under simulated solar light
illumination among all the samples. The improved light absorption from UV to IR
region and photocatalytic hydrogen production was attributed to the presence of Ti3+
point defects.

18.4.2 pn Heterojunction

pn heterojunctions are commonly used to restrict recombination reaction by facil-

itating the separation of photoinduced charges at interfacial contact and also to
decrease the effective band gap. A composite of two dissimilar semiconductors (p
and n) shows modified properties as compared to the individual semiconductors.
This is attributed to the heterojunctions formed at the interface of p and n semicon-
ductors. Depending on the band positions and band gap, the valence band (VB) and
conduction band (CB) of p are aligned with the VB and CB of n type semiconductor
in three different manners classified as type (I), type (II), and type (III) as shown in
Fig. 18.9. The band alignment at heterojunction facilitates the efficient transfer and
separation of charge carriers [71].
A composite consisting of two different semiconductors has the following advan-
tages (i) allows reduction and oxidation reactions to occur at different sites (ii)
enhanced light absorption in visible region can be achieved by combining TiO2 with
low band gap semiconductors, and (iii) helps in better separation of electron and hole,
and decrease in rate of recombination reaction. Among solid–solid interfaces, semi-
conductor—semiconductor heterojunction, semiconductor—carbon heterojunction,
and semiconductor—metal heterojunction have gained much interest. Interfacial
contact between the semiconductors is important for the facile charge transfer, and
this helps in lowering the recombination rate of charge carriers. Thus, to construct
intimate contact between the semiconductors, it is important to select appropriate
synthesis methods.

Fig. 18.9 Different types of pn heterojunctions (CB: conduction band, VB: valence band)
776 S. A. Rawool et al.

18.4.3 Semiconductor—Metal Heterojunctions

The light absorption and charge separation properties of TiO2 can be improved by
forming effective metal-semiconductor heterojunction. A Schottky barrier is formed
at the interface of metal and semiconductor which helps in the separation of photogen-
erated charge carriers [72]. Also, the surface plasmon resonance (SPR) effect shown
by metal nanoparticles further helps in absorption in the visible region [72, 73].
The metal nanoparticles dispersed on the surface of the semiconductor offer surface
active sites and act as a cocatalyst during the reaction. The photocatalytic activity is
strongly affected by the size, shape, and spatial distribution of the metal nanopar-
ticles; therefore, it is necessary to design a synthesis methodology to control the
properties of the metal nanoparticles. Methodologies like photodeposition method,
wet impregnation method, chemical reduction, chemical vapor deposition, deposi-
tion–precipitation, electrodeposition, atomic-layer deposition, sputtering, and phys-
ical mixing were explored to load metal over the semiconductor surface [74, 75].
Among all these methods, photodeposition is an attractive method because it allows
the deposition of metal nanoparticles at the active centers present on the surface using
light energy. Loading of Pt nanoparticles to improve the photocatalytic activity for
hydrogen generation is a common practice.
Recently, Jiang et al. [76] tuned the absorption of the plasmonic band in the near
IR region by changing the size and shape of the metal nanoparticles. To harvest
visible and NIR region, Au nanocubes and Au nanocages having plasmonic bands
in visible and NIR region, respectively, were deposited on TiO2 nanosheets (referred
as Au cube/cage–TiO2 ). Non-plasmonic Pd nanocubes were also deposited on TiO2
nanosheets as a cocatalyst. Anatase TiO2 nanosheets having average edge of 200 nm
and thickness of 5–7 nm with 95% of percentage of (001) facets over the surface,
were synthesized by hydrothermal method. Au nanocubes and Au nanocages were
deposited by ligand-exchange method. The capping agent cetyltrimethylammonium
bromide (CTAB) present on the Au nanocubes and Au nanocages surface were
replaced by the 3-mercaptopropionic acid (MPA). Thiol and carboxylic groups
present in MPA shows stronger interaction for Au and TiO2 , respectively. To form the
hybrid structure, the Au nanocubes, nanocages, and TiO2 were sonicated with MPA
solution. Proper interfacial contact is necessary for the transfer of electron from Au
to TiO2 . Thus, to further improve the interfacial contact between the two, evacua-
tion followed by annealing was performed. Subsequent to loading of Au nanocubes
and nanocages, Pd nanocubes were also deposited over it. The sample showed the
extended absorption upto NIR region as Au nanocubes and nanocages absorbs in
visible and NIR region, respectively. The sample showed the enhanced photocat-
alytic activity for hydrogen generation under NIR light illumination. The photogen-
erated electrons get transferred from Au metal to the TiO2 photocatalyst, while Pd
nanocubes acted as a cocatalyst to trap the charge carriers. This strategy resulted in
development of efficient catalyst with improved properties for hydrogen generation.
18 Synthesis—Activity Correlations Established for TiO2 … 777

18.5 Single Atom Catalysts (SACs)

Single atom catalysts (SACs) recently have gained tremendous attention over nano-
materials, nanoclusters, and bulk materials. SAC is an ultimate form of the dispersed
catalysts with distinct properties leading to exceptionally high activity and stability.
SACs offer a rational use of metals (advantageous in case of precious metals) with
high efficiency of utilization of atom, distinctive electronic structure, and active sites
with unsaturated coordination [77]. Zhang and co-workers [78] in 2011 deposited
single atoms of Pt over FeOx support by co-precipitation method. Presence of Pt-
O-Fe bonds suggested enhanced metal-support interactions with improved catalytic
activity and stability for CO oxidation reaction. Since then, the SACs have attracted
huge attention for its application in different fields.
Decoration of the single atom on the surface of the support is an important step
in the synthesis of the SACs [79]. Also, the prevention of aggregation of the single
atoms during the synthesis as well as while carrying out the catalytic reaction is a chal-
lenge in SACs. Different synthesis methodologies have been adopted to overcome
the challenges associated with it. Atomic layer deposition, coprecipitation, photode-
position and atom trapping approach are the methodologies adopted to synthesize
SACs. These methods are described in previous chapter by Pai et al. of the present
book.
Long et al. [80] introduced isolated Cu atoms in the Pd lattice deposited over TiO2
nanosheets by aqueous solution synthesis and evaluated its performance for photo-
catalytic CO2 conversion. K2 PdCl4 and CuCl2 were used as precursors for Pd and Cu
ions, respectively. Pdx Cu1 alloy nanocrystals were crystallized insitu over the TiO2
nanosheets by aqueous solution synthesis. The improved activity for CO2 conversion
was assigned to the increased CO2 adsorption and activation along with suppressed
hydrogen generation due to presence of the paired Cu-Pd sites with tunable d-band
centers of Cu sites. Pd7 Cu1 –TiO2 photocatalyst showed high selectivity (96%) for
CH4 generation at the rate of 19.6 μmol gcat –1 h–1 .
Similarly, Sui et al. [81] deposited single atom of Pt selectively over the (101) facet
of the nanosized TiO2 single crystal (referred as x-Pt/TiO2 -A where x is the Pt loading
in weight percent) by photodeposition method. Single atom decorated Pt catalysts
were found to be active and stable for photocatalytic hydrogen generation. Also,
its photocatalytic activity was compared with the commercially available anatase
nanoparticles with similar surface area (referred as TiO2 -0). Figure 18.10a shows the
High angle annular dark field-Scanning transmission electron microscopy (HAADF-
STEM) images of the 0.6Pt1 /TiO2 -A. It confirmed the dispersion of atomic size Pt
on TiO2 -A surface. It was found that the Pt deposited preferentially over the (101)
facets of the TiO2 -A. Figure 18.10b shows the representative model of Pt dispersion
over nanosized TiO2 single crystal. The size distribution in 0.6Pt1 /TiO2 -A showed
that 72% single atoms, 16% nanoclusters of 0.4–1 nm, and 12% particles were
in the region of 1–2 nm size. Also, it was found that size distribution altered after
loading same amount of Pt over TiO2 -0. In TiO2 -0 maximum, Pt particles were found
to be of greater than 2 nm (Fig. 18.10c). The photocatalytic hydrogen generation
778 S. A. Rawool et al.

Fig. 18.10 a HAADF-STEM images of the 0.6Pt1 /TiO2 -A, b representation of the Pt1 /TiO2 -A
sample, c distribution of particle size of Pt deposited over different samples, and d photocat-
alytic hydrogen generation using different samples. Reproduced with permission from Ref. [81].
Copyright 2017 Elsevier

using the different samples were evaluated and shown in Fig. 18.10d. The presence
of Pt enhances the photocatalytic activity for hydrogen generation of both TiO2 -A
and TiO2 -0. Highest hydrogen generation of 84.5 μmol h−1 was observed using
0.6Pt1 /TiO2 -A having Pt loading of 0.6 wt%. It was observed that on increasing the
Pt loading beyond 0.6 wt%, photocatalytic activity decreased. Also, the H2 yield on
0.6Pt1 /TiO2 -A was 4.5-fold greater than that of the 0.6Pt1 /TiO2 -0 though having the
similar Pt loading over TiO2 -A and TiO2 -0. It was also revealed that the 0.6Pt1 /TiO2 -0
possessed optimum amount of exposed (001) and (101) facets as it showed enhanced
photocatalytic hydrogen yield as compared to the sample with higher percentage of
(001) or (101) facets. Thus, dispersion of Pt at atomic level along with optimum
percentages of exposed (001) and (101) facets play a crucial role in modifying the
photocatalytic properties of TiO2 .

18.6 Development of TiO2 Based Photocatalysts

A brief account of the developmental activities taken place in our laboratory during
last few years is given here. It is needless to mention that success of photocat-
alytic water splitting process primarily depends on the properties of photocatalyst.
18 Synthesis—Activity Correlations Established for TiO2 … 779

In continuous search of efficient catalytic systems and surge for improving hydrogen
yield, we investigated and reported photocatalytic properties of several oxide semi-
conductors [44, 82–92]. The development in TiO2 based photocatalysts falls under
the purview of present chapter and will be discussed here. Several titania based
In2 TiO5 , Cu doped TiO2 , nanocomposites of NiO-TiO2 , CuO-TiO2 , and carbon-
TiO2 heterostructures were developed, and their properties were investigated by us.
Various investigative studies were undertaken to induce alterations in the lattice and
structure, which are manifested in light absorption, band structure, and photocat-
alytic properties of titanium oxide. Strategies such as cationic doping by Cu in TiO2 ,
composite formation with NiO and CuO inducing p-n heterojunctions, carbon incor-
poration in bulk TiO2 (C@TiO2 ) to improve electronic conductivity were adopted
to develop a promising photocatalyst. Photocatalysts were characterized by X-ray
diffraction, X-ray photoelectron spectroscopy, N2 -BET, Raman spectroscopy, induc-
tively coupled plasma-optical emission spectroscopy, high resolution transmission
electron microscopy/selected area electron spectroscopy, and diffuse reflectance UV–
visible spectroscopy. Photocatalytic properties of samples were investigated under
sunlight, visible, and UV–visible irradiation. The emission spectra of both light
sources along with reaction assemblies are shown in our earlier publications [83,
85, 86]. Density functional theory calculations were performed, and life time of
e− /h+ from PL decay curves was measured to support the activity trend. The present
section briefly discusses the significant results obtained from these studies.

18.6.1 Type-II pn Heterojunction

NiO is p-type semiconductor and shows absorption in the visible region because of
d-d transition, whereas TiO2 is n-type semiconductor having a band gap of 3.2 eV.
A combination of both p-type and n-type semiconductor forms pn heterojunction at
the interface of the two and will generate electric field which can be utilized to drive
the electron and hole in the opposite direction. Thus, pn junction formation helps in
separation of charge carriers and retards the recombination of the charges.
To prepare NiO-TiO2 composites, sol-gel method is preferred over other methods
as it is simple and cost-effective process required low temperature, easy to incorporate
the dopant ions, and produced fine powders [93]. Titanium isopropoxide and nickel
nitrate hexahydrate were used as Ti and Ni precursor, respectively. In this preparation
both Ni and Ti precursors were mixed in 1:1 molar ratio of Ni:Ti and allowed to form
the gel under acidic conditions. Then the gel was dried by evaporating the solvent and
the dried sample was calcined at different temperature to get desired crystallinity and
phase composition [85]. Figure 18.11 shows the schematic of synthesis methodology
adopted for the synthesis of NiO and TiO2 heterojunction. While carrying out the
synthesis it was observed that not only the calcination temperature but gel drying
temperature also has significant impact on formation of a binary phase (NiO and
TiO2 ), devoid of undesired NiTiO3 phase. Figure 18.11 shows the XRD pattern
of different samples synthesized by varying the gel drying temperature from 90 to
780 S. A. Rawool et al.

150 °C as well as the calcination temperature. LT and HT are abbreviations denoting

the samples synthesized by keeping the gel drying temperature at 90 °C and 150 °C,
respectively. Composite samples showed presence of both cubic NiO and anatase
phase of TiO2 along with NiTiO3 phase. It was found that the amount of NiTiO3
phase was maximum in the sample synthesized by drying the gel at 150 °C than the
sample obtained by drying the gel at 90 °C, even though the calcination temperature
was kept the same in both the cases (Fig. 18.11). From this study, it was revealed
that higher gel drying temperature, i.e., 150 °C favored formation of NiTiO3 phase.
To study the impact of the presence of different phases on photocatalytic properties,
hydrogen generation from water splitting reaction was carried out. The following
trend in activity was observed: NTC11-LT 600 °C, 10 h > NTC11 600 °C, 3 h >
NTC11-HT 600 °C, 10 h > NTC11 500 °C, and 5 h. The deterioration in activity
coincides with the appearance of the NiTiO3 phase in the samples. For comparison,
pure phase of NiTiO3 was also synthesized using solid state and sol gel method.
Both the samples synthesized by two different routes showed very poor activity
nearly 2.2 μmol of H2 g−1 h−1 under sunlight illumination.
To further understand the effect of crystallinity and phase composition, sample
synthesized by drying the gel at 90 °C calcined at two different temperatures 500
and 600 °C and also the duration of calcination time was varied from 3 to 10 h.
It was observed that the sample calcined at 600 °C for 10 h consisted of maximum
amount of NiTiO3 phase along with small amount of rutile as compared to the sample
calcined at 600 °C for 3 h. Thus, it was inferred that rutile phase of TiO2 reacted
preferentially with NiO to form NiTiO3 phase [85]. The poor crystallinity of the
sample calcined at 500 °C was one of the factors resulting in lowering of the activity
as compared to the sample obtained by carrying out calcination at 600 °C. From
the above experiments, it was evident that synthesis parameters such as gel drying
temperature and calcination temperature and also duration of calcination are crucial
in determining the phase composition, crystallinity of the sample and eventually
photocatalytic activities are affected. The highest H2 generation was observed using
sample synthesized by drying the gel at 90 °C and calcining it at 600 °C for 10 h.
This sample was referred as NiO-TiO2 (1:1)—LT 600 °C for 10 h or NTC11 for
convenience. Under these synthesis conditions, a heterojunction formed between
NiO and TiO2 having appropriate crystallinity and with minimum amount of NiTiO3 .
H2 yield at the rate of 204 μmol g−1 h−1 under sunlight illumination with AQE of
5.4% and SFE of 0.8% was observed using the sample NTC11 (Fig. 18.11c). Also,
it showed stable photocatalytic activity for 60 h of irradiation under sunlight.
On further characterization of NTC11 sample, it was observed that both the
phases of NiO and TiO2 co-exist together. Figure 18.12 shows scanning transmission
electron microscopy-high angle annular dark field (STEM-HAADF) images of the
NTC11 samples. The bright and dark contrast represents the presence of TiO2 and
NiO, respectively. Electron energy loss spectroscopy (EELS) confirms that the NiO
and TiO2 are in close contact (Fig. 18.12b). Also, the band alignment at the interface
of NiO and TiO2 in the NTC11 sample was derived using valence band XPS spectra
and DRS measurement data which indicated that the effective band gap at the inter-
face of NiO-TiO2 in NTC11 was lower, i. e., 2.67 eV as compared to the pristine
18 Synthesis—Activity Correlations Established for TiO2 … 781

Fig. 18.11 A Schematic representation of the synthesis of composite samples of NiO and TiO2 ,
B XRD patterns of the samples synthesized by varying the synthesis conditions such as gel drying
temperature and calcination conditions NTC11 obtained after a. drying the gel at 90 °C (LT) and
further calcined at 500 °C for 5 h (named as NTC11 500 °C, 5 h), b drying the gel at 90 °C (LT)
and further calcined at 600 °C for 3 h (named as NTC11 600 °C, 3 h), c drying the gel at 90 °C
(LT) and further calcined at 600 °C for 10 h (named as NTC11-LT 600 °C, 10 h), 10 h or also
referred as NTC11 for convenience and d drying the gel at higher temperature of 150 °C (HT) and
was calcined at 600 °C for 10 h (named as NTC11-HT 600 °C, 10 h). (A: Anatase phase of TiO2 ,
R: Rutile phase of TiO2 , N: NiO and NT NiTiO3 ) and C Comparison of photocatalytic hydrogen
yield using different samples. Reproducedwith permission from Ref. [85] Copyright 2018 Elsevier
782 S. A. Rawool et al.

