MXene-Filled Polymer

Nnocomposites
MXenes re  new fmily of two-dimensionl (2D) metl crbides, hving properties such s
metllic conductivity nd hydrophilicity. Adding polymer binders/spcers between tomiclly thin
MXene lyers or reinforcing polymers with MXenes results in composite lms tht hve excellent
exibility, good tensile nd compressive strengths, nd electricl conductivity. This book covers ll
dvnces in the eld of MXene-lled polymer nnocomposites to dte, illustrting fbriction nd
chrcteriztion, nd specic properties like nti-heling, ntifriction, nd microwve bsorption.
It further covers potentil pplictions like energy conversion, storge systems, ntibcteril, nd
drug delivery.
The book fetures

• exclusive mteril on MXene-bsed polymer nnocomposites;

• properties nd potentil pplictions of polymers upon ddition of MXenes;
• the effect of MXenes on vrious thermoplstic nd elstomer polymers;
•  focus on the properties, fbriction methods, nd pplictions of relevnt polymer
mtrices; nd
• extensive coverge of the role of MXenes in polymers.

This book is imed t reserchers, professionls, nd grdute students in mteril science, polymer
engineering, electronic mterils, composites, chemicl processing, chemicl sciences, re
engineering, nd biomedicine.
Emerging Materials and Technologies
Series Editor: Boris I. Kharissov

The Emerging Materials and Technologies series is devoted to highlighting publictions centered
on emerging dvnced mterils nd novel technologies. Attention is pid to those newly discovered
or pplied mterils with potentil to solve pressing societl problems nd improve qulity of life,
corresponding to environmentl protection, medicine, communictions, energy, trnsporttion,
dvnced mnufcturing, nd relted res.
The series tkes into ccount tht, under present strong demnds for energy, mteril, nd cost
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Gas Sensors
Mnufcturing, Mterils, nd Technologies
Edited by Ankur Gupta, Mahesh Kumar, Rajeev Kumar Singh, and Shantanu Bhattacharya

Environmental Biotechnology
Fundmentls to Modern Techniques
Sibi G

Emerging Two Dimensional Materials and Applications

Edited by Arun Kumar Singh, Ram Sevak Singh, and Anar Singh

Advanced Porous Biomaterials for Drug Delivery Applications

Edited by Mahaveer Kurkuri, Dusan Losic, U.T. Uthappa, and Ho-Young Jung

Thermal Transport Characteristics of Phase Change Materials and Nanouids

S. Harikrishnan and A.D. Dhass

Multidimensional Lithium-Ion Battery Status Monitoring

Shunli Wang, Kailong Liu, Yujie Wang, Daniel-Ioan Stroe, Carlos Fernandez,
and Josep M. Guerrero

Scanning Probe Lithography

Fundmentls, Mterils, nd Applictions
Yu Kyoung Ryu and Javier Martinez Rodrigo

Engineered Nanoparticles as Drug Delivery Systems

Nahid Rehman and Anjana Pandey

MXene-Filled Polymer Nanocomposites

Edited by Soney C. George, Sharika T. Nair, and Joice Sophia Ponraj

For more informtion bout this series, plese visit: www.routledge.com/Emerging-Mterils-nd-

Technologies/book-series/CRCEMT
MXene-Filled Polymer
Nnocomposites

Edited by Soney C. George, Shrik T. Nir,

nd Joice Sophi Ponrj

Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business
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First edition published 2023
by CRC Press
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CRC Press is an imprint of Taylor & Francis Group, LLC
© 2023 selection nd editoril mtter, Soney C. George, Shrik T. Nir, nd Joice Sophi Ponrj; individul
chpters, the contributors
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ISBN: 978-0-367-75979-7 (hbk)
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ISBN: 978-1-003-16497-5 (ebk)
DOI: 10.1201/9781003164975
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by Apex CoVntge, LLC
Contents
Editor Biographies ...........................................................................................................................vii
List of Contributors...........................................................................................................................ix
Preface............................................................................................................................................ xiii

Chapter 1 Introduction: MXene—A Novel Two-Dimensional Material:

Preparation, Properties, and Applications.................................................................... 1
Bibi Mary Francis, Joice Sophia Ponraj, Nivedita Lalitha Raveendran,
Rajesh Kumar Manavalan, and Sathish Chander Dhanabalan

Chapter 2 Overview of MXene-Based Polymer Nanocomposites: State of the

Art and New Challenges ............................................................................................ 27
Prajitha V, Jibin K P, Sisanth K S, Abitha V K, Hanna J Maria,
and Sabu Thomas

Chapter 3 Processing, Morphology, Mechanical, and Electrical Properties,

and Applications of Thermoplastic Polymer/MXenes Nanocomposites ................... 43
Pallishree Sahoo, Lipsa Shubhadarshinee, Pooja Mohapatra,
Patitapaban Mohanty, Bigyan Ranjan Jali, Priyaranjan Mohapatra,
and Aruna Kumar Barick

Chapter 4 MXene–Elastomer Nanocomposites.......................................................................... 71

Jeeshma R, Swapna V.P, and Ranimol Stephen

Chapter 5 Green Polymer Nanocomposites with MXenes ......................................................... 89

Nanoth Rasana, Karingamanna Jayanarayanan, and P. Sarath Kumar

Chapter 6 Thermoset/MXene Nanocomposites........................................................................ 109

Benjamin Tawiah and Sarkodie Bismark

Chapter 7 Thermal and Crystallization Behavior of MXene/Polymer Nanocomposites ......... 133

Sarkodie Bismark and Benjamin Tawiah

Chapter 8 Tribological Performance of MXene/Polymer Nanocomposites ............................. 153

Rodrigo Mantovani Ronchi, Hugo Gajardoni de Lemos,
and Sydney Ferreira Santos

Chapter 9 Self-Healing Activity of MXene/Polymer Nanocomposites.................................... 171

Shikha Agarwal, Ayushi Sethiya, Divyani Gandhi, and Jay Soni

v
vi Contents

Chapter 10 Microwve Absorption nd EMI Shielding Performnce of MXene-Filled

Polymer Nnocomposites......................................................................................... 191
Bhavya Bhadran, Avinash R. Pai, and Sabu Thomas

Chapter 11 MXene–Polymer Nnocomposites for Gs- nd Vpor-Sensing

Applictions.............................................................................................................. 211
Vishal Chaudhary

Chapter 12 Mxene-Bsed Nnocomposites in Energy Conversion nd Storge Systems .......... 235
Dana Susan Abraham, Margandan Bhagiyalakshmi, and Mari Vinoba

Chapter 13 Biomedicl Applictions of MXene/Polymer Nnocomposites............................... 247

Nupur Garg and Farhan J. Ahmad

Chapter 14 Flexible nd Werble Applictions of MXene/Polymer-Bsed

Nnocomposites ....................................................................................................... 259
Heera S and Amal George Cheriyan