Fig. 18.12 Low a and high c-d resolution scanning transmission electron microscopy-high angle
annular dark field (STEM-HAADF) images of NTC11 accompanied by electron energy loss spec-
troscopy (EELS) b of the selected area indicated as positions 1 and 2. B Schematic representation
of the proposed mechanism for photocatalytic hydrogen generation. Reproduced with permission
from Ref. [85]. Copyright 2018 Elsevier

NiO (band gap of 3.6 eV) and TiO2 (band gap of 3.2 eV) (Fig. 18.12). Based on the
above facts the mechanism was proposed as shown in Fig. 18.12B. The improved
crystallinity and surface area, minimum amount of NiTiO3 , suitable type II band
alignment at the interface, enhanced light absorption and lower recombination of
charges, contributed positively for the highest H2 production in composite NTC11
sample.

18.6.2 Carbon@TiO2 Composites

Carbon-semiconductor heterojunction is similar to the metal–semiconductor hetero-

junction. A series of carbon and TiO2 composites (referred as C@TiO2 ) were
prepared by varying the amount of carbon from 0.14 to 14.7 wt% using ethylene
glycol and tetrabutyltitanate as precursors for carbon and titanium, respectively. An
organic-inorganic polymer was formed on mixing the two precursors which was
calcined under inert atmosphere and resulted in C@TiO2 composite samples with
TiO2 as major phase. All the C@TiO2 composite samples showed improved light
absorption in the visible region as compared to pristine TiO2 sample. Presence of
carbon prevented the growth of TiO2 nanoparticles as evident by the increase in
crystallite size with an increase in carbon content. Among all samples, C@TiO2
composite with carbon loading of 3.8 wt% showed highest H2 yield @ 1360 μmol
of H2 h−1 g−1 under sunlight. Beyond 3.8 wt%, photo catalytic activity deteriorated.
Excess carbon content could hinder the light absorption of TiO2 , thus lowering the
18 Synthesis—Activity Correlations Established for TiO2 … 783

activity for hydrogen generation. Optimum amount of carbon enhanced the surface
area, light absorption properties, imparted favorable morphology and chemical inter-
action of C with Ti helped in limiting the recombination reaction and improving the
photocatalytic hydrogen yield over C@TiO2 composites.

18.6.3 Cationic Doping

Incorporation of cationic dopants introduces donor or acceptor levels within the band
gap of TiO2 and helps in enhancing visible light photoresponse. Thus, a series of
Cu substituted TiO2 Cux Ti1−x O2−δ (x = 0, 0.02, 0.06, 0.1, 0.2, 0.5) catalysts were
synthesized by sol–gel using appropriate amounts of cupric acetate and titanium
isopropoxide. It was observed that TiO2 lattice could tolerate upto 6 mol% of Cu
ions resulting in single-phase compositions in which Cu2+ occupied Ti4+ sites in TiO2
lattice. The modifications in bond length, coordination number, and disorder in the
lattice caused due to Cu incorporation were investigated by X-ray absorption spec-
troscopy at Cu edge [86, 87], while incorporation of Cu equal to or greater than
10 mol%, resulted in a biphasic mixture consisting of TiO2 and CuO phases. Among
all the samples, 2 mol% Cu doped TiO2 (referred as CuTi2) has shown maximum H2
yield under sunlight illumination. Cu incorporation has imparted favorable electronic
and optical properties. With an increase in Cu content the absorption in the visible
region increases. Figure 18.13 shows the DRS spectra of the samples recorded in
the region of 200–1000 nm. EXAFS studies revealed that doping of Cu into TiO2
lattice generated oxygen vacancies and lengthened Ti–O bonds. Doped samples

Fig. 18.13 DRS absorption spectra of samples synthesized by varying the amount of Cu in TiO2.
aTiO2 , b CuTi(2), c CuTi(6), d CuTi(1–9), e CuTi(2–8), and f CuTi(5–5), B Comparison of AQE and
SFE over CuTi(2) at different catalyst loadings, sacrificial agents (methanol and glycerol (GlOH)),
and form of catalysts. Reproduced with permission from Ref. [86]. Copyright 2016 Elsevier
784 S. A. Rawool et al.

have shown lengthened Ti–O bonds, introduced oxygen ion vacancies, and distor-
tion in TiO2 lattice. Along with this, XPS studies of fresh and spent photocatalysts
revealed that during light illumination CuO present on surface was reduced to Cu2 O
by photogenerated electrons. Based on exsitu investigations from XPS and other
experimental evidences, a mechanistic scheme involving the Cu2+ and Cu+ species
was also proposed [86]. Apart from development of photocatalysts, we also moni-
tored the effect of various experimental parameters such as amount of photocatalyst,
amount of sacrificial reagent, form of catalyst (powder/films), alignment of photore-
actor with respect to light source, effect of variation of flux of sunlight in different
months and day, on photocatalytic activity of most active CuTi(2) sample as shown
in Fig. 18.13c [86, 87]. Also, we attempted to improve the catalytic efficiency as well
as scale up the reaction for practical use by spreading the catalysts over the indium tin
oxide coated on polyethylene terephthalate (ITO-PET) films [86, 87]. For preparing
films of CuTi(2), doctor-blade technique was used to coat ITO-PET substrates. It was
found that the films resulted in better efficiency of 3.06% for photocatalytic hydrogen
generation rather than dispersed in the powder form (1.41%) (Fig. 18.13B). Also,
the easy processing, handling, and recovery of catalyst are the additional advantages
offer by spreading of catalyst over the film.
The most active TiO2 samples obtained after above modifications without co-
catalyst are compared under sunlight (Fig. 18.14). We summarize here that cationic
dopants, formations of pn heterojunctions, and dispersal of carbon are effective in
improving the optical and photocatalytic properties of TiO2 for its application in
conversion of solar energy to solar fuels.

Fig. 18.14 Comparison of 2 20

photocatalytic H2 generation H2 yield (L/h/m ) AQE (%)
terms of L h−1 m−2 and AQE 18 18
Cu-TiO2
of the Cu-TiO2 , NiO-TiO2
composite, and C@TiO2
C@TiO2 16
composite samples recorded
15
under sunlight illumination.
Note The experiments were 14
H2 yield (L/h/m )
2

carried out under direct

sunlight illumination. Flux 12 12
AQE (%)

variations are taken care by

AQE measurements 10
9
8
NiO-TiO2
6 6

4
3
2

0 0
18 Synthesis—Activity Correlations Established for TiO2 … 785

Experimental conditions: 50 to 100 mg of the catalyst dispersed in water +

methanol solutions (15 mol of 33% v/v of methanol) in a 81 ml volume quartz reactor
with geometric illumination area of 20 cm2 ). Reaction mixture was evacuated and
irradiated under direct sunlight on terrace of our institute. Hydrogen yield was
monitored intermittently using GC equipped with thermal conductivity detector.
Conclusions and future perspective
Present chapter acclaimed the role of synthesis in evolution of TiO2 based catalysts
over the decades for various photocatalytic applications. First part of chapter deals
with the photocatalytic processes, role of photocatalyst, their selection criteria, and
overview of the selected promising photocatalysts. Second part illustrated the role of
synthetic methods/conditions in modifying the morphology and structural character-
istics of TiO2 such as surface area, particle size, shape, phase, crystallinity, exposed
facets, and defects. The synthesis driven modifications enhanced the photocatalytic
properties of TiO2 nanomaterials for various applications. Some typical examples
in each category of 0D, 1D, 2D, and single atom TiO2 based photocatalysts were
discussed to establish the synthesis-property correlations. Different methodologies
such as metal doping, and heterojunction formation is also discussed by which elec-
tric, optical, and surface properties of TiO2 was improved further. Last section of the
above chapter presents the research work undertaken in our laboratory to improve the
photocatalytic properties of TiO2 based photocatalysts for sunlight assisted photocat-
alytic hydrogen generation. We conclude here that an understanding of the synthesis
methodologies is crucial for growth of TiO2 or other catalysts for photocatalytic
applications.

Acknowledgements The authors sincerely thank Dr. A. K. Tyagi, Director, Chemistry Group,
BARC for his support and encouragement.

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Chapter 19
Lasers in Materials Processing
and Synthesis

Sisir K. Sarkar

Abstract The laser is a central technology within photonics having a great economic
impact. Laser material processing has currently flourished into a full-scale discipline.
The present article conveys the basic essence of the subject with a few examples
but definitely not a comprehensive review. Here, the purpose is to bring scientists,
engineers, and manufacturers on a common platform to overview the understandings
of current developments of laser applications in material science and also of the
various new possibilities. We will first explore some processing segments of the
industry, namely, lasers in cutting, drilling, marking, engraving, and then follow it
up with further developments such as laser shock peening and laser surface treatment.
In recent times the market is witnessing a paradigm shift with newer applications of
laser annealing for thin films, additive materials deposition, and rapid prototyping.
Various strategies are discussed based on non-equilibrium processes at interfaces
and chemistry for the synthesis of materials including nanoparticles, nanocomposite
films, and nano patterning. The advent of ultrashort lasers and their commercial
availability has opened up novel applications in the processing industry.

Keywords Laser material interaction · Materials processing and synthesis ·

Ultrafast laser · Laser chemistry · Laser Isotope Separation · Chemical vapor
deposition · Nano and nanostructured materials · Laser-Induced Graphene · Laser
photochemical technology

19.1 Introduction

Albert Einstein in his paper on the theory of quantum and radiation described an
effect which is known as stimulated emission of radiation [1]. A new light source
that originated based on this process was named LASER, which is an acronym of

S. K. Sarkar (B)
Bhabha Atomic Research Centre, Mumbai 400085, India
National Centre for Free Radical Research, Savitribai Phule Pune University, Pune-411007, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 791
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_19
792 S. K. Sarkar

Light Amplification by Stimulated Emission of Radiation. Therefore, a theoretical

foundation was made in 1917 for today’s several billion-dollar industries.
After about 43 years, the theoretical knowledge was realized experimentally and
the first laser was “born” on May 16, 1960. Theodore Maiman, working at Hughes
Research Laboratories, USA, built the first laser with a ruby rod, emitting red light
pulses at 693.4 nm. It took another seven years to employ this laser for the first
industrial applications for drilling a hole into a diamond. The hole drilled had the
dimension of 4.7 mm in diameter by 2 mm deep and was accomplished in 15 min.
This feat was remarkable since a similar application was needed one day at that time.
The laser is a central technology within photonics having a great economic impact
and it can be classified as “general-purpose technology”. Laser technology has
progressed by a series of important innovations and a large number of lasers have
been developed over the last sixty years. Advances in lasers have widened the appli-
cations of this technology, many of which have shaped remarkable enhancements
in the performance of technologies utilizing lasers. It has altogether transformed
medicine, opened up communication through the internet, and plays a pivotal role
in linking economic, cultural, and political aspects of society worldwide. Nurturing
global awareness about light-based technologies can offer solutions to challenges in
agriculture, education, energy, health care, and security.
The application of lasers in material science and technology has flourished into
a full-scale discipline. This area is attracting the attention of scientists, engineers,
and manufacturers equally. Scientists are looking at the basic laser material interac-
tion, while others are exploring it as a device to make faster, cheaper, and cleaner
manufacturing processes. All these efforts are also opening up newer technologies
and manufacturing processes. The most recognized application areas are machining
which includes drilling, cutting and shaping, welding, recrystallization, glazing, and
surface treatments. Chemical processing which includes reaction, material deposi-
tion, micro-patterning, and extended-area processing has applications in material
science, optoelectronics, and sensor technology. Progressively, they are being used
in biotechnology, medicine, and also in the restoration/conservation of artworks.
The present article conveys the basic essence of the subject with a few examples
but definitely not a comprehensive review. There are many excellent books and review
articles on various aspects of the field available in the literature [2–11]. Here, the
purpose is to bring scientists, engineers, and manufacturers on a common platform
to overview the understandings of current developments of laser applications in
material science and also of the various new possibilities. We will first explore some
processing segments of the industry, namely, lasers in cutting, drilling, marking,
engraving, and then follow it up with further developments such as laser shock
peening and laser surface treatment. In recent times, the market is witnessing a
paradigm shift with newer applications of laser annealing for thin films, additive
materials deposition, and rapid prototyping. Next, various strategies will be discussed
based on non-equilibrium processes at interfaces and chemistry for synthesis of
materials including nanoparticles, nanocomposite films, and nano patterning. The
advent of ultrashort lasers and their commercial availability has opened up novel
applications in the processing industry [2].
19 Lasers in Materials Processing and Synthesis 793

19.2 Back to the Basics: Light Industry

Lasers are photon energy sources with unique properties. For a detailed understanding
of the subject, refer to many excellent books in the literature [12–17]. The basic laser
system consists of the lasing medium, the resonator optics, the pumping system, and
the cooling system if required (Fig. 19.1) [10]. The lasing medium according to its
energy level structure generates the primary wavelength of the output beam. The
lasing mediums, such as crystals or gas mixtures, are pumped by various methods
such as flash lamp, electrical discharge or diode laser stack. Population inversion
is achieved in the lasing medium by exciting with the proper pumping system and
photons are generated within the optical resonator due to stimulated emission. The
optical resonator design governs the photon energy to a narrow range, and only those
photons along the optical axis of the resonator can be continuously amplified. The
front mirror allows a certain fraction of laser energy to come out of the resonator
as laser output. The output beam may pass through further optics to be adapted to
specific applications such as polarizer, beam expander and lens, and beam scanner,
etc. The use of nonlinear optical elements can generate different wavelengths from
the primary wavelength. The Nd:YAG (neodymium-doped yttrium aluminum garnet)
laser emitting 1.06 μm wavelength can be frequency doubled (532 nm) or tripled
(355 nm) by inserting nonlinear crystals inside the resonator cavity.
Understanding the physics of laser-material interaction is crucial for gaining
insight into material processing. When a laser beam hits the target material, its
energy being partitioned in three different ways, namely, reflection, transmission,
and absorption. The absorbed energy is utilized for heating or dissociating the mate-
rial. From the microscopic viewpoint, first, the free electrons absorb the laser energy
and then the absorbed energy gets transferred to the lattice ions via the associated
electron network as illustrated in Fig. 19.2 [10].

Fig. 19.1 Configuration of a basic laser system

794 S. K. Sarkar

Fig. 19.2 Laser material interaction and energy absorption by the target material

At sufficiently high laser intensities, the material surface rapidly attains melting
and vaporization temperature, and at the same time, heat is being dissipated into the
material via thermal conduction. This leads to the melting and vaporization of the
target material. By raising the intensities further, the vaporized materials start losing
their electrons and plasma is formed which is a cloud of ions and electrons. Rapidly
expanding vapor/plasma above the target generates a strong shock wave along with
the thermal effects.
The heat penetration depth D through which the heat can be transported within the
laser pulse duration is estimated as: D = [4 × α × tp ]1/2 , where α is the diffusivity of
materials, and tp is the laser pulse duration. The well-known Lambert’s law provides
the transmission of laser energy in the target material, I(z)
 
I(z) = I0 . exp (−a . z )

where I0 is the incident laser intensity at the surface, a is the wavelength-dependent

absorption coefficient and z is the distance from the surface. Metals are mostly opaque
to all laser wavelengths and a is in the range of 105 cm−1 , which indicates that laser
energy decays to 1/e of the energy at the surface within a depth of 0.1 μm. Liquids,
glasses, and many nonmetals have different a values, and therefore, laser energy
during its transmission may be absorbed over a much longer distance.
The three quantities: A the surface absorptivity, R the reflection, and T the trans-
mission are related through the relation: A = 1 − R – T. For opaque material, it
simplifies to A = 1 – R since T being zero. It may be noted that reflection and
absorption are dependent on various parameters like wavelength, temperature, and
surface condition. Thus, copper having an absorptivity of 2% for 10.6 μm CO2
laser can have much higher absorptivity of about 60% for UV laser. At elevated
temperatures, absorption usually increases due to more availability of free electrons.
19 Lasers in Materials Processing and Synthesis 795

19.3 Analysis of Material Processing System

From the discussion above, it is obvious that laser material interaction can be
complex, involving a wide range of phenomena like thermal conduction, fluid
dynamics, melting, vaporization, plasma, and shock wave formation. It is possible
to get insight into the underlying physics in laser material processing by modeling.
However, without going into the actual modeling, as a process engineer or manager,
one can get a relatively complete picture following the four-factor analysis of time,
spatial, frequency, and magnitude.

19.3.1 Time Attribute

CW laser has the capability of power modulations such as ramping up or down the
power, focusing control, and energy-motion synchronization which are very attractive
features for laser processing system. Though the CW laser delivers an average power
ranging from W to tens of kW, its peak power is relatively lower compared to pulsed
lasers.
There are several types of pulsed lasers delivering typically from millisecond to
nanosecond pulses. One way to produce such pulses from several tens to hundreds
of nanoseconds (10–9 s) is by a technique known as Q-switching. In this mode, the
cavity is rapidly changed from a low-Q to a high-Q state, where Q represents the
ratio of energy stored to the energy dissipated within the cavity. Material processing
by such Q-switched solid-state lasers and CO2 lasers is benefited from their high
peak power and reduction of thermal diffusion. Even shorter pulse durations can be
achieved with other techniques and their application will be discussed in the later
section. Currently, large varieties of pulsed lasers can deliver pulse energies from nJ
to over 100 J and can have kHz–MHz repetition rate. From the basic parameters of
pulse energy, duration, and repetition rate, the peak power and the average power
of the laser can be calculated. Peak laser intensity is obtained, dividing the pulse
energy by pulse duration and beam area. With the availability of several orders of
pulse duration, the pulsed laser can achieve peak laser intensities much in excess of
108 W/cm2 , while CW lasers normally provide laser intensities less than 108 W/cm2 .

19.3.2 Spatial Attribute

For laser material processing, the spatial distribution of the beam is of importance
which governs the thermal field on the target. Normally, the output laser beam from
the resonator cavity can have one or several modes, which are called transverse
electromagnetic mode (TEM). The lowest order TEM00 mode has Gaussian beam
distribution and is quite useful for processing. For a material with absorption A (= 1
796 S. K. Sarkar

– R), processed with a Gaussian beam of radius r, the spatial distribution of absorbed
laser intensity on the material surface is given by
   
I(x, y, t) = (1 − R) x I0 (t) x exp − x2 + y2 / r2

where I0 (t) = 2P(t)/πr2 is the average laser intensity and P(t) being the time-
dependent laser power. In general, the transmission of laser energy at depth z is
expressed as

I(x, y, z, t) = A x I0 (t) x exp ( −az ) SP(x, y)

where A = fraction of laser energy absorbed by the material surface, I0 (t) = initial
distribution of temporal intensity, a = absorption coefficient, and SP = spatial distri-
bution of intensity. Other beam shapes like hat-top profile having uniform laser
intensity at the center are also being employed.
Laser beam radius is estimated as the length from the beam center within which
86.4% [(1 − 1/e2 )] of total energy resides. By using a focusing lens, the beam radius
can be reduced and the beam radius at the focus is called the focused spot size.
For lower intensity laser, an energy profiler can be used to directly measure the
intensity distribution. However, it is difficult to measure spot size smaller than tens
of microns or when the laser power is high. By burning holes in appropriate thin sheet
material, the spot size is measured for high-power laser. A more accurate solution is
obtained in case of a Gaussian beam by combining the experimental measurements
with optical calculations. More than three measurements at different locations are
measured to obtain (Zn , Dn ), n = 1, 2, 3… where Dn is the beam size at location Zn .
The propagation of laser beam in the air is expressed as
 2  
D2n = D20 + 4M2 λ / π (Zn − Z0 )2 / D20 ; n = 1, 2, 3 . . .

where D0 is the beam waist, Z0 is the beam waist location, and M2 is the beam quality
parameter. M2 can be determined by measuring D0 , Z0, and (Zn , Dn ), and then it is
possible to determine the spot size at any location along the optical axis. Knowing
M2 , one can also calculate the beam divergence and depth of focus (DOF), which is
the range of distance over which the spot size changed from the focused spot size by
5 percent. Figure 19.3 illustrates the propagation, the beam waist, and the DOF of a
laser beam [8].
Laser material processing is claimed to be noncontact because the highest intensity
is at the focus while laser optics are some distance away from the target. It is not
always convenient to change the focus in processing. The limited depth of focus
limits laser machining to relatively thin materials (usually < 15 mm). In material
processing, one has the option of moving either the beam or the job and also both of
them if the need arises. An XY or XYZ motorized stage is commonly used. Laser
beams can be quickly scanned across specified locations by computer controlled
19 Lasers in Materials Processing and Synthesis 797

Fig. 19.3 The depth of focus of laser light

reflection optics. This makes high-speed marking or drilling possible. The spatial
resolution of laser material processing is influenced by the focused spot size. Shorter
wavelength lasers are thus used for precision machining tasks.

19.3.3 Frequency Attribute

Since interaction of materials is a function of laser frequency, the processing

frequency is one of the important parameters in deciding the outcome. The frequency
governs the energy associated with the laser photon. Lasers being monochromatic
have very narrow spectral width, while conventional energy sources have wide and
complex spectral distributions. For circular beams, the focal spot size is given by Dmin
= 2.44 f x λ / D, where f is the focal length of the lens, λ is the wavelength, and D is
the unfocused beam diameter. Therefore, shorter wavelength lasers are preferred for
high-precision applications. The ablation of organic polymers by UV laser can have
different mechanisms compared to visible or infrared laser ablation. While the UV
laser ablation proceeds mainly through photodissociation, the visible and infrared
laser ablation occurs via photothermal route.
Metals normally having high absorption at UV, the absorption decreases with
increasing wavelength (CO2 laser 10.6 μm). Liquids and nonmetals like ceramics
have strong absorption at UV, then it decreases in visible and again increases in the
infrared region. Almost all materials absorb strongly in the vacuum UV region. Based
on this understanding, different materials need to use lasers of different wavelengths
for efficient energy coupling. Absorption also depends on temperature, purity, and
surface condition. Defects or impurities in transparent media may strongly absorb the
laser energy, and thus create a local thermal point and finally break down the trans-
parent condition. At high enough laser intensity, multiphoton absorption may occur;
material reacts nonlinearly to the irradiation. Once the surface temperature rises,
798 S. K. Sarkar

absorption tends to increase, which forms a positive feedback. In this meaning, very
high laser intensity may be regarded as wavelength-independent material processing.

19.3.4 Magnitude Attribute

The characteristic magnitudes of laser energy are power (watt), pulse energy (Joule),
and intensity (unit: W/m2 ). The interaction is governed by energy intensity when
the interaction between the laser and the material is not continuous. The variation
of laser pulse energy can be from nJ to well above 1 J, pulse duration from several
femtoseconds (fs = 10–15 s) to about 1 s, and the spot size from micrometer to over
1 cm. As indicated earlier for pulsed lasers, the laser intensity is equal to E0 /(tp x
πr2 ), where E0 is pulse energy, tp is pulse duration, and r is beam radius. For laser
pulse energy of 0.1 J, if the pulse repetition rate can vary in the range from 1 Hz
to 4 kHz, then the average power is 0.1−400 W. Let’s vary the pulse duration and
the irradiation area and then compute the peak intensity. With r = 0.5 μm, the peak
intensity of a 10 fs pulse is 1022 W/cm2 , the intensity of a μs pulse is 107 W/cm2 ,
and the intensity of a ms pulse is only 104 W/cm2 . From this, it is quite clear that
laser intensity can be flexibly controlled over a very wide range.
Depending on the absorbed laser intensity, different physical phenomena are
involved [2]. Applications at various laser intensities and deposition times are shown
in Fig. 19.4 [10] and Table 19.1 [2, 4, 10]. We tacitly assume that only one photon
is absorbed by one electron at a specific time at normal laser intensities, but when
the laser intensity is extremely high, as in the case of ultrafast lasers (pulse duration
< 10–12 s), more than one photon can be absorbed by one electron simultaneously.
This is termed as multiphoton absorption. Material optical property is then highly
nonlinear and is very different from single-photon absorption. Material can act as if

Fig. 19.4 Correlation of the

laser power density and
interaction time deciding the
material processing map.
This was reproduced with
permission from the Laser
Institute of America [9]
19 Lasers in Materials Processing and Synthesis 799

Table 19.1 Applications of lasers in material processing [2, 4, 9]

Applications Intensity (W/cm2 ) and laser material
interaction
Laser surface transformation hardening, laser <105 W/cm2 , target heated below melting
forming, laser assisted machining, etc temperature, phase transformation may occur
that can harden the material, elevated
temperature can soften the material. Pulse
duration > 10− 3 s, CW lasers are used
Laser welding, laser cladding and alloying, From 106 W/cm2 to 108 W/cm2 , material
rapid tooling, and laser machining melts, some vaporization and plasma formation
possible. Pulse duration > 10 −3 s, CW lasers
are used
Higher intensity laser machining like marking, From 107 W/cm2 to 109 W/cm2 , material melts
grooving, drilling, and cutting and strong vaporization occurs, shock wave
and plasma formation possible. Pulse duration
normally < 10–3 s, 10–9 to 10–6 s pulse
duration are common, while for
micromachining even shorter pulses are used.
CW lasers or pulsed lasers are used
Laser shock processing, laser surface cleaning Intensity > 109 W/cm2 and pulse duration <
10–7 s, very intense surface vaporization
induces strong shock pressure toward the target

it were irradiated by a frequency doubled or tripled laser source. In a sense, we can

say that an extremely high magnitude of laser intensity can be equivalent to shorter
wavelength experiments. From the above discussion, it is seen that four attributes
analysis is quite useful in laser material processing.

19.4 Application Areas

A laser material processing system consists of the laser source, the beam delivery
system, the motion and material handling system, and the process control system.
Some systems may integrate the sensing unit to improve process quality. The indi-
vidual laser material interaction for specific jobs is discussed below (Fig. 19.5)
[10].

19.4.1 Laser Drilling

Laser drilling is one of the initial applications of laser machining processes. It is a

process by which holes are formed by the removal of material through laser material
interaction. Graduating from drilling hole in diamonds, now a days, it has found
successful applications in automobile, aerospace, electronic, medical, and consumer
800 S. K. Sarkar

Fig. 19.5 Typical laser material processing areas

goods industries. One recognized example is the laser drilling of airfoil cooling holes
of aircraft engines.
Lasers used for drilling require higher laser intensities than the intensities used in
laser cutting. With finite pulse energy, high laser intensity can be achieved by tight
focus and by short pulse duration. Normally, pulsed Nd:YAG lasers or pulsed CO2
lasers are used. Similar to laser cutting, CO2 lasers are a better fit for nonmetals and
Nd:YAG lasers are better suited for metals. The laser pulse duration is normally less
than 1 ms. The average power of the laser may not be as high as that used in laser
cutting, but the achievable laser intensity is higher than laser cutting due to shorter
pulse duration and smaller spot size. Lasers can drill very small holes with high
accuracy and high repeatability. The diameters of holes range from several microns
to about 1 mm. For extremely small diameter holes, tighter focus is needed and green
or UV lasers, such as frequency doubled or tripled Q-switched Nd:YAG lasers, are
used. When the pulse duration is short and the pulse repetition rate is high, the laser
can drill even when the part is moving, resulting in high drilling speed.

19.4.2 Laser Cutting

Important process parameters in laser cutting are power, spot size, stand-off distance,
focus position, scanning speed, gas pressure, gas flow rate and direction, and gas
composition. The quality of laser cutting depends on both the material and the laser.
With suitable control of the process parameters, high quality cutting can be achieved.
The lasers used in laser cutting are mainly CO2 , Nd:YAG, and excimer lasers.
Industrial lasers for cutting typically have power levels from 50 W to 5 kW, although
higher powers are used to cut thick sections. With robust technology of producing
higher average powers with cheaper cost / W, CO2 lasers are being used for the
majority of cutting operations, particularly for nonmetals. The Nd:YAG laser emitting
at1.06 μm having better absorption with metals than CO2 lasers can have smaller
focused spot size and also be fiber-coupled onto the target. All these advantages
19 Lasers in Materials Processing and Synthesis 801

have made the YAG laser a better choice for metal cutting industry. Excimer lasers
emitting in the ultraviolet (193 nm: ArF, 248 nm:KrF or 308 nm: XeCl) are quite
effective for nonmetals, metals, polymers, and semiconductors. Because of their
shorter wavelengths, these UV lasers have better spatial resolution and are used
for high-precision cutting jobs. Recently, advanced technology of diode lasers and
diode-pumped conventional lasers not only have made these lasers compact, but also
increased their average power and they are quickly replacing the bulky conventional
lasers in the market.
In laser micromachining, a much wider variety of lasers with short pulse durations
and high pulse repetition rates are used, such as frequency doubled (Green 532 nm)
and tripled (UV 355 nm) Nd:YAG laser, copper vapor lasers, ultrashort pulsed lasers,
and excimer lasers. The shorter wavelength and shorter pulse duration help to increase
spatial resolution and reduce the heat-affected zone in laser cutting. The higher pulse
repetition rate at smaller pulse energy makes it easier to get a smoother machined
edge. But the average power of these systems is much lower than industrial lasers,
typically < 50 W. High-power industrial lasers are commonly used to cut through
larger thickness parts with sufficient speed, while micromachining lasers are used to
generate small features with high precision.