Chapter 15 Theory, Modeling, nd Simultion of MXene/Polymer Nnocomposites ............... 277

Benjamin Tawiah, Sarkodie Bismark, and Charles Frimpong

Chapter 16 Future Perspective of MXene-Filled Polymer Nnocomposites.............................. 295

Y C Goswami and Bhavya Pandey
Index ..............................................................................................................................................309
Editor Biographies
Soney C. George is Den of Reserch nd Director, Centre for Nnoscience nd Technology, Aml
Jyothi College of Engineering, Kerl, Indi. He is  Fellow of the Royl Society of Chemistry
nd  recipient of KTU best resercher wrd. His pper in International Hydrogen Energy hs
been selected for the best cittion wrd. He hs published more thn 200 ppers in peer-reviewed
ntionl nd interntionl journls nd conferences. He is lso edited nd contributed severl books
nd chpters published by Elsevier, Wiley, Springer, nd others. He hs guided severl PhD. nd
mster’s students. He is concentrting on structure—property reltions in polymer-bsed nnomte-
ril. He hs lso successfully completed severl centrl- nd stte-funded projects.

Sharika T. Nair works s Assistnt Professor, St. Xvier’s College Vikom, Kerl, Indi. Her
reserch res include preprtion of polypropylene/nturl rubber-bsed blends nd nnocom-
posites, their chrcteriztion, nd their pplictions. She hs published mny reserch ppers
in interntionl journls nd presented ppers in ntionl nd interntionl Conferences. She hs
lso published mny book chpters. She hs completed one UGC (New Delhi) funded project nd
guided severl msters students.

Joice Sophia Ponraj is  resercher t Tyndll Ntionl Institute, Cork, Irelnd. She obtined her
Doctor of Philosophy from Ann University, Chenni, Indi. She ws bestowed “Itlin-Indin
Bilterl Progrmme” hosted by UniFe, Ferrr, Itly nd Ntionl Doctorl Fellowship by AICTE,
Indi during her PhD. She ws wrded TRIL fellowship three times by ICTP to work in IMEM-
CNR, Prm, Itly during 2011 to 2014. She hs worked s  postdoctorl fellow t Suzhou University,
Chin, INL in Portugl, nd s n ssistnt Professor in UIST, Ohrid, Republic of Mcedoni. She
bgged INSPIRE Fculty Awrd in Indi. Her reserch interests re two-dimensionl mterils,
nnophotonics, nd semiconducting device fbriction.

vii
Contributors
Dana Susan Abraham Sathish Chander Dhanabalan
Deprtment of Chemistry Centre for Advnced Mterils,
Centrl University of Kerl Integrted-Inter-Deprtment of LiWET
Periye, Indi Communictions
Aivlym-Dynmic Integrted Reserch
Shikha Agarwal Acdemy nd Corportions (A-DIRAC)
Synthetic Orgnic Chemistry Lbortory, Coimbtore, Indi
Deprtment of Chemistry
MLS University Bibi Mary Francis
Udipur, Indi Centre for Advnced Mterils,
Integrted-Inter-Deprtment of LiWET
Farhan J. Ahmad Communictions
Deprtment of Phrmceutics, School of Aivlym-Dynmic Integrted Reserch
Phrmceuticl Eduction & Reserch Acdemy nd Corportions (A-DIRAC)
New Delhi, Indi Coimbtore, Indi

Aruna Kumar Barick Divyani Gandhi

Deprtment of Chemistry Synthetic Orgnic Chemistry Lbortory,
Veer SurendrSi University of Technology Deprtment of Chemistry
Smblpur, Indi MLS University
Udipur, Indi
Bhavya Bhadran
PG Deprtment of Chemistry Nupur Garg
St. Thoms College Deprtment of Phrmceutics, School of
Pl, Indi Phrmceuticl Eduction & Reserch
New Delhi, Indi
Margandan Bhagiyalakshmi
Deprtment of Chemistry Y. C. Goswami
Centrl University of Kerl Nno Reserch Group, School of Sciences
Periye, Indi ITM University
Gwlior, Indi
Vishal Chaudhary
Deprtment of Physics, Bhgini Nivedit S. Heera
College University of Kerl
University of Delhi Plym, Kerl
New Delhi, Indi
K. Jayanarayanan
Amal George Cheriyan Deprtment of Chemicl Engineering nd
Mhtm Gndhi University Mterils Science
Kottym, Kerl Amrit Vishw Vidypeethm
Coimbtore, Indi
Hugo Gajardoni de Lemos
Center of Engineering, Modeling nd Applied R. Jeeshma
Socil Sciences Deprtment of Chemistry
Federl University of ABC St. Joseph’s College (Autonomous)
Snto André (SP), Brzil Clicut, Indi

ix
x Contributors

Keloth Paduvilan Jibin N. Rasana

School of Chemicl Sciences Deprtment of Chemicl Engineering nd
Mhtm Gndhi University Mteril Sciences
Kottym, Indi Amrit School of Engineering
Coimbtore, Indi
Abitha Vayyaprontavida Kaliyathan
School of Chemicl Sciences Nivedita Raveendran
Mhtm Gndhi University Centre for Advnced Mterils,
Kottym, Indi Integrted-Inter-Deprtment of LiWET
Communictions
Rajesh Kumar Manavalan Aivlym-Dynmic Integrted Reserch
Institute of Nturl Science & Mthemtics Acdemy nd Corportions (A-DIRAC)
Url Federl University Coimbtore, Indi
Ekterinburg, Russi
Rodrigo Mantovani Ronchi
Hanna Joseph Maria Center of Engineering, Modeling nd Applied
School of Energy Mterils Socil Sciences
Mhtm Gndhi University Federl University of ABC
Kottym, Indi Snto André (SP), Brzil

Patitapaban Mohanty Pallishree Sahoo

Deprtment of Chemistry Deprtment of Chemistry
Veer Surendr Si University of Technology Veer Surendr Si University of Technology
Smblpur, Indi Smblpur, Indi

Pooja Mohapatra Sydney Ferreira Santos

Deprtment of Chemistry Center of Engineering, Modeling nd Applied
Veer Surendr Si University of Technology Socil Sciences
Smblpur, Odish, Indi Federl University of ABC
Snto André (SP), Brzil
Priyaranjan Mohapatra
Deprtment of Chemistry P. Sarath Kumar
Veer Surendr Si University of Technology Amrit Vishw Vidypeethm
Smblpur, Indi, Coimbtore, Indi

Avinash R. Pai Bismark Sarkodie

Interntionl & Inter University Center Key lbortory of ultrne mterils of the
for Nnoscience nd Nnotechnology Ministry of Eduction
(IIUCNN) School of Mterils Science nd Engineering
Mhtm Gndhi University Shnghi, Chin
Kottym, Indi
Ayushi Sethiya
Bhavya Pandey Synthetic Orgnic Chemistry Lbortory,
Nno Reserch Group, School of Sciences Deprtment of Chemistry
ITM University MLS University
Gwlior, Indi Udipur, Indi

Bigyan RanjanJali Lipsa Shubhadarshinee

Deprtment of Chemistry Deprtment of Chemistry
Veer Surendr Si University of Technology Veer Surendr Si University of Technology
Smblpur, Indi Smblpur, Indi
Contributors xi

Sisanth Krishnan Sidharthan V. P. Swapna

Centrl Institute of Petrochemicls Deprtment of Chemistry
Engineering & Technology (CIPET) St. Joseph’s College (Autonomous)
Chenni, Indi Clicut, Indi

Jay Soni Benjamin Tawiah

Synthetic Orgnic Chemistry Lbortory, Kwme Nkrumh University of Science nd
Deprtment of Chemistry Technology
MLS University Ghn, Indi
Udipur, Indi
Sabu Thomas
Joice Sophia Vice-Chncellor
Centre for Advnced Mterils, Integrted- Mhtm Gndhi University
Inter-Deprtment of LiWET Kottym, Indi
Communictions
Aivlym-Dynmic Integrted Reserch Prajitha Velayudhan
Acdemy nd Corportions (A-DIRAC) School of Chemicl Sciences
Coimbtore, Indi Mhtm Gndhi University
Kottym, Indi
Rani mol Stephen
Deprtment of Chemistry Mari Vinoba
St. Joseph’s College (Autonomous) Kuwit Institute for Scientic Reserch
Clicut, Indi Kuwit City, Kuwit
Preface
Over the yers, polymer nnocomposites hve been widely reserched becuse lling nnoprticles
into polymer mtrix provides verstile routes for enhncing the processing nd physicl proper-
ties of polymers owing to the size effect of these tiny solid prticles. The lst twenty yers hve
witnessed signicnt progress in the eld of polymer nnocomposites, nd they hve shown fs-
cinting properties compred to net polymer. A vriety of nnoprticles hve been blended with
polymers to form nnocomposites. Among these, MXenes hve become  huge reserch interest in
this decde.
MXenes re  reltively new nd exciting clss of two-dimensionl (2D) mterils, which offer
 wide rnge of compositions nd excellent properties. MXenes re known s 2D metl crbides or
nitrides nd hve ttrcted gret ttention in recent yers due to their high electricl conductivity,
high hydrophilicity, chemicl stbility, nd ultrthin 2D-sheet-like structure. MXene hve drwn
ttention for mny pplictions in the elds of sensors, supercpcitors, hydrogen storge, nnoelec-
tronics, btteries, hybrid ion cpcitors, nd more.
Due to their specil properties, MXenes hve tremendous potentil s dvnced composite
structures, especilly those bsed on polymers due to  gret fnity between mcromolecules nd
the terminting groups of 2D MXenes. Adding polymer binders/spcers between tomiclly thin
MXene lyers or reinforcing polymers with MXenes results in composite lms tht hve excellent
exibility, good tensile nd compressive strengths, nd electricl conductivity tht cn be djusted
over  wide rnge. Owing to their mechnicl strength nd impressive cpcitive performnce,
these lms hve the potentil to be used for structurl energy storge devices, electrochemicl ctu-
tors, nd rdiofrequency shielding, mong other pplictions. To the best of the editor’s knowledge,
there is currently no single book tht focuses exclusively on MXene-lled polymer nnocomposites.
The chpters of this book re orgnized s follows: Chpter 1 introduces MXene mteril by
covering its preprtion, properties, nd pplictions. Chpter 2 provides n overview of MXene-
lled polymer composites. This chpter exmines emerging trends in MXene-lled polymer com-
posites in reserch nd development. Chpters 3 through 6 summrized the effect of MXene on
the vrious properties of thermoplstic, elstomers, nd thermoset polymers. All these chpters
cover the preprtion, properties, nd pplictions of MXene-lled polymer composites t vrious
structurl levels. The therml nd crystlliztion behvior of MXene-lled polymer nnocompos-
ites is discussed in Chpter 7. Chpters 8 through 14 exmines the vrious pplictions of MXene-
lled polymer nnocomposites, with these chpters covering ntifriction performnce, self-heling
nture, electromgnetic interference shielding, sensing, energy storge, nd biomedicl pplictions
of vrious MXene-lled polymer composites. Chpters 15 nd 16 discuss the simultions nd future
perspective in MXene-lled polymer nnocomposites.
The book is the result of commitments by top reserchers in the eld of MXene with vrious
bckgrounds nd expertise. This book introduces reders to the fundmentl spects, properties,
fbriction methods, nd the numerous pplictions of MXene nd MXene-lled polymer nno-
composites with  strong focus on novel ndings nd technologicl chllenges. This book is  one-
stop reference for MXene mterils nd overviews up-to-dte literture in the eld of MXene-lled
polymer nncomposites nd pplictions. This book is unique in the sense tht it covers ll dvnces
in the eld of MXene-lled polymer nnocomposites to dte. It serves s n invluble guide to
professionls, reserchers, industrilists, grdute students, nd senior undergrdutes in the elds
of polymer science nd engineering, mterils science, nno-devices, energy storge, exible elec-
tronics, polymer chemistry, nd nnoscience nd who work in similr res or re interested in the
eld of polymer blends nd nnocomposites.
All chpters were contributed by renowned professionls from cdemic, industry, nd govern-
ment lbortories from vrious countries nd were peer reviewed in ccordnce with the guidelines

xiii
xiv Preface

utilized elsewhere by top-rted polymer journls. The editors would like to thnk ll contributors
for believing in this endevor, shring their views nd precious time nd obtining documents. The
editors would like to express their grtitude to the externl reviewers whose contributions helped to
improve the qulity of this book. The editors re indebted to the orgniztion for their seless sup-
port in this venture. Finlly, the editors lso express their grtitude to CRC Press for its continuous
encourgement.
 1 MXene—A Novel Two-Dimensional
Introduction

Material: Preparation, Properties,

and Applications
Bibi Mary Francis, Joice Sophia Ponraj,
Nivedita Lalitha Raveendran, Rajesh Kumar Manavalan,
and Sathish Chander Dhanabalan

CONTENTS
1.1 Introduction ............................................................................................................................... 1
1.2 Synthesis of MXenes................................................................................................................. 3
1.3 Properties................................................................................................................................... 5
1.3.1 Physicl, Chemicl, nd Mechnicl Properties ........................................................... 5
1.3.2 Electronic Properties ..................................................................................................... 6
1.3.3 Mgnetic Properties ...................................................................................................... 6
1.3.4 Opticl Properties.......................................................................................................... 8
1.3.5 Rheologicl Properties .................................................................................................. 9
1.4 Appliction.............................................................................................................................. 10
1.4.1 Electronic Applictions ............................................................................................... 10
1.4.2 Photonic Applictions ................................................................................................. 11
1.4.3 Biomedicl Applictions ............................................................................................. 11
1.4.4 Electrochemicl nd Energy Storge Applictions ..................................................... 12
1.5 Conclusion............................................................................................................................... 15
References........................................................................................................................................ 16