19.4.3 Laser Marking and Engraving

Laser marking is a thermal process that creates permanent contrasting marks in

target materials by scanning or projecting intense laser energy onto the material. In
some cases, a shallow layer from the target is removed to make the marks, while in
other cases, strong laser irradiation can create a color contrasting from non-irradiated
area. Lasers are also used to engrave features into materials such as wood or stone
products. Laser marking holds around 20% market share of all laser applications and
represents the largest number of installations among all laser applications. Lasers can
mark almost any kind of material and are used for showing production information,
gemstone identification, engraving artistic features, imprinting complex logos, etc.
Lasers used for marking and engraving are again pulsed CO2, Nd:YAG, and excimer
lasers.
In general, there are two fundamental marking schemes: one is marking through
beam scanning or direct writing, and the other is marking through mask projection.
In beam scanning or direct writing method, the focused laser beam is scanned across
the target, and material is ablated as discrete dots or continuous curves. In the mask
projection method, a mask with desired features is put into the laser beam path. Laser
energy is thus modulated when it passes through the mask and a feature is created on
the target. The mask can contact the target directly or can be away from the target and
be projected onto the target by optics. This method has been used in the IT industry to
produce very minute and complex features with the assistance of chemical etching.
Beam scanning marking has more flexibility than mask projection marking, while
mask projection marking can be much faster than beam scanning marking.
802 S. K. Sarkar

19.5 More Applications

We have seen already that laser energy is flexible, accurate, easy to control, and has
a wide range of freedom in spatial, temporal, magnitude, and frequency of laser. In
this section, we will present some more applications other than the already described
above processes.

19.5.1 Laser Hardening

In laser hardening, a laser beam scanning across the metal surface can rapidly heat
the top thin layer of the metal during laser irradiation without melting, and after
the irradiation, it quickly cools down due to heat conduction into the bulk material.
This is equivalent to the quenching process in conventional thermal treatment. When
favorable phase transformation occurs in this laser quenching process, such as in
the case of carbon steels, the top surface hardness increases strikingly. Commonly
used systems are Nd:YAG, diode, and CO2 lasers. The hardened depth can be varied
up to 1.5 mm and the surface hardness can be improved by more than 50%. Laser
hardening can selectively harden the target, such as the cutting edges, guide tracks,
grooves, interior surfaces, dot hardening at naps, and blind holes. The neighboring
area remains uninfluenced during laser hardening. By suitable overlapping, a larger
area can be treated.

19.5.2 Laser Glazing

In laser glazing, the laser beam scans over the surface to produce a thin melt layer
while the interior of the work piece remains cold. Re-solidification occurs very rapidly
once the laser beam passes by, thus the surface is quickly quenched. As a result, a
surface with special microstructure is produced that may be useful for improved
performance such as increased resistance to corrosion. The surface layer usually has
finer grains and may even be amorphous. Laser glazing of cast iron and aluminum
bronze has demonstrated much enhanced corrosion resistance.

19.5.3 Laser Cladding

Laser cladding normally involves covering a relatively low performance material with
a high-performance material for enhancing the wear resistance and check corrosion.
In laser cladding, the overlay material is spread over the substrate or continuously fed
to the target surface. A thin top layer is melted which bonds with the overlay material
19 Lasers in Materials Processing and Synthesis 803

metallurgically. The difference with laser alloying is that the overlay material doesn’t
intermix with the substrate. Cladding allows the bulk of the part to be made with
low-cost material and coat it with a suitable material to gain desired properties and
a good surface finish. Compared to conventional cladding processes, such as plasma
spraying, laser cladding has the advantage of low porosity, better uniformity, and
good dimensional control of the cladding alloy.

19.5.4 Laser Shock Peening

High intensity (>GW/cm2 ) laser ablation of materials generates plasma that has
high temperature and high pressure. In open air, this pressure can be as high as sub
GPa and the expansion of such high-pressure plasma imparts shock waves into the
surrounding media. With the assistance of a fluid layer which confines the expansion
of the plasma, 5 to 10 times stronger shock pressure can be induced. This multi-GPa
shock pressure can be imparted onto the target material and the target is thus called
laser shock peened (LSP).
Laser shock processing can harden the metal surface and induce in-plane compres-
sive residual stress distribution. The compressive residual stress refrains from crack
propagation and greatly increases the fatigue life of treated parts. LSP when compared
to mechanical shot peening, especially for irregular shapes, provides a profound layer
of compressive residual stress and is a more flexible process. LSP can increase the
fatigue life of aluminum alloy by more than 30 times and increase its hardness
by 80%. Materials such as aluminum and aluminum alloys, iron and steel, copper,
and nickel have been successfully treated. Laser shock processing has become the
specified process to increase the fatigue lives of aircraft engine blades.
Conventional laser shock processing requires laser systems that can deliver high
pulse energy (~50 J) with a very short pulse duration (~50 ns) with a Q-switched
Nd:YAG laser. Such laser systems are expensive and the repetition rate is low (several
pulses per minute). This situation is improving with cheaper high-power systems
becoming commercially available. On the other hand, this technique can be extended
to low pulse energy lasers with short pulse duration and tight focus. Two key require-
ments for successful processing are laser intensity >GW/cm2 and short enough pulse
duration (<50 ns). It is shown that the efficiency of the process can be more than 300
percent by treating the sample with a 50 ns pulsed UV laser.
There are many other laser material processing applications, in which difficult
problems are solved by lasers, such as laser-assisted machining of super alloys and
ceramics, laser-assisted etching, laser surface cleaning, and laser coating removal.
In laser-assisted machining, the laser is used to locally heat the work piece prior
to the cutting tool in an attempt to improve the machinability of difficult materials
such as super alloys and ceramics. Etching rate is sensitive to temperature, thus laser
beam can be used to enhance the etching rate locally. This is, in fact, one way of
direct writing on the material. With the combination of laser heating and chemical
etching, semiconductor devices can be etched 10 to 100 times faster than conventional
804 S. K. Sarkar

procedures. Laser-induced shock waves can be used to clean very minute particles
on a silicon wafer, and laser ablation has also been used to remove rust or peel-off
coatings by affecting a very thin surface layer.

19.6 Shifting of Landscape

In recent times, the laser materials processing market is witnessing a paradigm shift
boosted by a multitude of advances—in Europe and in Asia-Pacific (APAC) coun-
tries such as India, Japan, China, and South Korea. Figure 19.6 shows the mate-
rials processing accounts in the total laser market compiled by European Photonics
Industry Consortium (EPIC) [8]. This consortium keeps track of potential users in
various sectors like avionics, automotive, electronics, medical, jewelry, etc.
High-power lasers govern the materials processing sector. The umbrella of mature
laser technology encompasses a variety of lasers - nanosecond, picosecond or
femtosecond; ultraviolet, green; CO2 , diode-pumped solid-state (DPSS), and fiber
lasers. Now with so many choices at hand, the processing industry has to decide
whether there is a strategic laser that can be customized to cater several applications
or one suitable laser per application.
Traditionally, laser materials processing has been subtractive meaning materials
are removed from the work piece. Of late laser additive processing, also known as 3D
printing, is complementing to these operations. Though initially, additive processing

Fig. 19.6 Materials processing accounts in the total laser market compiled by EPIC
19 Lasers in Materials Processing and Synthesis 805

remained as the curiosity, it has now picked up to generate 13% of total revenues
in 2014. Now several years on, this area is showing annual growth of 20% and is
estimated to contribute 30% of revenues by 2020 [18].

19.6.1 Rapid Prototyping and Additive Manufacturing

Rapid prototyping is finding applications in designing either prototypes or quick

fabrication of complex parts in low volume without the requirement of complex
tooling. The process can be one of the two, namely, stereo-lithography using a photo-
sensitive epoxy polymer or selective laser melting using ceramic or metal powder.
The first one uses a low-power UV laser to selectively harden the polymer in a
bath to form the part, while the latter builds up the part with a CO2 laser or 1-μm
fiber laser. In both of these processes, a 3D Computer Aided Design model is sliced
into many layers and then moved to the respective tool. Layer-by-layer processing
is done by directing the laser beam with a galvanometric scanner head. After each
layer processing, polymer or powder is deposited on top of the part, and then the
next laser processing step is initiated to complete the job.

19.7 Ultrafast Laser Processing of Materials

Ultrafast lasers have been developed for quite some time and are becoming more user-
friendly and cost-effective. While the technology is advancing beyond the attosecond
(1 as = 10–18 s) regime, presently the lasers in the nano, pico, and femtosecond time
regimes have been routinely used for processing various materials. Ultrafast pulses
are unique having exceedingly large peak intensities and interact with materials
faster than heat diffusion and lattice disorder time. These two characteristics permit
ultrafast lasers to both control and manipulate the states of materials very precisely
[19].
The advances made in chirped pulse amplification process facilitated the building
of ultrafast lasers. Figure 19.7 shows the schematic of such laser system with the
crucial steps of first the beam stretching, then amplifying, and finally compressing
the beam back [10].
The fs-pulse controls the kinetics of melting and re-solidification of the target
material. Under fs-pulse irradiation, the material undergoes several regimes of exci-
tation and relaxation, before returning to its initial equilibrium state. These are (i)
carrier excitation, (ii) thermalization (iii) carrier removal, and (iv) thermal and struc-
tural effects. The fs-laser pulses can generate huge electric fields, which are even
greater than the binding coulomb fields of electrons in the atom (109 V/m). High
peak pulse energies result in nonlinear absorption within short absorption depths,
limiting the volume of laser energy deposition.
806 S. K. Sarkar

Fig. 19.7 Schematic of ultrashort pulse laser system

It is interesting to discuss the interaction dynamics of ultrafast pulse irradiation of

semiconductors. First; the pulse delivers energy to the material at a faster rate than the
electron–phonon coupling relaxation time. Thus, the laser energy is supplied only to
the electrons and the ions remained completely “cold.” Only after the pulse is turned
off, thermal energy gets transferred to the lattice. Therefore, laser-semiconductor
interactions can be described by unique processes of decoupled optical absorption
and lattice thermalization. Second, high peak intensities of ultrashort pulse facilitate
multiphoton absorption processes.
Compared to the above ultrafast process, when ns laser pulse interacts with a
material, we have already seen that during the excitation process, the excited elec-
trons transfer their energy to the lattice. Thus, during the entire excitation process,
electrons and the lattice remain in equilibrium and the material gets heated to its
melting temperature. The ns absorption process being linear resulted in a much
longer absorption depth and generates a smaller temperature gradient over a longer
distance between the molten layer and the solid material. Consequently, the melt
duration is longer, and the re-solidification front speed is slower, resulting in a crys-
talline structure such as in case of silicon. In case of negligible absorption of material
at the employed laser wavelength, both ultrafast and ns lasers can induce multiphoton
processes. However, ns lasers with lower peak powers ablate materials via thermal
mechanism. This thermal ablation resulted in a poor quality job characterized by a
large heat-affected zone (HAZ) which can also favor melt re-deposition and generate
shockwaves leaving behind defects like chipping and cracks.
Due to the flexibility, speed, and precision, ultrafast lasers are finding large-scale
applications in micromachining. It should be mentioned that they are also being
19 Lasers in Materials Processing and Synthesis 807

utilized as material characterization tools such as surface-enhanced Raman spec-

troscopy (SERS) [17] and laser-induced breakdown spectroscopy (LIBS), besides
providing the basic understanding of the dynamics of ultrafast chemical processes
pioneered by Zewail [20].

19.8 Lasers in Materials Synthesis

Laser chemistry brings to mind the intention that in principle it should be possible
to provide lasers tuned to a given energy level of atoms/molecules so that one can
break the required specific bonds, make specific additions at a particular location, and
prompt specific rearrangements eliminating the wasteful side reactions. Chemists are
so excited about these possibilities that some of them have been talking about the
arrival of laser alchemy. But laser chemistry is not alchemy—at least not yet, because
they are not powerful enough to achieve nuclear transmutation. So far they have been
used to cause changes only on the periphery of the atom—by enlarging the orbits of
electrons, breaking molecular bonds, and making molecules rotate and vibrate faster.
But even these achievements constitute a major breakthrough.
The first milestone in laser chemistry was achieved in 1972 when fairly powerful
UV and IR lasers came into the market. The development of laser isotope separation
(LIS) demonstrated the new potential of lasers in chemistry and material science [21–
23]. Further progress was made by the ground-breaking works of Zewail leading
to femtochemistry, which revealed the dynamics of ultrafast chemical processes
and also helped in realizing the long-cherished dream of controlling the chemical
reactions [24, 25].
The laser-induced synthesis of materials has the root in laser chemistry. The initial
works in material science as discussed in earlier sections were confined to mechan-
ical processing of materials. However, more knowledge-intensive information on
laser-matter interaction accumulated over time and they were used for the produc-
tion of new materials. Laser ablation of a substance in a vacuum or in a liquid is
used to produce nanomaterials. A large variety of novel materials including carbon
nanotubes, fullerenes, and graphene were synthesized by laser. Deposition of thin
films can be carried out with great accuracy by laser ablation since one nm thickness
film can be obtained with only several hundred laser pulses. It is quite easy to instan-
taneously alter the composition of the deposited film by simply switching the laser
beam from one target to another. As discussed earlier, pulsed lasers readily produce
highly non-equilibrium conditions favorable for synthesizing new materials and also
permit access to new states of matter that enhances our understanding based upon
bulk phase diagrams. These states are short-lived, dynamically evolving, and at the
same time, they pose challenging problems to theoretical researchers.
In essence, it can be put as the chemist is able to reach into the molecular structures
with his hands and rearranging the structure at will. Laser chemistry has blossomed
into a full-scale discipline so much so that, we must restrict our attention to infrared
laser chemistry, leaving mostly any excited electronic state photochemistry. Within
808 S. K. Sarkar

this restriction, various types of laser-driven reaction can be addressed from purely
thermal to bond-specific reaction in a phenomenological way [26–30]:
1. Laser pyrolysis, where the laser is used as Bunsen burner, with the difference
of providing homogeneous chemistry at high temperatures.
2. Laser enhancement of chemical reaction, where the reaction rate can be
accelerated by one or two quanta of excitation.
3. Molecule-specific reactions, where laser not only triggers the reaction, but also
supplies all the energy required thermodynamically to complete the reaction,
e.g., isotope separation, ultrapurification, etc.
4. Bond specific chemistry, where the normal thermochemical route of a chemical
reaction can be changed by the laser.