1.1 INTRODUCTION
MXenes re two-dimensionl (2D) lyered mterils tht re obtined from their bulk prent mte-
ril, MAX phses, by the selective etching of element ‘A’, where A stnds for toms such s lumi-
num or silicon tht belong to group 13 to 16 in the periodic tble (Ansori et al., 2019). For exmple,
the most common MXene is Ti3C2Tx, which is exfolited from its 3D-MAX phse, Ti3AlC2, by
selectively removing Al. The chemicl formul for MXenes is Mn+1XnTx, in which M represents
erly trnsition metls; X represents crbon, nitride, or crbon nitride; T represents the functionl
groups –OH, –F nd/or –O tht ttch to MXene during its etching process; nd n = 1, 2, 3 (Nguib
et al., 2014; Abdelmlk, 2014). The in- nd out-of-plne ordering of metl toms s shown in
Figure 1.1; different surfce termintions nd combintions of them nd the possibility of forming
solid solutions t the M nd X sites led to numerous 2D-MXenes with possible distinct properties
(Jeon et al., 2020; Ansori et al., 2015; Yury Gogotsi nd Qing Hung, 2021).
In other 2D mterils, such s grphene, TMDs, nd h-BN, it is the vn der Wl’s bond tht
holds different lyers together, but in  MAX phse, the tom A binds with M nd X vi metllic
bonding. Therefore, breking the bond is  difcult tsk in  MAX phse vi regulr sher or other
mechnicl methods. However, chemicl exfolition is found to be n effective method to exfolite
DOI: 10.1201/9781003164975-1 1
2 MXene-Filled Polymer Nanocomposites

FIGURE 1.1 MXenes with three different formule—M2X, M3X2, nd M4X3. The formul cn contin sin-
gle-M elements (e.g., Ti2C or Ti3C2),  solid solution of minimum two different M elements (e.g., (Ti,Nb)4C3),
nd ordered two-M elements in which one type of trnsition metl element occupies the lyers in the perimeter
nd the other one occupies M lyers t the center (e.g., (Mo2V2)C3).

MXene from its corresponding MAX phse without disrupting the MX bond, which is  mix of
covlent, ionic, nd metllic bonds (Nguib et al., 2014). MXene synthesis is hence performed pri-
mrily using uoride-bsed cid solutions such s hydrogen uoride or  mix of hydrochloric cid
nd lithium uoride (Ansori et al., 2019). Chemicl exfolition llows selective etching nd this
gives MXenes n edge over the other two-dimensionl mterils considering the esiness for lrge-
scle production (Ansori et al., 2019; Jeon et al., 2020). The surfce termintion ttches to the
MXene during the exfolition vi  top-down method (Jeon et al., 2020). It is possible to synthesize
MXenes without surfce termintion using  bottom-up method. However,  bottom-up method
for MXene synthesis needs to be explored better (Ansori et al., 2019). The synthesis method hs
signicnt role in determining the lterl size, thickness, nd defects in MXene (Jeon et al., 2020).
MXenes hve interesting electronic properties s they cn be tuned by vrying the elementl
composition or the surfce termintion of MXene. Density functionl theory (DFT) studies show
tht monolyers of bre MXene re metllic nd hve  high electron density in proximity of the
Fermi level, in fct, higher thn wht is observed in its MAX phse (Nguib et al., 2011, 2014;
Shein nd Ivnovskii, 2012; Khzei et al., 2013; Xie nd Kent, 2013). However, like semiconduct-
ing mterils, their Fermi levels re tunble with externl stimuli (Gogotsi nd Hung, 2021). Like
other 2D mterils, MXene lso exhibits high electricl conductivity (~2.0 × 104 S cm−1 for Ti3C2Tx;
Guo et al., 2018), high surfce re (externl surfce re of Ti3C2 MXene 2D kes is found to be
61.56 m2 g−1; Rozmysłowsk-Wojciechowsk et al., 2020), porosity (micropore surfce re is found
to be 31.52 m2 g−1; Rozmysłowsk-Wojciechowsk et al., 2020), strength (for Ti3C2, in  perpen-
diculr direction to the bsl plne, Young’s modulus is found to be bout 80–100 GP nd tensile
strength of  40-nm thin nnoke is found to be 670 MP; Firestein et al., 2020), hydrophilicity
(~60-nm-thick membrne of MXene showed wter ux in the rnge of 85.4 L m−2 h−1; G. Liu et al.,
2018), high negtive surfce chrge (ζ-potentil for Ti3C2 is between −30 mV nd −80 mV) nd the
bility for energy storge (M et al., 2017; Akuzum et al., 2018). The conductivity of MXene-Ti3C2
Introduction: MXene—A Novel Two-Dimensional Material 3

nd its trnsition metl tom’s redox ctivity hs resulted in its wide ppliction in btteries nd
supercpcitors (Gogotsi nd Hung, 2021; VhidMohmmdi et al., 2021; Luktsky et al., 2013;
Pomerntsev nd Gogotsi, 2017; Grg nd Agrwl, 2020; C. J. Zhng et al., 2018). Other impor-
tnt pplictions re electronic devices (e.g., eld-effect trnsistors; Kim nd Alshreef, 2020;
Wng et al., 2020), photovoltics (Husm et al., 2020; Yin et al., 2021), polymer nnocomposite
llers (Zhnget al., 2013; Nguib et al., 2016), photoctlysis (Rn et al., 2017), nd biomedicl
pplictions (George nd Kndsubrmnin, 2020; Sivsnkrpilli et al., 2020).

1.2 SYNTHESIS OF MXenes

Widely dopted synthesis method of MXenes re top-down methods in which  lyer of A toms
is removed from the MAX phse, thus forming loosely pcked 2D-ntured-MXene lyer. This is
further reduced to  monolyer of MXene kes (Nguib, Mshtlir, et al., 2012). The metllic bond
between M nd A toms is strong (compred to vn der Wl’s bond in other 2D mterils) such tht
chemicl or electrochemicl selective etching tht is ided by bonding energy difference nd chemi-
cl rectivity of bonds in MAX precursors is needed (Nguib et al., 2011, 2014; VhidMohmmdi
et al., 2021). Different methods used for the synthesis of 2DMXenes re wet chemicl etching using
HF/uoride slt nd HCl/NH4HF2, non-HF etching using NOH solutions t high tempertures,
HCl vi electrochemicl methods, ZnCl2 molten slt, iodine etching, nd hlogen etching. Finlly,
the sclble production of freestnding nd stble Ti3C2Tx Mxene is chieved vi  blde-coting
technique (VhidMohmmdi et al., 2021).
In the wet chemicl etching method, uoride ion contining strong cids, like hydrouoric cid
(HF) is employed to remove Al from its MAX phse, resulting in terminted, multilyer MXene
powders (Gogotsi, 2013; Nguib et al., 2011; Pomerntsev nd Gogotsi, 2017). In the multilyered
MXene, the 2D lyers will be bonded by hydrogen bonds (Nguib et al., 2011). Once the etching is
over, next step is wshing to remove the residul cid nd ttin  pH of round six. During wshing,
the etched solution is repetedly centrifuged to segregte multilyer MXene from the cidic solu-
tion, fter which decnttion of cidic superntnt is done. Once the pH reches the desired vlue,
multilyered MXene kes re collected using vcuum-ssisted ltrtion nd drying (Alhbeb et al.,
2017). Since the synthesis is crried out in n queous solution contining uoride, MXenes re sur-
fce terminted by functionl groups –O, –OH, nd –F (Nguib et al., 2011; Ahmed nd Yi, 2017).
The multilyered MXene is then delminted into monolyer to  few-lyered MXene using chemi-
cl intercltion using orgnic molecules like tetrbutylmmonium hydroxide (TBAOH), dimethyl
sulfoxide (DMSO), n-butylmine, or tetrmethylmmonium hydroxide (TMAOH) (Mshtlir et al.,
2013; Nguib et al., 2015), nd this is followed by soniction if required (Alhbeb et al., 2017). The
delminted MXene kes—Mn+1XnTx—will form  stble colloidl solution. During etching, the
concentrtion of HF hs n impct on the number of defects formed in MXene, nd this ffects the
qulity, s well s properties, of the synthesized Mxene (Sng et al., 2016; Liptovet al., 2016).
Vrious MXenes were successfully etched from their MAX phses, Ti3AlC2, Ti2AlC, V2AlC,
Nb2AlC, nd others, to nme  few (Nguib et al., 2021). The concentrtion of HF, temperture,
nd time of etching hd to be vried for different MAX phses since the bond strength of trnsition
metls with Al vried for ech MAX phse (Alhbeb et al., 2017; Nguib et al., 2021). Additionlly,
tuning the etching conditions lso help mintin  high yield nd reduce the degrdtion of 2D
MXene in cid (Nguibet al., 2021). One of the mjor disdvntges of this method is tht HF is 
strong cid; hence, it is highly corrosive nd poses risk to helth. MILD, minimlly intensive lyer
delmintion, is  comprtively sfe method. The MILD method uses  mixture of uoride slts
like LiF/NF/KF nd HCl cid (Ghidiu et al., 2014). Another dvntge of this method is tht the
uoride slt–HCl mixture produces both HF tht etches nd n interclnt (Li ion if LiF is used)
tht delmintes side by side (Alhbeb et al., 2017). The resulting MXene kes exhibit clylike
behvior due to the Li ions tht re present between the kes (VhidMohmmdi et al., 2021). It
cn be further delminted into  single lyer using soniction. MILD method offers better control
4 MXene-Filled Polymer Nanocomposites

over ke size nd qulity of Mxene (Liptov et al., 2016b; Choi et al., 2018). Additionlly, this
method opened the reserch on electronic nd opticl reserch with its cpcity for enhnced scl-
bility nd synthesis of MXene, especilly Ti3C2Tx (Shekhirev et al., 2021). NH4HF2, mmonium
biuoride, hve been used t room temperture for etching MXene from MAX phses (Hlim et al.,
2014; Feng et al., 2017). An Al tom from Ti3AlC2 is etched in both wter nd in polr orgnic sol-
vent (N,N-dimethylformmide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nd propylene crbon-
te) (Nguib et al., 2021; Zhoet al., 2020; Husmnn et al., 2020). During wshing, n Al tom is
extrcted s AlF3 nd (NH4)3AlF6. Due to the low solubilities of Al slts formed in orgnic solvents,
 mix of HCl nd propnol is used for wshing. The cly for medi of MXene thus delminted into
 mono- or  few lyers using ultrsoniction nd stble colloids of 2DMXenes cn be obtined in
the sme orgnic solvents (Zho et al., 2020). Two-dimensionl Ti3C2Tx hs been produced from
MAX phses using NH4HF2 (Zho et al., 2020; Husmnn et al., 2020; Hlim et al., 2014). A sum-
mry of wet chemicl synthesis method is given in Figure 1.2.
Two-dimensionl MXene–Ti3C2 hs been synthesized from the MAX phse, Ti3AlC2 in choline
chloride nd deep eutectic solvents bsed on oxlic cid in the presence of NH4F. The solid precur-
sor nd product t room temperture delivered  high purity of 98% in comprison with 95% seen
in HF-etched Ti3C2 (J. Wu et al., 2020).
Fluorine-free electrochemicl etching using HCl hs been demonstrted to produce Ti2CTx. In
this method, porous Ti2AlC is used s electrodes in dilute HCl electrolyte. Electrochemicl rec-
tion results in the formtion of lyer of Ti2CTx on Ti2AlC electrode (Sun et al., 2017). Ti2AlC will
be etched into  three-lyered structure consisting of CDC (crbide-derived crbon), MXene, nd
unetched MAX from outside to inside. The MXenes cn be seprted from this lyer using bth soni-
ction. These MXenes possess –Cl, –O, nd –OH termintions (Sun et al., 2017). Another uoride-
free etching hs been done electrochemiclly to synthesize Ti3C2 using binry electrolyte (NH4Cl/
FeCl3 with NH4OH). In this method, both cthode nd node used re Ti3AlC2 (Yng et al., 2018).
Chloride ions in the electrolyte enbled rpid etching by breking Ti–Al bonds t the node under
mbient conditions (Yng et al., 2018). The subsequent intercltion of mmonium hydroxide opened
the edges of the node tht is etched, which led to the further etching of surfces tht were below.

FIGURE 1.2 Schemtic digrm of two methods of MXene synthesis—wet chemicl nd molten slt etching.
Introduction: MXene—A Novel Two-Dimensional Material 5

In this method, only –O nd –OH termintions re found nd uorine termintion is bsent (Yng
et al., 2018). Multilyer Ti3C2Tx, which is free of uorine termintion, hs been prepred using lkli
(NOH) tretment. The product ws in powder form with 92 wt% purity (Li et al., 2018). Molten slt
(ZnCl2, CuCl2), nd hlogen (Br2, I2 nd/or Cl2 in cyclohexne) hve lso been used to etch MXenes
(Min Li et al., 2019; Kmysbyev et al., 2020; Shi et al., 2021; Ali et l, 2021; Usmn et al., 2021).
Bottom-up synthesis method, chemicl vpor deposition (CVD) hs lso been used to synthesize
MXenes, such s α-Mo2C, with lterl size of up to 100μm on  bilyer copper foil substrte bove 
foil of molybdenum (Xu et al., 2015). A lrger lterl size hs been observed for MXene synthesized
vi this method, which ws fcilitted in nlyzing their intrinsic properties (Gogotsi, 2015; Xu
et al., 2015). Other MXenes, such s tungsten crbide (WC) nd tntlum crbide (TC) hve lso
been demonstrted using CVD (Xu et al., 2015). Thus,  bottom-up method of synthesis is explored
more for MXene monolyer synthesis.