19.9 Selectivity of Photoexcitation

Before overviewing the above reactions, we should understand the types of selectivity
expected from photoexcitation and also develop some methodology to establish for
IR laser specific reactions from thermal ones.
The rate of excitation for a molecule, Wexc nm , for the stimulated transition m ← n
is given by Wexc nm = σnm I(νnm ) where σnm and I(νnm ) are the absorption cross section
and radiation intensity at the resonant frequency νnm . Owing to the small magnitude
of the infrared quanta, the population of the corresponding vibrationally excited state
by thermal equilibrium is not as a rule negligibly small compared with the population
induced by the radiation. Until the advent of high-power IR lasers, there had been
no IR-source with sufficiently high intensity to be capable of generating excited
species at a higher rate than in thermal equilibration processes. Till then, only IR-
spectroscopy existed, but no IR-photochemistry. Under the influence of an intense
IR laser pulse, energy can be deposited at a very fast rate (1–10 eV during 10–8 −
10–12 s amounting to 1013 eV/s) which can far exceed the relaxation rate Wrelax . For
such a strong deposition Wexc = σabs I > τpulse > Wrelax , considerable excitation of the
internal degrees of freedom is possible without any heating. Therefore, by considering
different relaxation processes, we can obtain different kinds of selectivity. Typically,
there are three kinds of relaxation processes:
(i) intramolecular vibrational energy redistribution (IVR) among vibrational
modes with a typical time scale of τstochastic ≈ 10–13 − 10–11 s.
(ii) inter-molecular vibrational–vibrational (v-v) energy transfer τv-v ≈ 10–9 −
10–6 s.
(iii) vibrational–rotational/translational (V-R/T) energy transfer with τV-R/T ≈ 10–6
− 10–3 s.
Since the first process is intramolecular, it may occur without collisions, while
the other two processes are governed by collisions. Thus, the times τVV and τVT are
mostly dependent on the particular experimental conditions.
19 Lasers in Materials Processing and Synthesis 809

Fig. 19.8 Hierarchy of relaxation times vis-à-vis laser excitation rate and various laser chemical
process

Now depending on the magnitude of τexc (≡Wexc −1 ) relative to various τrelaxation ,

in principle, it is possible to achieve four different types of chemistry (Fig. 19.8)
[21]. They are considered below:
[A] Under the condition: τexc << τstoch , it is possible to realize mode (bond)-
selective excitation of molecules in a non-equilibrium state under the influence
of intense IR laser field. With such excitation, a certain mode or functional
group of a molecule attains a higher vibrational temperature than the remaining
modes or functional groups. Apparently, success can be obtained with the use
of ultrafast laser pulse and appropriate choice of large molecules.
[B] Under a more moderate condition: τstoch << τexc < < τvv , it is possible to achieve
molecule-specific chemistry. The molecules which are resonant with the IR
field attain a higher vibrational temperature than the remaining molecules. But
all the molecules in the mixture retain their initial translational temperature.
This type of molecule-selective chemistry has been developed extensively,
which started in landmark experiments on laser isotope separation.
[C] Further moderating the condition: τvv << τexc << τVT , vibrational equilibrium
can be established among all the components in the mixture, but the vibrational
excitation does not degrade to heat by that time. This is possible when no
molecular component in the mixture has a very fast VT rate. In such case,
non-selective vibrational chemistry during the time ≤ τVT can take place
due to the difference between the vibrational and translational temperatures
in the mixture. Based on this principle, indirect activation of molecules can
810 S. K. Sarkar

be achieved through efficient vibrational energy transfer from the chemically

passive sensitizer molecule that absorbs the laser radiation. This method is
successfully utilized for the investigation of dissociation kinetics.
[D] Finally, under the condition: τVT << τexc , there is equilibrium thermal excita-
tion of all the molecules in the reactor volume, but there is no heat transfer to the
reactor wall. In this case, pulsed thermal homogeneous heating of molecular
gas occurs.
From the above understanding, it is apparent that a methodological difference has
to be ascertained for the contribution of laser-specific reaction over thermal one. A
few criteria for distinguishing the two modes are given below:
1. demonstrate isotopic selectivity in a mixture.
2. time resolve the evolution of reaction products with a resolution comparable or
less than the mean collision time.
3. in case the reaction follows two routes, demonstrate that specific vibrational
excitation accelerates two routes by different amounts.

In the context of various material synthesis strategies, however, we will particularly

examine laser pyrolysis and molecule-selective chemistry schemes in the following
sections.

19.10 Laser Pyrolysis

Laser initiated bulk reaction (case D) can be categorised as “black-box” vessels for
efficient synthesis and chemical process control. CW laser irradiation of a substance
at high sample pressure (p ≥ 10 torr) or collisional energy transfer (from chemi-
cally inert laser absorbing molecule like sulphur hexafluoride) inevitably leads to
equilibrium thermal heating owing to V-T relaxation. Here, laser serves as a Bunsen
burner and naturally gives rise to thermochemistry. Still, laser-driven reactions could
be very different from the corresponding ones, in which, an equivalent amount of
translational energy is deposited by a conventional heat source. In these reactions, the
key to understanding the mechanism may be that the laser induces high-temperature
chemistry away from the vessel walls or homogeneous chemistry, whereas conven-
tional high-temperature chemistry often has a dominant heterogeneous component.
This technique has many advantages over hot flow tube reactors such as use of very
simple apparatus, small sample size, and strictly homogeneous pyrolysis.
Remarkably specific yields of unusual products have been found: (i) icosaborane
(B20 H16 ) from irradiation of diborane (B2 H6 ) with 1.5 W CW CO2 laser and (ii)
high yield of paraformaldehyde from CO2 laser radiation of ethylene/air mixture.
SF6 has been used to provide vehicle for absorption of CW infrared laser radiation
in those instances where the reactants are transparent to such radiation, thereby
generating controlled temperatures from 500 to 1500 K. Since SF6 is quite stable up
to 1500 K and has a reasonably fast vibrational-translational (V-T) relaxation time, the
19 Lasers in Materials Processing and Synthesis 811

absorbed energy is rapidly (within millisecond) transferred to the ambient gas. Many
gases like CH4 , C2 F6, and t-butylchloride are decomposed by this laser-powered
homogeneous pyrolysis technique to give various unique products [31]. Interesting
studies on telomerization of C2 F4 and CF3 I induced by TEA CO2 laser were carried
out in conventional and waveguide photoreactors. The product distribution in two
cases differed and was understood in terms of perfluoroalkyl radical concentration
generated in the irradiated volume and their various competing rate constants [32].

19.10.1 Synthesis of Defined Solids and Catalysts with Lasers

Catalytically active solids of adjustable composition can be obtained by laser pyrol-

ysis of various gas mixtures (Fig. 19.9). Rapid heating of well-mixed gaseous reagents
by the laser beam produced very small solid particles with homogeneous struc-
ture and large surface area. Figure 19.10 shows the yield of alkanes and alkenes
obtained from the Fischer–Tropsch synthesis with such Fe/Si/C catalysts. Whereas
with saturated hydrocarbons, mainly, methane is formed, with olefins, considerably
longer chains are obtained. By adjusting the composition of the laser-synthesized
catalysts, better selectivity and preferential formation of the valued light olefins
(C2 -C4 ) can be achieved [33]. In a similar process, powders of specialty ceramics

Fig. 19.9 Synthesis of Fe/Si/C catalysts by CO2 laser pyrolysis. Partial pressures of the gaseous
components and the laser intensities can be varied to produce catalysts with varying properties. This
was reproduced with permission from Wiley Publisher [33]
812 S. K. Sarkar

Fig. 19.10 Yield of alkanes and alkenes obtained from the Fischer–Tropsch synthesis with laser-
produced Fe/Si/C catalysts. The amount of product in % is c and n is the number of C atoms. This
was reproduced with permission from Wiley Publisher [33]

with defined composition can be obtained [34–36]. Irradiation of Fe(CO)5 /SiH4 ,

NH3 /SiH4 , (Me3 Si)2 /NH3 orSiH4 /NH3 /CH4 gas mixtures with a CO2 laser leads to
particularly fine, pure, spherical, relatively non-clumping, and uniform sized Si/Fe,
Si3 N4 , and Si/C/N grains for the production of special ceramics.

19.10.2 Laser-Induced Powder Generation

Ceramic materials are extremely useful materials for manufacturing high-

performance engine parts, such as the turbine, combustion chamber’s inner walls,
injector nozzles, caps and rings for pistons, and rotors for turbo-chargers. Normally,
these materials are brittle and sometimes fail disastrously. However, they can be
strengthened by proper sintering to fuse them into dense parts. This can be achieved
if the starting powder has the following requisite properties:
1. Uniform particle size distribution (<0.5 μm)
2. The particles must be free of contaminants, agglomerates, and multiple
polymorphic phases
3. The particles must have spherical morphology, i.e., the microstructure must be
equiaxed
Conventionally, materials like Si3 N4 and SiC are produced by using: (a) high-
temperature vapor phase reactions in tube furnaces, (b) nitriding or carbiding of
19 Lasers in Materials Processing and Synthesis 813

Si, and (c) DC arc plasma techniques. However, none of these processes produce
particles with all the above specifications.
Ceramic powders of Si3 N4 and SiC with improved properties such as low density,
high-temperature strength, hardness, corrosion resistances were synthesized by
Haggerty et al. by laser-induced chemical reactions [37]. Various mixtures of the
reactant gases, such as SiH4 /CH4 or SiH4 /C2 H4 for SiC and SiH4 /NH3 for Si3 N4 , were
flowed vertically across a horizontally propagating CO2 laser beam. Representative
reactions are given below:
1. SiH4 (g) + CH4 (g) → SiC (s) + 4 H2 (g)
2. SiH4 (g) + C2 H4 (g) → 2 SiC (s) + 6 H2 (g)
3. SiH4 (g) + 4NH3 (g) → Si3 N4 (s) + 12 H2 (g)
The absorption coefficient of SiH4 at 10P(20) CO2 laser line (944.18 cm−1 ) attains
a maximum value at about 0.025 atm, while the absorption coefficient of NH3 goes
to a minimum at about 0.25 atm pressure. Considering these facts, a 10:1 NH3 to
SiH4 mixture at a total pressure of 1 atm was irradiated, where about 70% of the laser
energy gets absorbed within a few cm lengths of the mixture, making the synthesis
process quite efficient. This method produced 5–20 nm sized Si3 N4 and SiC particles
with a narrow size distribution. Morphologically, the shapes are generally spherical
with a large surface area up to 200 m2 /gm and no aggregation or internal porosity.
Based on this, a plant for low-cost production of tens of kilograms of nanometric-
sized powder has been operated with 2.5 kW CO2 transverse flow laser. The plant
has a production rate of 500gm/hr while operating continuously for several hours
[38].
To date, oxides such as titanium oxide (TiO2 ) and titanium vanadium oxide
(Ti1-x Vx O2 ) and non-oxides such as SiC, Si3 N4 and Six Cy Nz ternary compounds with
continuously adjustable between pure carbide and pure nitride have been synthesized.
Synthesis of niobium, tungsten, and tantalum-doped TiO2 , SnO2, and ZnS has also
been carried out by such laser-assisted process.

19.10.3 Synthesis of Metastable Materials

The synthesis of metastable materials can be carried out depending on the high
heating and cooling rates achievable with lasers. The cooling rates achieved in stan-
dard splat cooling or melts pinning techniques (about 106 K/s) can easily be obtained
with scanned cw-laser-heated surfaces. This rate can be further enhanced to about
1010 − 1012 K/s using Q-switched or mode-locked pulsed lasers. With such enormous
cooling rates, it was possible to make glassy alloys for the first time. Binary alloys
consisting of two transition metals, and for combinations of metals with group-
IV elements were made and detailed investigations have been performed. Among
the binary transition metal systems, glasses of Cu–Ti, Co–Ti, Cr–Ti, V–Ti, Au–Ti,
and Ag–Cu have many interesting features [39]. The most studied system of binary
alloys consisting of metals and group-IV elements is the silicides. However, such
814 S. K. Sarkar

glass formation will not be possible if the glass is unstable at ambient temperatures
and if single-phase crystallization is possible from the melt.

19.11 Molecule-Selective Chemistry

Tunable and intense infrared radiation can be interacted with one species which may
be one component in a gaseous mixture or even one isotope in a chemically pure
compound (case B, Sect. 19.9). These molecules undergo multiphoton excitation and
lead to stable products by irreversible dissociation or isomerization in the ground
electronic state. When standard chemical and physical methods of purifications fail,
such selective molecular photodissociation can be used to purify materials.
As already stated, photochemical and photophysical approaches to the separation
of isotopes present major challenges in laser research in chemistry. We will present
a brief account of the vast amount of work concentrating mainly on those aspects
studied in our laboratory.

19.11.1 Laser Ultra-Purification

The selective photochemical removal of impurities with lasers is exemplified by

the purification of gaseous SiH4 (the starting material for the preparation of pure
silicon for semiconductor production) from compounds such as AsH3 , PH3 , and
B2 H6 , which are difficult to remove chemically. Contamination of such p- and n-
charge carriers, even at a ratio of 1:109 , can negatively influence the functioning of
integrated circuits. The beauty of the process is that, laser acts only on the impurities,
whereas in conventional methods, the entire material is subjected to the purification
process. Thus, laser radiation at λ = 193 nm is absorbed four orders of magnitude
more strongly by PH3 and AsH3 and two orders of magnitude more strongly by
B2 H6 than by SiH4 . For purifying an impure (1%) sample, only 1% of the SiH4
gets photolyzed while more than 99% AsH3 , and 40% PH3 and B2 H6 are removed
[40–42]. The end products of this photolysis are readily separable solid polymers or
gaseous compounds. Laboratory experiments show that the purification process even
proceeds efficiently at atmospheric pressure, so that, for impurities of several ppm,
typical absorption cross sections of 10–17 cm2 and reactor lengths of several meters,
more than 50% of the laser light is absorbed. Extremely high-purity silane is important
for the economic production of electricity from sunlight, since the efficiency of silicon
solar cells depends strongly on the impurities present. Further examples of efficient
purification of gases are the separation of COCl2 from BCl3 and of CCl4 from AsC13
and the destruction of dioxin.
Lanthanides and actinides can be efficiently separated and purified by exciting
the narrow absorption bands of their compounds in the visible and UV [43]. The
excitation is still selective even for higher absorber densities in the liquid phase. The
19 Lasers in Materials Processing and Synthesis 815

Fig. 19.11 Laser-induced

separation of lanthanides.
The absorption spectra of
europium in various
oxidation states show that
the Eu3+ ions can be
selectively reduced in the
liquid phase with 193 nm
ArF laser. The Eu2+ ions
formed are precipitated as
EuSO4 after reaction with
sulfate ions. This was
reproduced with permission
from Wiley Publisher [33]

new oxidation states formed by the photoredox processes enable the compounds to
be readily separated. Figure 19.11 shows the separation of europium as an example,
whereby the hydroxyl radical has to be scavenged, e.g., by isopropanol, to avoid
the reverse reaction [33]. The quantum yield for Eu3+ photoreduction at 193 nm
was given as 5% at 90% conversion, whereby up to a three-100-fold enrichment
of europium was measured in the precipitate after irradiation of binary europium/
lanthanide mixtures.

Eu3+ + H2 O → Eu2+ + H+ + OH
Eu2+ + SO2−
4 → EuSO4

H2 S in CO/H2 synthesis gas was photolyzed selectively with an ArF laser and
the sulfur released was removed by adsorption on a metal surface [38]. In this way,
sulfur impurities could be reduced from 10 to 1 ppm. A spectroscopic selectivity
(excitation only of H2 S in the synthesis gas) of 107 was measured in the wavelength
range 210–220 nm. Quantum yields of H2 S decomposition of 0.4 (1 atm) to 1.0
(10 torr) were achieved. In particular, the use of a laser is interesting for the removal
of “fine impurities” (< I ppmH2 S), since catalysts based on copper (e.g., those used
for the production of methanol from synthesis gas) have lifetimes of about one year
if the H2 S impurities in the CO/H2 mixture can be reduced to less than I ppm.