1.3 PROPERTIES
MXenes re of exceptionl interest in the world of 2D mterils s they possess unique properties
nd chrcteristics tht mke them promising for  myrid of pplictions like energy storge,
chemicl sensing, electromgnetic interference (EMI) shielding, wireless communictions, ctly-
sis, nd werble electronics (Nguib et al., 2012).

1.3.1 PHYSICAL, CHEMICAL, AND MECHANICAL PROPERTIES

One of the most notble fetures of MXenes tht contributes to their unique properties is surfce
functionlity. During the different processing steps, including intercltion nd etching, there re
these ctive functionl groups tht strongly couple to the surfce of MXenes nd hve effects on
their properties. Both the physicl nd chemicl properties of n MXene re dependent on the host
MAX phses, the processing, nd postprocessing methods. Some of the properties, in lieu of the
erlier rgument, re discussed here. MXenes re environmentlly sensitive mterils, nd the pres-
ence of wter nd oxygen fcilittes their degrdtion, lthough vcuum ltrtion signicntly coun-
tercts the process (Double et al., 2020). Due to the ttched surfce termintion groups, MXenes
re hydrophilic in nture nd hve wter contct ngle of bout 21.5–35°(Ling et al., 2014; Zho
et al., 2017). It’s been observed tht F nd O functionliztion contributes to higher work functions
while hydroxyl group tones it down (Khzei et al., 2015; Thini nd Smith, 2017). A work function
rnging from 1.6 eV for Sc2C(OH)2 nd 8.0 eV for Cr2CO2 hs been reported (Khzei et al., 2015;
Liu et al., 2016). The use of Li+ ction insted of HF during intercltion gives better electricl con-
ductivity nd modultes their structurl response to reltive humidity nd hydrtion degree (Ghidiu
et al., 2014; Ghidiu et al., 2016). Mechnicl testing on MXenes hve shown tht they re stronger
nd stiffer thn their MAX counterprts. The mechnicl properties of MXenes depend on the sur-
fce termintions, nd it is observed tht MXenes with O-termintion re stiffer in comprison with
–F nd –OH terminted ones (Zhn et al., 2020). Ti3C2Tx cn support pproximtely 4000 times its
own weight, nd it cn be rised by the formtion of composites with polymer up to bout 15,000
times its own weight (Ling et al., 2014). Ti3C2Tx hs demonstrted  Young’s modulus of bout 330
GP, which is higher thn other solution-bsed 2D mterils (Liptov et al., 2018). MXene com-
posites with Polyvinyl lcohol (PVA), Polycrylmide (PAM), nd Ultr-high-moleculr-weight-
polyethylene (UHMWPE) hve reported higher toughness nd yield strength (Nguib et al., 2016b;
Zhng et al., 2016; Myerberger et al., 2017). MXene composites with polymers hve enhnced
therml, mechnicl, nd electrochemicl properties. In Ti3C2Tx MXene/poly (vinylidene uoride-
triuoro-ethylene-chlorouoroethylene) (P[VDF-TrFE-CFE]) polymer composite (Tu et al., 2018),
 signicntly high dielectric constnt is observed, wheres Ti3C2Tx MXene-bsed PVA hydrogel
(Zhng et al., 2018) exhibits good stretchbility, symmetricl strin sensitivity in ddition to the
bility for self-heling. Reinforcement of elstomers to improve their mechnicl nd functionl
6 MXene-Filled Polymer Nanocomposites

properties is  frequent prctice. Tensile tests done on Ti3C2Tx-reinforced nitrile butdiene rubber
shows enhnced strength nd incresed electricl nd therml conductivity (Akyiir et al., 2020).

1.3.2 ELECTRONIC PROPERTIES

The mjority of MXenes belong to the fmily of metls, semimetls, or semiconductors. Although
lmost ll pristine MXenes re metllic, surfce functionliztion chnges their nture to semicon-
ducting mostly due to the shift in Fermi level or due to the modiction of the crystl eld round
the trnsition metl in them (Khzei et al., 2017). The metllic conductivity origintes from the
highly ligned structure nd high free-electron density in ech MXene nnosheet pving the wy for
severl electricl pths. The electricl properties of MXenes lso depend on the lower concentrtions
of defects nd lrger size of ke, which promote higher conductivity (Come, et al., 2012). This, in
turn, is dependent on the synthesis, delmintion, nd smple preprtion techniques. In the cse of
supported or freestnding lms nd compressed discs, both inter- nd intr-ke resistnce contrib-
ute to its conductivity, but for single-ke MXenes, electronic conduction is dependent on intr-ke
nd contct resistnce. There is still room for in-depth investigtion of MXene electronic conductiv-
ity tht vries from less thn 1 S cm−1 for pressed multilyered MXene disk to 1000s of S cm−1, the
highest being pproximtely 10,000 S cm−1 for Ti3C2Tx thin lms (Zhng et al., 2017). The MXene
conductivity is observed to be dependent on the etchnts used during processing. HF–etchnt results
in smller kes with more defects, high –F termintions, nd extremely low concentrtion of crri-
ers t the Fermi level. However, signicnt improvement in conductivity is observed when  LiF–HCl
mixture is used s the etchnt (Ren et al., 2016; Zho et al., 2016). Trnsprent thin MXene lm
smples tend to exhibit high conductivity, in which the possibility of nding well-ligned kes with
miniml inter-ke resistnce occurs (Sng et al., 2016). For  better understnding of the intrinsic
trnsport properties of MXenes, it is impertive tht studies must be conducted on singe kes.
However, the fbriction of single-ke MXenes of sufcient lterl size hs been difcult. There
re  few reports of successful studies on trnsport properties of mechniclly exfolited Ti2CTx (Li
et al., 2015) nd monolyer Field-effect trnsistors (FETs) (Sng et al., 2016; Liptov et al., 2016b).
Another interesting electronic property of MXenes is its cpbility for EMI shielding effective-
ness (SE). The good electricl conductivity, lminte structure, nd ese of processibility with tun-
ble surfce chemistry ttributes to excellent EMI SE. The lms of Ti3C2 nd its composites hve
shown EMI shielding cpbilities comprble to metls nd outperforming similr 2D mterils.
This outstnding performnce of the MXene, Ti3C2Tx is due to their high electricl conductivity
(high electron density) nd ttenution due to multiple reections in the lyered thin lms (Iqbl
et al., 2020). Like other 2D mterils, MXenes lso exhibit nisotropy of electronic conductivity
tht is entirely dependent on the intrinsic vn der Wls gp nd stcked lyers, nd this mkes it
useful for multiple nnoelectronics devices.

1.3.3 MAGNETIC PROPERTIES

Although mny MXenes hve been theoreticlly predicted nd experimentlly synthesized, 
mjority of them re nonmgnetic, which limits their use in res like spintronics. There re  few
MXenes tht re predicted to be intrinsiclly mgnetic, like, Ti2C nd Cr2C, of which  few re
ferromgnetic nd  few re ntiferromgnetic (Go et al., 2016). In this quest to develop/discover
mgnetic MXenes, more ttention is being given to hlf-metllic MXenes, since they hve one
spin chnnel s metllic nd the other s semiconducting, resulting in  Fermi level with com-
pletely spin-polrized electrons. Although cler prediction of ferromgnetic nd ntiferromgnetic
MXenes hs been done, it is difcult to replicte the exct sme result s the surfce functionliz-
tion of these compounds during termintion is still not completely controllble. A few exmples of
mgnetic MXenes re Ti2C, Ti2N, Cr2C, Cr2N, nd Mn2C, mong others (Ling et al., 2014; He et al.,
2016; Wng, 2016; Xiong et al., 2018). (See Figure 1.3.)
 Introduction: MXene—A Novel Two-Dimensional Material

FIGURE 1.3 An outline of electronic nd mgnetic properties of M2CTx crbide MXenes nd M2NTx nitride MXenes tht re predicted theoreticlly. Here, M is n
erly-trnsition metl element nd Tx is functionl groups –O, –OH, or –F. The electronic bnd structure nd ground-stte mgnetic congurtion re shown.
7
8 MXene-Filled Polymer Nanocomposites

1.3.4 OPTICAL PROPERTIES

A wide rnge of opticl properties, such s plsmonic properties nd the nonliner opticl behvior
of MXenes, hve led the wy to its ppliction in sturble bsorption for mode-locked lsing, pls-
monic brodbnd bsorber, surfce-enhnced Rmn scttering (SERS) substrte nd phototherml
therpy (Dong et l., 2018; Srychev et al., 2017; Stheeshkumr et al., 2016; Szuplewsk et al.,
2019). Surfce termintions re found to mostly ffect the opticl properties of MXenes (Wng
et al., 2017; Bi et al., 2016).
The mterils exhibit two types of plsmonic behvior—surfce plsmon nd bulk plsmon
(Mier nd Atwter, 2005). While bulk plsmons re oscilltions of electrons seen deep inside
the free crrier’s body, surfce plsmons (Figure 1.4) re electron oscilltions t the surfce t 
metl–dielectric interfce. Plsmonic excittion results in loss of energy due to the interctions
of high-speed electrons within the solid (Mier nd Atwter, 2005). The wek interlyer coupling
of the MXene results in bulk plsmon energy tht is not dependent on the thickness of the lyers
(El-Demellwi et al., 2018). Additionlly, Ti3C2Tx MXene hs been reported to exhibit high surfce
plsmon excittions (Muchmp et al., 2014). The surfce plsmons cn be observed t nnometer-
scle nd t mid-infrred spectrl rnge, nd this spectrl rnge suitble for chemicl-sensing ppli-
ctions (Ross Stnley, 2012). Depending on the functionliztion, the surfce plsmon wvelength
of Ti3C2Tx MXene cn be vried or kept constnt over  wide spectrl rnge (6–2 μm for thicknesses
with  spectrl rnge between 5–45 nm). The vritions cn be mde by controlling the thickness
of MXene. Thus, the possibility to tune nd enhnce surfce plsmons mke MXenes promising
mterils for plsmonic pplictions (Muchmp et al., 2014). Additionlly, plsmon energies of
bre Ti2C, Ti2N, Ti3C2, nd Ti3N2 re theoreticlly found to be 10.00, 11.62, 10.81, nd 11.38 eV,
respectively (Bi et al., 2016; Khzei et al., 2017; Hntnsiriskul nd Gogotsi, 2018).
MXenes exhibit photoluminescence in n queous solution, which is n importnt feture for
biologicl pplictions (Wng et al., 2020). Quntum dots (QDs) re developed using MXene s
quntum connement, nd edge effects re enhnced with tomiclly thin quntum dots (Medintz
et al., 2005; Pn et al., 2010). Mxene QDs with  photoluminescence property hve been synthesized
vi hydrotherml method, which exhibited excittion-dependent photoluminescence behvior with 
quntum yield of pproximtely 10% (Pn et al., 2010; Xue et al., 2017). Additionlly,  Ti3C2TxQD
tht exhibits white photoluminescence nd uorescence bsed on two photons hs been reported to
be synthesized using  solvotherml method, with  quntum yield of 9.36% (Lu et al., 2019).
Nonliner bsorption of light by mterils rises from nonliner opticl response of  mteril
with the increse in intensity of illuminting light. This property hs been pplied in vrious elds
like opticl communictions, sensing, lsers, nd photonic devices (Wng et al., 2020). Sturble
bsorbers (SAs) re importnt nonliner opticl devices used to convert continuous lser output to

FIGURE 1.4 MXene surfce plsmon. (A) Energy-loss spectr vs Intensity of Ti3C2(OH)2 with vrious
thicknesses (B) STEM-HAADF imges of Ti3C2Tx tringulr ke displying longitudinl SP, trnsversl SP,
nd interbnd trnsition SP.
Introduction: MXene—A Novel Two-Dimensional Material 9

FIGURE 1.5 Nonliner opticl properties of MXene. (A) Z-scn mesurement of n MXene thin lm (B),
(C) SA property of MXene, (D) Absorption coefcient vs lser intensity of MXene t 1064 nm (E) Ti3CNTx-
bsed mode locker in ring-cvity erbium-doped ber lser.

 trin of lser pulses nd re incorported into ber lser cvity (Ismil et al., 2016). SAs hve n
bsorption coefcient tht decreses with incresing light intensity (Liu, 2009; Figure 1.5). The
intensity-dependent opticl trnsmission is  key fctor in the SA (Yi et al., 2019). The bsorption of
light by Ti3C2Tx is reported s nonliner, nd Ti3C2Tx exhibits sturble bsorption for wvelengths
from 800 to 1800 nm (Dong et al., 2018). Ti3C2Tx hs been reported to exhibit brodbnd nonliner
opticl response nd hs ppliction in femtosecond lser genertors (Jing et al., 2018). The opticl
properties of MXenes re  eld tht requires more extensive reserch for pplictions in photonic,
optoelectronic, nd plsmonic devices.