19.11.2 Organic Synthesis with Lasers

The photolytic ring opening of 7-dehydrocholesterol (7-DHC) (Fig. 19.12) to give

vitamin D3 , via previtamin D3 (P3 ), has long been employed for the large-scale
816 S. K. Sarkar

Fig. 19.12 Scheme for the synthesis of vitamin D3 . This was reproduced with permission from
ACS Publisher [39]

synthesis of vitamin D3 . The three isomers: lumisterol (L3 ), tachysterol (T3 ), and
P3 can be interconverted by irradiation with UV light, whereby the photostationary
composition depends strongly on wavelength. Table 19.2 and Fig. 19.12 show that
the use of two laser wavelengths rather than irradiation with a Hg lamp leads to a
considerable improvement in the yield of the desired vitamin D3 precursor P3 [33,
45, 46]. Irradiation with short UV light pulses in the picosecond range decreases the
photolysis of P3 , and improves the ratio of P3 to the undesired T3 by another factor
of 3.

Table 19.2 Photostationary composition of the mixture on irradiation of the vitamin D3 precursor
[45]
Light Source % 7-DHC % T3 % L3 % P3
Low pressure Hg lamp 1.5 75.0 2.5 20.0
Medium pressure Hg lamp 3.4 26.0 17.0 53.0
248 nm KrF laser 2.9 71.0 – 26.0
308 nmXeCl laser 13.0 3.4 42.0 35.0
KrF + N2 laser ( 337 nm) 0.1 11.0 9.0 80.0
19 Lasers in Materials Processing and Synthesis 817

The results of the laser experiments allow improvements in the conventional

photochemical process, namely, the KrF laser (248 nm) and the N2 laser (337 nm)
are replaced by a low-pressure Hg lamp (254 nm) and a medium-pressure Hg lamp
equipped with a suitable filter, respectively. In the production of special vitamin D3
metabolites for medical diagnostics, an increase in yield by a factor of 5 is achieved
by the use of lasers [47].

19.11.3 Laser Isotope Separation (LIS)

The main aim is to develop an effective isotope separation route for uranium-235,
the fissile isotope of uranium which is used as fuel in light water moderated nuclear
reactors. Additionally, a potential market exists for lighter element isotopes like
deuterium, 6-lithium, 10-boron in energy production sectors. Non-radioactive tracers
like 13-carbon, 15-nitogen, 17 & 18-oxygen, 34-sulphur, etc., are very useful in
medical, analytical, and environmental studies. When compared with the current
methods of isotope separation, LIS has the potential to deliver a product with higher
enrichment per stage, energy economy, and savings in capital investment.
Mostly, all laser enrichment processes have three similar requirements: (1) the
isotopic species must have well-resolved spectroscopic absorption features with a
discernable isotope shift. The dense collection of electronic transitions in the visible
or UV spectrum of gaseous atoms or molecules, display very little isotope shifts
arising out of dissimilar nuclear mass, size, shape, and spin. Such isotope shift varies
from 1:105 to 1:108 of electronic transition energy. Whereas the vibrational transi-
tions of molecules in the infrared spectral region are directly linked to the reduced
mass of the constituent atoms. In this case, the relative isotope shift is usually in
the range of 1:100 to 1:1000. (2) the processing laser must be monochromatic and
tunable so that selective excitation of the desired isotope can be performed. (3) an
extraction step must be there which can efficiently remove the desired isotope. The
step could be electrical, magnetic, optical or chemical that operates preferentially
on the excited species before various processes of isotopic scrambling like relax-
ation, collisional energy and/or charge transfer can take place. The last one is the
most rigorous condition for practical implementation of any LIS process. Based on
the above criteria, several strategies have been investigated on a laboratory scale:
(a) single-step electronic excitation via hν1 ; (b) two-step electronic excitation with
hν3 via vibrational state excitation with hν2 ; and (c) multiple- photon (n) excita-
tion via nhν4 in the ground electronic state (Fig. 19.13) [48]. Few isotope selective
experimental results are presented in Table 19.3.
It may be worth mentioning that naturally occurring carbon isotope 13-C has an
abundance of 1.11% and is required to be enriched at a much higher level for its use.
The current technology of enrichment is based on a cryogenic distillation of carbon
monoxide has inherent drawbacks of low separation factor (1.0076), high energy
expenditure, huge distillation tower, and very long time for equilibrium attainment
leading to a high production cost. In order to meet a projected 100-fold increase
818 S. K. Sarkar

Fig. 19.13 Selective excitation schemes in LIS: a single step electronic excitation via hν1 ; b two-
step electronic excitation with hν3 via vibrational state excitation with hν2 ; and c multiple-photon
excitation via nhν4 in the ground electronic state

in demand at lower cost, BARC has developed an energy-efficient LIS process to

produce 50% and ≥ 90% enrichment level products in single and two-stage processes,
respectively (Table 19.3; 48, 49). A prototype facility has been built for demonstrating
plant scale technology, consisting of a 5 J commercial pulsed CO2 laser, photochem-
ical reactor based on multipass refocussing Herriott cell and product separator, with
computerized process monitoring and control.

19.12 Laser Chemical Vapor Deposition (LCVD)

LCVD is a well-established strategy for obtaining thin film deposition on a substrate

by inducing chemical reactions of various materials by laser [50]. This technique
can be of two types depending on the reaction mechanism: (1) pyrolytic and (2)
photolytic. In pyrolytic process, usually Nd:YAG or CO2 laser is employed to create
a hot zone. In this zone, thermally induced chemical reactions take place producing
the film material that is finally chemisorbed onto the substrate. The precursors for
this process must be selected carefully so that the chemical reactions can occur below
the substrate melting point.
19 Lasers in Materials Processing and Synthesis 819

Table 19.3 Isotope selective laser photochemistry at Bhabha Atomic Research Centre [48, 49]
Isotopes Typical results
Pressure (Torr) Laser line Fluence (J/cm2 ) Selectivity
Sulphur SF6 10 P(20) 2.0 10
34 / 32 1.0 CO2 laser
Uranium UO2 (hfacac)2 .THF 10 P(4) 0.08 1.2
235/238 Molecular Beam CO2 laser
Carbon CF3 Cl 9 P(18) 3.0 80
13 / 12 15.0 CO2 laser
Carbon CF2 HCl 9 P(20) 4.0 60
13 / 12 100.0 CO2 laser
Stage 1 CF3 Br/Cl2 (1:4) 9 P(32) 4.5 65
50.0 CO2 laser
Stage 2 CF3 Cl/Br2 (1:6) 9 P(8) 1.7 200
20.0 CO2 laser
Deuterium CHF3 /Ar (1:2) 10 R(10) 30.0 > 40
D/H 75.0 CO2 laser
Tritium CHF3 /Ar (1:2.5) 9 R(8)-9 R(14) 65.0 38
T/H 28.0 (0.2 ppm CTF3 ) CO2 laser
T/D CDCl3 /Ar (1:5) 828 cm−1 21.0 5000.0
12.0 NH3 laser

On the contrary, photolytic LCVD depends on the interactions of the laser beam
directly with the reactants. After absorbing the laser photons, the reactant molecules
dissociate to yield a final product which gets deposited on the surface of the substrate.
Normally, the UV and visible lasers are used in this scheme because the photon
energy is in excess of bond dissociation energy. The precursors and the processing
laser are carefully chosen so that the precursors have a satisfactory absorption coef-
ficient at the laser wavelength. It is apparent that the photolytic LCVD technique
offers deposition of films at lower temperature compared to conventional deposition
techniques. This is a beneficial feature for the semiconductor devices fabrication,
since at lower temperature, impurity redistribution and thermally induced residual
stress are minimized.
Further LCVD process looks promising by eliminating several disadvantages of
other film-depositing techniques like plasma-assisted deposition, chemical vapor
deposition (CVD), molecular beam epitaxy (MBE), etc. Some of the advantages are
(i) better deposition rate (ii) spatial resolution and control, and (iii) least damage to
film/substrate materials.
820 S. K. Sarkar

19.12.1 Metal Films

For preparing metal film, metal alkyls are a promising starting material. Most exhaus-
tive studies have been made on photolytic LCVD of Cd(CH3 )2 and Al2 (CH3 )6 .
. Based on their well-known photochemistry, these molecules undergo single-photon
excitation and dissociation with a UV Ar+-laser
 
Cd(CH3 )2 + hν(257 nm, Ar + -laser) → Cd 1 S0 + 2CH3

Photolysis can be affected in the gas phase and also on the surface, and the gener-
ated free methyl radicals subsequently dimerize to form ethane. With UV intensities
of about 104 W/ cm2 , reasonable deposition rates for Cd of up to 0.1 μm/ s have
been obtained and direct writing with line widths as fine as 0.7 μm has also been
established.
Both pyrolytic and photolytic LCVD have been employed to obtain very good
quality aluminum film from Al2 (CH3 )6 [51]. Direct writing of aluminum lines with
deposition rates up to 0.1 μm/ s and line widths of 2–3 μm was demonstrated. Further
studies have been carried with photolytic LCVD on Ga(CH3 )3 , In(CH3 )3 , Te2 (CH3 )2 ,
Zn(CH3 )2 , and Zn(C2 H5 )2 [52].

19.12.2 Deposition from Metal Carbonyls

Metal carbonyls are attractive candidates for making extended thin film of metals by
photolytic decomposition of Ni(CO)4 , Fe(CO)5 , Cr(CO)6 , Mo(CO)6 , and W(CO)6 .
Typically, metal carbonyls undergo fragmentation process below 350 nm. Using cw-
and low-power pulsed laser, single-photon sequential elimination of CO ligands can
be affected
• M(CO)m + hν → M(CO)* m−1 + CO,
• M(CO)* m−1 + hν → M(CO)* m−2 + CO,
• M(CO)∗ + hν → M∗ + CO,
where the star indicates electronically excited molecule/fragments. Removal of the
remaining ligands after absorption of one or two photons can also be induced by colli-
sions. Pulsed laser excitation at higher power can lead to multiple-photon dissociation
releasing all CO groups together instead of single-photon sequential elimination of
CO ligands.
The literature in this area has been well documented in reference [4]. Metal
films of Cr, Mo, and W were deposited on Si substrates using Ar+ -laser radiation at
257 nm. The temperature rise of the substrate was estimated to be less than 50 K
with the employed laser powers. Deposits were analyzed by Auger technique to get
information on surface photo dissociation and dissociative chemisorption processes.
19 Lasers in Materials Processing and Synthesis 821

19.13 Chemical Transformations in Bulk and Within Thin

Film Materials

Chemical transformations inside organic materials using light encompass photode-

composition, polymerization, and photochromic reactions. Among these, photopoly-
merization has become an active area of research and development in polymer
science and technology. A well-known instance is the transformation of methyl
methacrylate (MMA) into PMMA by using UV or visible radiation. Various tech-
niques employing laser direct writing, interference and laser-light projection are used
for localized polymerization. Additionally, multiple-photon-induced photopolymer-
ization has opened new prospects in 3D-photoprocessing. Frequency-multiplied
Nd:YAG and excimer lasers are mainly used for the fabrication of 3D optical data
storage, optical waveguides, and photonic bandgap structures. The other significant
applications of laser-induced chemical transformations include the following:
(i) Laser lithography: Hg-lamps (λ = 436 nm or 365 nm) were employed earlier
in optical lithography for microelectronic chip fabrication. They are presently
substituted by ArF / KrF excimer lasers [53]. For the fabrication of low-
resolution patterns, maskless techniques are gaining increasing importance.
For the next generation, optical lithography and extreme ultraviolet (EUV)
radiation at 13.5 nm is being developed [54].
(ii) Stereo lithography: Using a CAD program and laser-beam interference for
layer-by-layer polymerization, 3D periodic structures have been fabricated
[55]. Based on two-photon absorption, 780 nm Ti:sapphire laser radiation (ϕ
= 44 mJ/cm2 , τp = 60 fs, rep rate = 90 MHz), can induce polymerization
in viscous liquids like acrylate, epoxy, silica sol–gel, etc. The feature sizes
obtained are well below 100 nm [56]. The technique has been employed for
the fabrication of many devices and, in particular, for 3D photonic crystal
structures [57].

19.14 Pulsed Laser Synthesis of Nanomaterials

Different nanostructured materials have been synthesized by pulsed laser synthesis

(PLS) using a host of gas, liquid, and solid precursors [58, 59]. This versatile tech-
nique has the potential for industrial manufacturing since high pressure or temper-
ature conditions are not required. Various experimental setups are used to optimize
the product yield and size homogeneity depending on the starting materials and the
processing lasers. Typically, the processing laser beam is focused (i) within a gaseous
precursor filled reactor, (ii) in colloidal solution, and (iii) on a solid target positioned
in a pure solution.
822 S. K. Sarkar

19.14.1 Synthesis by Pulsed Laser Ablation (PLA)

Synthesis of inorganic and carbon-based materials can be carried out by ablation [60]
which is a top-down synthesis procedure for nanotubes, nanowires, nanoribbons, and
quantum dots. The procedure is conveniently categorized into the liquid phase and
gas phase with pulsed laser ablation (LP/GP-PLA). The processing laser beam is
focused on the target inside the reactor containing liquid–solid or gas–solid interfaces.
The generated plume of nanoparticles from the ablated target material subsequently
reacts with the liquid or gas. The synthesized material can conveniently be doped by
selecting a precursor containing the dopant element [61].

19.14.1.1 Synthesis by GP-PLA

The GP-PLA is nothing but laser chemical vapor deposition LCVD technique which
has been already discussed (Sect. 19.9). The gas in GP- PLA is used simply to control
the plasma plume dynamics. This setup with low laser power in conjunction with an
external temperature arrangement is used to produce nanomaterials such as carbon
nanotubes (CNT) [62]. With increased laser power, produced plasma itself provides
the high temperature needed for the synthesis of some nanomaterials [63].

19.14.1.2 Synthesis by LP-PLA

Laser irradiation of the solid target positioned in a liquid medium kept inside the
reactor undergoes vaporization followed by the formation of a plume containing
ions, atoms, molecules, clusters, and particles. The generated species react with the
liquid molecules, producing novel nanostructures consisting of both target and liquid
atoms. The liquid layer and high temperature/pressure generated by the focused laser
beam create a confinement situation. This confinement offers a suitable condition for
the formation of metastable phases, which, in turn, helps in various nanostructures
synthesis [64]. The choice of the solid target, the liquid, laser power, and wavelength
are the crucial parameters in producing nanostructured materials of specific prop-
erties and sizes. The synthesized nanomaterials can be collected by filtration from
the colloidal suspension or by evaporation of the homogenous mixture of soluble
nanoparticles.

19.14.1.3 Synthesis by Pulsed Laser-Induced Breakdown (PLIB)

A pulsed infrared laser is focused inside a reactor containing a liquid hydrocarbon

such as toluene and benzene to achieve breakdown [65]. The strong electric field
generated by the focused laser prompts the ionization of the hydrocarbon. In the
ionized volume, the free electrons are further accelerated by the intense field.
19 Lasers in Materials Processing and Synthesis 823

These accelerated electrons collide with the hydrocarbon molecules eject more elec-
trons and results in avalanche multiplication, which induces the breakdown of the
hydrocarbon.

19.14.1.4 Synthesis by Pulsed Laser Photolysis (PLP)

The synthesis method is suitable for both carbon-based and organic materials [66],
and inorganic nanoparticles [67, 68]. Pulsed Laser Photolysisis carried out by irradi-
ating room temperature colloidal suspension with UV or IR pulsed laser. Nanoparti-
cles of FePt were synthesized by irradiating a solution containing iron acetylacetonate
and platinum acetylacetonate. By changing the laser energy, it is possible to control
the size and the ratio of the metals. Photochemical reaction pathways have been
proposed for such nanostructures formation.

19.14.1.5 Synthesis by Pulsed Laser Deposition (PLD)

PLD is employed for the thin film synthesis of semiconductors [69, 70], hetero-
structures of complex-oxide [71], and ceramics [72–74]. Generally, the high-power
laser is focused inside a vacuum chamber to vaporize the bulk target onto a substrate
kept near the target. The laser-ablated material produces the plasma plume which
contains neutrals and ionic species and these species get deposited on the substrate.
For deposition of oxides, the chamber can be filled with appropriate pressure of
oxygen.

19.14.1.6 Synthesis of Graphene Quantum Dots (GQD)

Of late, considerable attention has been received by Graphene Quantum dots (GQDs).
They have many novel properties like excitation-dependent photoluminescence,
resistance to photobleaching, biocompatibility, and low toxicity. They are basically
planar nanoflakes (2–20 nm) of graphene material which is a few atomic layers thick
and have a high surface-to-volume ratio. They have potential applications in photo-
dynamic therapy, drug delivery, bio-imaging, and photocatalysis [75, 76]. However,
the synthesis of good quality GQDs with narrow size distributions and high yield
is still challenging. Recently, a new method using pulsed laser for the synthesis of
intrinsically luminescent GQDs has been reported [77].

19.14.1.7 Synthesis Using PLS of Boron Nitride Nanostructures

Nanostructures of boron nitride (BN) have currently attracted many investigations

due to its various interesting properties, like hardness, low thermal expansion, good
thermal conductivity, better thermal shock resistance, high electrical resistance, and
824 S. K. Sarkar

Table 19.4 Pulsed laser

Target Methodology Synthesized Literature
synthesis of boron nitride
nanostructure
nanostructures [80]
h-BN/acetone LP-PLA Nanofibers [73]
h-BN/acetone LP-PLA Nanotubes [73]
BN Plasma-assisted Nanocapsules [66]
PLD
h-BN PLD Nanosheets [67]
h-BN PLD Thin Films [68]
h-BN Ion assisted PLD [72]

chemical inertness [78–80]. Further, the synthesis procedure has been initiated for
obtaining various forms of BN, such as cubic (c-BN), hexagonal (h-BN), and boron
nitride nanotubes (BNT), which are having many potential applications.
A large number of reports are available in the literature on the synthesis of BN
nanostructures using various techniques [72–74, 78, 79]. Table 19.4 summarizes the
different experimental procedures.
Recently, nanostructures of c-BN and h-BN in high yields were synthesized using
PLS in the gas phase [75]. The characteristic particles produced have a size of 20–
100 nm range and a composition of boron to nitrogen = 1. Borazine vapor was
irradiated with two wavelengths simultaneously (1064 and 532 nm) generated from
the same pulsed Nd:YAG laser for an hour in a high vacuum reactor. Product material
was collected on a substrate placed inside the reactor.
The Raman spectrum (Fig. 19.14a) revealed two sharp peaks at 803 and
1356 cm−1 , and two broad bands at ca. 1000 and ca. 1400 cm−1 . The sharp ones
are assigned to the h-BN and the two broad bands correspond to c- BN. This indi-
cates that both the form were simultaneously synthesized. The porous nature of the
nanostructures of BN with nanocrystals of 20–100 nm covering the silicon substrate
is quite evident from the SEM and TEM images (Fig. 19.14b).

19.14.2 Laser for Biomaterial Coatings

Laser has brought revolutionary progress in the field of biomaterials, where ceramics
are employed for quality betterment of our life. Specially developed ceramics are
used for the reconstruction and repair of bone defects or traumatic diseases [81].
Hydroxyapatite (HAP) has emerged as an important bioceramic which forms good
bonding with the surrounding bone tissues after implantation. It has found application
in both dentistry and orthopedics [82]. However, bulk HAP is not suitable for load-
bearing applications and large bony defects since it is brittle and weak. Therefore,
bone fillers use HAP in granular form and it is coated for osteointegration of various
cement-less titanium-based implant devices.
19 Lasers in Materials Processing and Synthesis 825

Fig. 19.14 a Characteristic two bands at 803 cm−1 and 1356 cm−1 revealed in Raman spectrum
assigned to hexagonal BN and b (i) BN nanostructures as seen in SEM images; (ii) BN nanostructures
(20–100 nm) as seen in TEM image; (iii) synthesized cubic BN nanostructures revealed in TEM
image. This was reproduced with the permission from Hindawi Publisher [80]

The first method developed for making a calcium phosphate coating on metallic
implants was by plasma spraying [83]. Currently, three laser-based methods are devel-
oped for coating metallic substrates with bioceramics. LCVD (Sect. 19.12) technique
has been successfully employed to deposit simple ceramics such as silicon nitrides,
silicon oxides, chromium oxide, or boron carbide on metallic substrates. The other
two techniques are laser ablation and laser cladding. Between them, laser ablation
has become more advanced and routinely used to coat commercial orthopedic spine
screws and dental implants. Both corners and sidewalls of implants can receive
uniform coating by this technique [84, 85].
826 S. K. Sarkar

19.15 Laser-Induced Graphene

The wonder material of the twenty-first century, graphene, has been investigated
extensively right from the basics to the applications [86]. In quest of material having
a large area and matching morphologies, native two-dimensional (2D) forms of
graphene were improved as graphene foams. Several routes have been worked out to
produce graphene foams by wet-chemical and chemical vapor deposition methods.
These methods require high-temperature furnaces, pure gases, and strong acids and
oxidants. However, the growing need for attractive applications has prompted the
technologist and manufacturer for macroscale production of graphene material.
Recently, laser synthesis has come to lead the way by producing what is known
as Laser-Induced Graphene (LIG).
Irradiating polyimide (PI) plastic films using a commercial laser scribing system
in air leads to the formation of LIG. This simple technique being a one-step method
eliminates high temperature, solvent or subsequent treatments. Produced LIG has
atomic arrangements comprising of several five-and seven-membered rings. This can
be considered as “kinetic graphene”, because this synthesis route does not provide
any annealing which normally favors the rearrangement to the ideal all six-membered
ring form [87].
It is quite apparent that the conversion of PI to LIG goes via photothermal route
caused by the high temperature and pressure produced by focused laser irradiation.
In this case, LIG offers about 340 m2 /g of surface area with a hierarchical struc-
ture along with plentiful wrinkles. This is quite comparable to that of 3D graphene
prepared by the wet-chemistry procedure. The aberration-corrected scanning trans-
mission electron microscopy images unveil an unusual polycrystalline character of
LIG. Instead of the conventional hexagon lattice, the carbon of LIG exists in a hybrid
lattice of pentagon-heptagon and hexagon. The irradiation parameters are crucial in
determining the physical and chemical properties of LIG. Generally with increased
laser power, one can get thicker LIG, which, in turn, enhances the conductivity.
Using a 4.8 W laser, irradiation product LIG attains its highest crystallinity with
fewer defects and maximum domain size. It may be noted that laser fluence of about
5.5 J/cm2 converts PI into LIG quite efficiently. The control of LIG morphology can
be achieved by the image density. The image density is governed by the pulses and
the lines per inch (PPI and LPI). Typically, with 100 μm laser spot size and an
image density of 1000 PPI × 1000 LPI, LIG adopts an in-plane porous structure. By
decreasing the image density (500 PPI × 500 LPI) and the laser spot size (60 μm),
LIG converts to out-of-plane fibers (LIGF) and forms a vertically aligned forest
morphology [88].
With hectic investigations all over the world, LIG has already established wide
applications in catalysis, sensors, microfluidics, renewable energy devices, water
purification, etc. Moreover, there are exciting possibilities for preparing LIG from
natural products which can be used for the fabrication of biodegradable devices for
reducing e-waste. With these emergent advancements, the transfer of technology to
commercially synthesize LIGis expected very soon [89–92].
19 Lasers in Materials Processing and Synthesis 827

19.16 Conclusions and Future Perspectives

The attractive features associated with laser do not come without disadvantages.
The single, most important disadvantage is their high cost. Laser photons are gener-
ally expensive ingredients. Normally, the capital and operating costs of lasers are
relatively high in comparison to the cost of processing and synthesizing chemicals.
In this brief overview, we have shown that laser material processing has slowly but
steadily become indispensable engineering solution for a large number of applica-
tions. Traditionally, laser materials processing has been subtractive, meaning mate-
rials are removed from the workpiece. Recently, laser additive processing, the 3D
printing, is complementing these operations. Though initially, additive processing
remained as curiosity, it has now picked up and showing annual growth of 20% and
is estimated to contribute 30% of laser system revenues by 2020 (Sect. 19.6). More-
over, the appearance of new applications and markets for lasers has created strong
incentives for further investment in innovation in lasers. All of this feedback and
self-reinforcing dynamics are classic features of general-purpose technology.
Periodic assessments of the potential for exploiting lasers in the chemical industry
are being made as the development of laser technology and the exploration of new
and exciting laser photochemical synthesis processes are continued as discussed from
Sect. 19.8 onwards. All these expertise will provide an infrastructure for future thrust
areas of “laser photochemical technology” and affect the chemical industry in three
broad areas as envisaged presently:
(i) Laser-based processes that offer lower costs, improved yields, higher product
purity, and fewer unwanted side products.
(ii) Laser-based analytical methods have already achieved the ultimate in sensi-
tivity: detection of single atom in the gas phase and single molecule in solution.
These new analytical methods will change the way product specifications are
defined currently and will provide new opportunities for process monitoring
and control.
(iii) In addition, reaction diagnostics using lasers provide the detailed mechanistic
and kinetic information required to design new processes and synthesize new
materials. During the last ten years, lasers have been put to use for controlling
chemical reactions as well, often with additional selectivity provided by the
unique properties of laser radiation.
It may be worth mentioning that nuclear engineering is a potential field for such
application requiring enriched fuel, moderator, synthesizing new strategic materials
by isotopic tailoring of structural material (90-Zr), burnable poisons like (157-Gd
and 155-Gd). A brief description of several isotope separation efforts is given in
Sect. 19.11.3. Laser processes are being employed in reprocessing of spent nuclear
fuel and recovering noble metals like Ru, Rh, Pd, other elements Sr, Cs, etc., and
long-lived elements Am, Cm, Np, etc. Additionally, reactor technology requires
developing new materials with low neutron absorption cross section. It is required
not only to improve the neutron economy, but also to suppress the activation and
828 S. K. Sarkar

disintegration of materials due to α-particle decay. The interesting materials to be

developed are 50-Ti, 53-Cr, 56,57,58-Fe, and 96,97-Mo.
In the material processing field, there are numerous opportunities for laser
processes. Some of them are laser welding of end plug of reactor fuel clad tube,
development of graded overlay of stellite on SS 304, laser cladded refurbishment of
Ni superalloy based turbine blades. These techniques are also unique in the sense
that remote handling/operation is possible, for example, cutting of zircaloy fuel pins
for extraction of fuel pellets, cutting of end plates of irradiated fuel bundles, welding
of miniature radiotherapy capsule, and cutting thick concrete blocks for possible
decontamination/decommissioning of the radioactive facility.
Judging from the development since the days of drilling holes in diamonds, it is
quite clear that laser application is a dynamic field, and even today new and interesting
technology is being pursued throughout the world. Therefore, assessment of evolving
technology must also be a continuing activity, not only to recognize the impact of the
scientific achievements themselves, but also to keep the entire processing endeavor
in step with a changing worldwide economic and political environment.

Acknowledgements The author acknowledges the works of many researchers in the field on which
the article is based and apologies for not representing many other works. He is also grateful to the
Department of Atomic Energy for grant of Raja Ramanna Fellowship to work at National Centre
for Free Radical Research, Savitribai Phule Pune University, and Bhabha Atomic Research Centre
for continuing support for his research activities.

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Chapter 20
Ultra Fast Electrically Exploding Wire
Method for Production of Raw Material
for Additive Manufacturing Based 3D
Printing

Rohit Shukla and Archana Sharma

Abstract 3D printing nowadays is considered as a very smart method for producing

structures with very fine and intricate internal features. The process is now going
through a very fast scientific development, and laser based 3D printing tools are
already available to the users. Strong and intense laser pulses are bombarded at well-
defined locations on a 2D plane covered by particles through a proper alignment
process controlled by computers as per the instructions given to it. These intense laser
pulses cause the melting of the target which is composed of scattered small particles.
Because of this melting and subsequent cooling, these particles start making metallic
bonds with the substrate which is already solidified cold metal. This way, three
dimensional growth of the structure using fine granules of metals can be achieved.
Since the process depends upon the metal granules and intensity of the laser, hence,
a fine degree of structure growth control can be obtained in the case of dissimilar
material being used for the construction of the model or structure. If alloys are fed
as raw material into the printing system then an alloy structure can be obtained
through this 3D printing. High power portable lasers which can be focused onto very
tiny spots may give additional advantages such as achievement of the temperatures
in a very controlled fashion so that almost all the possible combinations of alloy
manufacturing can be incorporated into a single system of 3D printing requiring
different melting points in constituent metals. Not only laser based printing but also
electron beam based printing can be used in this manufacturing process. Vacuum
may be an additional requirement of the environment in which such electron beam
based additive manufacturing is contemplated. In order to have better control of
the structure fabrication process, the computer-based monitoring and controlling of
various parameters will be helpful for the advanced manufacturing process.

R. Shukla · A. Sharma (B)

Pulsed Power & Electro-Magnetic Division, Beam Technology Development Group, Bhabha
Atomic Research Centre, Mumbai 400085, India
e-mail: [email protected]
Homi Bhabha National Institute, Mumbai 400094, India
R. Shukla
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 833
A. K. Tyagi and R. S. Ningthoujam (eds.), Handbook on Synthesis Strategies
for Advanced Materials, Indian Institute of Metals Series,
https://doi.org/10.1007/978-981-16-1803-1_20
834 R. Shukla and A. Sharma

Keywords Nanoparticles · Action integral · Compact pulsed power system · High

voltage · Additive manufacturing

20.1 Introduction

Production and characterization of nanoparticles produced using electrical explosion

of metal wire is well reported by Kotov [1], Das et al. [2]. Nanoparticle produc-
tion for very interesting application points of view in various media is studied by
Nazarenko et al. [3, 4] In another article [6] Nazarenko et al. have reported the effect
of various gas environments (reactive gas and non-reactive gas combinations) for the
nanoparticle production by electrical exploding wire scheme. They have suggested
less than 2% reactive gas for metal nanopowder production which otherwise leads
to the oxide formation. Károly Lázár et al. [6] have reported the iron nanopowder
reaction in different media using electrical explosion of wire. An interesting, molec-
ular dynamics based simulation is presented by Kryzhevich et al. [7] for exploding
wire based nanoparticle production. Earlier Go Kawamura et al. [8] have reported
oxygen resistant copper based nanoparticles by wire explosion. Chung et al. [9] have
presented a superior oxygen stability copper silver nanoparticle layers sintered by
flash lights to achieve the electrical conductivity close to copper. Suitable environ-
ment study and findings are reported for tungsten carbide nanopowder production in
this method by Ranjan et al. [10]. Taek-Kyun Jung et al. have reported production of
nickel nanopowder by exploding wire method [11], and earlier [12] titanium nitride
nanopowder production is reported in electrical explosion in nitrogen environment.
Beketev et al. [13] have studied magnetic nanoparticles production by electrical
explosion of iron wires.

20.1.1 Concept of Pulsed-Power Plasma Method

In order to generate ultrafine nanopowder of the size less than 10 nm, the capacitor
bank discharges into the wire has to be optimized such that the energy inside the
wire is dissipated at very fast rate which means that before the plasma formation
takes place the considerable amount of energy is given to the wire. Because of the
conducting nature of the plasma, further resistance (I2 R) heating becomes practically
impossible and hence the burst phase is relatively less violent. Higher the energy given
to the atoms, higher is the kinetic energy or the pressure in plasma state. Because
of this generated high pressure, the atoms form very fine coagulation in the form of
nanoparticles.
In the case of the generation of micron sized particles, a very simple scheme of
melting is followed similar to the electrically exploded nanoparticle system. In this
case, the wire is fed longer in the dimensions and is allowed to reach only to the
melt state or liquid state, and the thrust is given by the return conductor current to
20 Ultra Fast Electrically Exploding Wire Method for Production of Raw Material … 835

form the droplets of the tens to even hundreds of microns in size. The thrust is J X
B thrust (J is the current density, and B is the magnetic field) or the repulsive force
or hoop force acting between current carrying conductors with current in opposite
directions. In this way, only a single pulse power system can support the fabrication
of micron-sized to nano-sized particle synthesis of any metal. As this method of
particle synthesis is based on the electrical conductivity and phase-transformation
based on heating (resistive), therefore any conducting metal can be used as a feed
material and its particle size can be easily controlled and hence well determined.
As alloys are constructed mostly from metal atoms, they show finite or considerable
electrical conductivity constructed from most of the metals therefore they can also
equally efficiently be used for the production of particles from micron to nano size.
We have used copper, zinc, aluminum, Iron and Tungsten for producing nanopar-
ticles during this method.

20.1.2 Merits and Demerits of This Method

Certainly any process of commercial/academic interest needs to be compared with

the other processes being used for the similar jobs. Therefore, this process also needs
to be compared with other methods.
Now as explained that getting nano-sized particles as well as micron sized particles
required different types of approaches to obtain the desired extreme size particles
results, a proper experimental approach which is achieved comfortably may give
a broad spectrum of the sizes in between these two extremes. For this purpose, in
order to meet both the ends a simple and single pulsed power system is used, which
is so portable that a single person can handle it and operate it safely. Its mobility
also allows it to arrange the whole setup at a place where the particle consumption is
taking place. This reduces coagulation probability because of very less transit time
especially in the case of very fine nano-powder. Losses during transit, if any, can also
be further minimized by connecting powder generator output to its consumption unit
directly. For high voltage insulation between two units (particle generator to particle
consumption units) conveyor duct or transmission duct of insulator material will be
a good choice for the operator. A normal supply available even in households can be
used for the purpose because capacitor banks are slowly charged with low wattage
power supply, but they deliver higher powers during the electrical discharges. Based
on the simplicity, versatility and portability, the device plays a very important role
in commercial/academic terms also apart from the safety aspects.
836 R. Shukla and A. Sharma

20.2 Characterization and Other Properties

For the characterization of Nano powder X Ray Diffraction (XRD) Scanning elec-
tron microscopy (SEM) and Photon Cross Correlation Spectroscopy (PCCS) tech-
niques have been used. The results have revealed that faster discharges are capable of
producing nanosized metal particles. Some of the images and the results are attached
in the figures in this chapter.
Coating the metal nanopowder on the fabric has been accomplished. A cluster
coating is successfully obtained by the method followed and particles produced by
this method. The size of the particles forming clusters on the fabric is confirmed in
the nano form and can solve the purpose.
Now it has also been shown in the experiments that non optimized dimensions
of the wire lead to the production of larger size of particles which implies that the
pressure at the burst phase is relatively lower and hence particles of larger size are
produced.
In the case of production of larger (micron sized) particles produced by melting
of wire and driving by J X B forces, the analysis part has been done mostly on the
optical microscopes.

20.3 Application of Advance Materials Prepared By This

Route

Various metals like copper, silver, zinc, Iron and tungsten have been used in our
experiments. Of course for the largest particles as discussed above the feeder wire
dimensions can be increased first in terms of width and then in terms of length also.
A challenging metal with conducting nature and not producing nanopowder by this
technique is still being found out.
Usually nanoparticles are the particles with the size below 100 nm. There are the
methods by which nanoparticles may be generated in quite a good amount of quan-
tity and hence support the construction of materials using additive manufacturing
techniques which may be laser based or electron beam based for fusing these parti-
cles. Plasma based techniques have successfully been implemented for the produc-
tion of bulk nanoparticles and the consumption rate of laser based additive manu-
facturing can be fulfilled easily by the plasma based production technique. In this
context Bhabha Atomic Research Centre, Visakhapatnam, has developed a minia-
turized machine for the continuous production of nanopowder by using electrically
exploding wire technique. It has been understood during the experiments that if the
current discharges through the exploding conductor are very quick and intense, then
the energy being dissipated in the metal plasma formation can be sufficiently high to
generate fine nano particles. For this purpose up to 180 kA (short circuit current) has
been dissipated for exploding metal wire of copper, silver, zinc, Iron and tungsten at
size of nearly half a millimeter diameter, and the system is compact and portable and
20 Ultra Fast Electrically Exploding Wire Method for Production of Raw Material … 837

can generate nanoparticles, repetitively. Because of this inherent advantage of porta-

bility and repeatability of the nanopowder generator, nearly 50 mg of nanopowder
is produced every 6 s. In a similar pattern, generating larger size the particles of
metal has also been experimented by exploding wire technique but limiting to the
liquid state. The system is optimized in such a way that the liquid metal experi-
ences hoop force or JXB force at the time of melting. This ensures that the metal
droplets are formed and thrown away from its initial location and are collected on
the bottom of the chamber in which the melting or discharge is taking place. With the
same electrical parameters of the capacitor bank, which are used for the nanopowder
generation of nearly 50 mg material, 500 mg of larger sized (micron sized) particles
of the same metal has been produced in a different chamber fitting. The procedure
gives the flexibility to the operator or the user so that depending upon the requirement
of additive manufacturing one can feed either nanopowder or micron sized powder
depending upon the size and the surface finish of the product.

20.4 Nanoparticle Production

It is noteworthy that while producing the nanoparticles from the electrically exploding
wire method any metal can be fed which has optimized dimensions according to the
pulsed power machine and hence the process is similar for all metals. This fact
greatly introduces the flexibility of the process selection for ablative manufacturing
feed material. Therefore, pure metals as well alloys can directly be used for ablative
manufacturing. One need not worry about the availability of alloys in the form of
powder feed. The nanoparticle generator based on the electrically exploding wire
is only dependent upon the resistivity parameter of various phases of the mate-
rial. It has been experimented using this powder generator and is found that copper
nanopowder of less than 10 nm particle size is being produced by the machine with
good reproducibility.
In Fig. 20.1, the repetitive metal nanoparticle generator is shown. Electrical
schematic is shown in Fig. 20.2 in which the reaction chamber boundary is shown with
the blue circle. Inside this chamber, the repetitive wire loading assembly/mechanism
is also fitted.
Figures 20.3 and 20.4 are showing the size distribution of copper nano powder
produced by the system. Similarly Figs. 20.5 and 20.6 are showing the particle size
distribution produced by aluminum wire in this method. It has been done using the
PCCS technique of analysis. Coagulation on nanoparticles is remarkably seen in the
case of aluminum metal.
Figure 20.7 is a typical current waveform of the current pulse obtained during
capacitor bank discharge inside optimized wire. The calibration of the current
measurement probe is 100 kA per Volt for the study undertaken. Single pulse
discharge is another indication of optimized wire dimensions being used inside the
system.
838 R. Shukla and A. Sharma

Fig. 20.1 Repetitive metal nanoparticle generator

Fig. 20.2 Electrical schematic for compact pulsed power system for metal particle generation
20 Ultra Fast Electrically Exploding Wire Method for Production of Raw Material … 839

Fig. 20.3 Al powder (coagulation) produced by ultrafast wire explosion collected after
30 min (Cumulative Density)

Fig. 20.4 Al powder (coagulation) produced by ultrafast wire explosion collected after
30 min (Density)

In recent covid-19 pandemic times, some reports suggested that the coating of
Personal Protective Equipment (PPE) fabric material can be conducted using metals
in the nanopowder form in order to increase the efficacy of the PPE kit in fight
against various infections. For this purpose recently copper, zinc and aluminum
nanopowders were produced using this ultra fast system and coating over the clothes
was successfully conducted for the demonstration of the technique and process.
Clusters of the nanoparticles are distributed over the cloth surface indicating a non-
uniform coating by metal particles. Some of the images of the coating conducted by
840 R. Shukla and A. Sharma

Fig. 20.5 Copper nanopowder (distribution) produced by ultrafast wire explosion

Fig. 20.6 Copper nanopowder (cumulative) produced by ultrafast wire explosion

the aforesaid method are shown in Fig. 20.8. SEM analysis of the PPE fabric is also
conducted, and similar results are observed.
Zinc oxide nanopowder produced by the generator is shown in Fig. 20.9 which is
collected in a plastic bag. This experiment was conducted in a normal air environment
and hence no inert gas environment was used. But in the case of Fig. 20.10, the inert
gas environment of Argon was used inside the chamber and hence the pure zinc metal
nanopowder is visible after opening the chamber. It is collected all over the internal
surfaces.
The images of the particles generated in the case of Micron size production are
shown in the attached Fig. 20.11 which is obtained from similar discharge of the
capacitor bank but with wire heating up to liquid state only.
20 Ultra Fast Electrically Exploding Wire Method for Production of Raw Material … 841

Fig. 20.7 A typical current discharge curve from the nanoparticle generator (1 V corresponds to
100kA)

Fig. 20.8 Personal Protective Equipment (PPE) fabric coated with copper nanopowder produced
by electrically exploded wire

20.5 Tailoring of Particle Size

The important point is that the action integral data for burst in pure metals are reported
by Tucker and Toth [14] in a capacitor bank discharge machine in particular current
rise rate. As far as the nanoparticle generator is concerned for the generation of the
842 R. Shukla and A. Sharma

Fig. 20.9 Zinc oxide nanopowder produced using pulsed power

Fig. 20.10 Zinc metal

nanopowder produced using
pulsed power system

particles below 10 nm using electrically exploding wire method, the energy dissi-
pation in the form of electrical energy inside the wire material should be conducted
at a considerably fast rate. Since the conductivity of the wire reduces, till the wire
reaches plasma state through the liquid and the vapor states starting from solid state,
the energy dissipation rate or heating rate is quite fast up to the onset of plasma state
but as soon as the plasma state is reached, the conductivity of the metal increases
20 Ultra Fast Electrically Exploding Wire Method for Production of Raw Material … 843

Fig. 20.11 Micron sized

particles of zinc produced
from pulsed power system

abruptly and this reduces further heating of the wire metal and subsequent dissipa-
tion of electrical energy in the wire. Hence it becomes very difficult from this stage
onwards to further increase the temperature of the wire metal. However, it is reported
in the literature [15, 16] that the faster current rates can raise the temperature of the
wire metal relatively higher than that compared with the slower current rates. It may
be partially considered as a kind of thermal inertia in reaching the plasma state or
conducting state at faster current discharge rates and some higher amount of energy
compared to the ionization energy of the metal can be given to the metal atoms.
844 R. Shukla and A. Sharma

20.6 Effect of Various Parameters on Powder Properties

20.6.1 Effect of Medium

As plasma is highly reactive, the produced metal plasma reacts with the surrounding
after the discharge. In order to form oxides, oxygen inside the reaction chamber is
required. If pure metal nanopowder is desired then filling the reaction chamber with
non-reactive gases is the required condition. It has been observed that experiments
in air lead to the formation of oxides while experimenting with aluminum and zinc.
Copper in the Argon environment yielded pure metal powder.
Interestingly in the formation of micron size particles it is observed that even
in an air atmosphere, copper micro particles are produced in the pure form. It is
also noteworthy that since this is a high voltage discharge method of production of
particles from the metal wire, the system needs to be filled with some insulating
media otherwise the electrical discharge may take place in surrounding media and
this may lead to a loss of electrical energy in undesirable processes of discharge. It
suggests that the gas pressure of the system should not be in the Paschen-minimum
region of the breakdown curve. Rather a higher insulation strength of gas is suggested
to be used in the process.

20.6.2 Pressure Control

If high pressure gases of inert nature are filled in the reaction chamber or discharge
chamber then the particles produced after explosion will not travel longer distances
and this is due to enhanced drag resistance offered by the surrounding media. This
way the reaction chamber diameter dimensions may be restricted to the smaller
values. Successful operation of the system up to three or four atmospheric pressures
inside the reaction chamber has been observed. When inert gas is used in the case of
nanoparticle formation, then it has been further observed that the continuity between
electrode in repetitive shots is well maintained subsequently helping to conduct
repetitive shorts whereas in the case of oxide or nitride nanopowder formation the
nanopowder, which gets deposited over the electrodes, may be insulating if the fill
gas is reactive. So the accumulation of nanopowder over the electrodes leads to
poor electrical connections between the running feed wires in between these two
electrodes. Now in this situation, the electrical energy tries to find out some other
ways to discharge, which is not through the wire, like from the surfaces or the system
starts malfunctioning and gets stopped for the subsequent discharges. This affects the
performance of the system. So in repetitive operation it is recommended, based on the
experimental evidence, that an inert gas environment is the most suited environment
for the production of metal nanopowder. It is also suggested that other reactions of
chemical interest may be conducted separately after pure nanopowder is continuously
produced in the chamber.
20 Ultra Fast Electrically Exploding Wire Method for Production of Raw Material … 845

20.6.3 Production of Nanoparticles Inside the Liquid

Since the pulsed power system is very fast and in the sub-microsecond regime of
operation, the nanoparticle producing discharges can be done in the liquid submerged
conditions as well. This will additionally require the structural integrity analysis in
consideration as the pressure generated in the burst phase will be transmitted to the
boundaries more intensely and rapidly than that in the case of air/gas. Repetitive
wire feed system is the component which is in the close proximity of the metal wire
explosion zone and is most vulnerable to the pressures. Hence a proper protection
of the system from repetitive shock pressures will be required in the planning and
design stage.

20.7 Conclusions

A repetitive operation of a portable and miniaturized capacitor bank is reported

earlier [17]. The bank is further augmented with energy and automation in order to
be used for the production of metal particles from nanometer size to micron size in a
single electrical unit. The discharge chambers are different as per the required size of
the particles. This portability leads to further exploration of applications of particles
in other fields. The optical isolation of the system from high voltage and confined
production of the particles has another feature of enhanced electrical safety chemical
safety. In future the particles produced in the bulk quantity are to be fed to the laser
or other like electron beam based 3D printing or additive manufacturing setups.

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