1.3.5 RHEOLOGICAL PROPERTIES

Rheologicl properties of mterils in suspension help in understnding its ppliction in solution
processing, s well s mnufcturing, methods. MXenes hve been studied for viscous nd visco-
elstic properties using colloidl dispersions to high-loding slurries, which showed tht  multilyer
MXene suspension with bout 70 wt.% re cpble of uidity (Akuzum et al., 2018; Ghidiu et al.,
2014; Mleskind Gogotsi, 2017). It is seen tht MXene single-lyer kes possess high viscosity
t extremely low concentrtions nd single-lyer colloidl solutions exhibited prtil elsticity even
for the lowest concentrtion. Vrious pplictions hve been demonstrted utilizing the rheologicl
10 MXene-Filled Polymer Nanocomposites

property of MXene (Akuzum et al., 2018). A high spect rtio nd  negtive surfce chrge result
in complex hydrodynmics nd electrosttic force between prticles, nd these spects re found to
hve lrge impct on the rheology of mteril dispersions (Bergenholtz et al., 2002; Russel, 1980).
Single-lyer nd multilyer dispersions of MXene hve been studied for vrious concentrtions to
understnd rheologicl properties nd demonstrted in vrious pplictions (C. [John] Zhng et al.,
2019; Yo et al., 2020; Li et al., 2020; Wng et al., 2021).

1.4 APPLICATION
1.4.1 ELECTRONIC APPLICATIONS
Metllic MXenes with high/low work functions (WFs) show enormous potentil s Schottky br-
rier (SB)–free metl contcts to 2D semiconductors. It is predicted tht –OH-terminted MXenes
with ultrlow WFs my form n-type brrier-free Schottky contcts with 2D semiconductors, like
trnsition metl dichlcogenides nd blue phosphorene (Zhn et al., 2020). It ws reported tht
there re greter chnces for Ti3C2Tx to form Ohmic contct, thereby improving crrier injection
efciency, due to its wide tunbility of work function. Six MXenes—V2CO2, Mo2CO2, Cr2CO2,
Cr2NO2, V4C3O2, nd V2NO2—re found to be useful s metl contcts to MoS2 (You et al., 2019).
It pves the wy for its ppliction s electrode mteril in FETs (Lyu et al., 2019).
An Ti3C2Tx MXene is used s contct electrodes in the fbriction of orgnic thin-lm trn-
sistors (OTFTs) nd complementry logic circuits (Lyu et al., 2019). Ti3C2Tx MXene-bsed elec-
trodes in orgnic eld-effect trnsistors (OFETs) demonstrted excellent crrier mobility of bout
1 cm2 V−1s−1 nd on−off current rtio of bout 107 for p-nd n-type on exible plstic substrtes (Lyu
et al., 2019). The sme MXene is lso used s  contct for n Si–solr cell with better power conver-
sion efciency (PCE) nd s Schottky junction heterostructures in self-driven photodetectors (Kng
et al., 2017; Fu et al., 2019). There is lso  recent report in which MXene is used in  perovskite
solr cell to improve its work function nd interfce to enhnce PCE (Agresti et al., 2019).
A study of the mechnicl properties of ultrthin MXene-rmid nnober (ANF) composite hs
proved to be efcient in EMI shielding. Even  lower MXene content of <10 wt% hs been shown
to improve the mechnicl properties of pure ANF pper. A mximum of 197 MP, 9.8% tensile
strength nd the frcture strin hve been reported, respectively. With the ddition of more MXene,
it is seen tht there is n increse in the electricl conductivity nd EMI SE of  17-μm-thick lm to
170 S cm−1 nd 33 dB, respectively (Xie et al., 2019).
Five different MXenes, nmely, Ti2CTx, Ti3C2Tx, Mo2CTx, Nb2CTx, nd V2CTx re found to
exhibit plsmonic fetures nd re used in the fbriction of plsmonic photodetectors. Among
the nlyzed MXenes, Mo2CTx exhibited the best performnce with excellent stbility (Velusmy
et al., 2019).
MXene/polymer composites like hydroxyethyl cellulose (He et al., 2020), PEDOT:PSS/PANI
(R. Liu et al., 2018; Y. Zhng et al., 2019) with Ti3C2TxMXene hve been developed for EMI shield-
ing pplictions. Other forms of MXene composites used for EMI pplictions re in the forms of
hybrid structures (CNT/MXene/CNF (Co et al., 2019); PVDF/MXene/Ni (Wng et al., 2019)), lm-
inte structures (TiO2-Ti3C2Tx/grphene (Xing et al., 2019), MXene–grphene–PVDF (Rguln
et al., 2018), porous foms (Weng et al., 2019; X. Wu et al., 2020), nd erogels (Hn et al., 2019),
ll of which hve found prcticl implementtion in erospce nd militry pplictions. Hydrogels
bsed on Ti3C2Tx/PVA or CNT or PDAC (An et al., 2018; Ci et al., 2018; Y. Z. Zhng et al., 2018)
re developed nd exhibits high sensitivity under strin, mking it possible to sense vocl sounds of
similr phonetics nd nger motion sensing.
Severl MXene-bsed sensors for sensing mechnicl strin, biomolecules, nd gses (ethnol,
methnol, cetone, mmoni) hve been developed. It is observed tht MXene-bsed gs sensors
show  high-selectivity response to hydrogen-bonding gses over cidic gses underlining the
importnce of the functionl group (Lee et al., 2017; Kim et al., 2018). A piezoelectric sensor tht
Introduction: MXene—A Novel Two-Dimensional Material 11

is sensitive to externl pressure nd mechnicl strin is developed, nd it exhibits  guge fctor
of 180.1–94.8 (0.19–0.82% strin) nd 94.8–45.9 (0.82–2.13% strin) which is much higher when
compred to the existing mterils (M et al., 2017).
This estblishes the concept of using multiple MXenes for  rnge of 2D devices, like eld-effect
devices, Schottky junctions, ohmic contcts photodetectors, nd memory devices, femtosecond
pulsed lser, piezoresistive sensor, nd contct electrodes for solr cells, mong others.

1.4.2 PHOTONIC APPLICATIONS

Recent reports show tht MXenes hve been widely used for photonic-bsed pplictions. For exm-
ple, V2CTx (T = F, OH, O) is used s conductive electrodes s it hs bsorption in the 500–2700-nm
rnge with high conductivity (Ying et al., 2018). MXenes like Ti3C2Tx (Lin et al., 2017), Nb2CTx
(Lin et al., 2017), T4C3Tx (Di et al., 2017) modied by soyben phospholipid (SP) or polyvinyl-
pyrrolidone (PVP) for improved colloidl stbility, show high bsorption coefcient in visible nd
ner-infrred (NIR) regions, mking them prticulrly suitble for phototherml therpy pplic-
tions. A lef–vein network-bsed MXene-coted exible freestnding electrode is prepred, nd its
conductive nd mechnicl properties re found to be exemplry. The lef-bsed electrode is used
to fbricte  semi-trnsprent ultrviolet photodetector, which hs  very cler photo response nd
outstnding exibility, mintining 90% of the photo response fter being bent 1000 times (Chen
et al., 2020). A self-powered photodetector with n MXene–silicon vn der Wls heterostructure
is developed nd tested (Zhng et al., 2017). In nother cse,  Ti3C2Tx trnsprent, exible, con-
ductive lm with n opticl gure of merit bout 15, trnsmittnce s high s 93%, nd electri-
cl conductivity of pproximtely 9880 S cm−1 hs been developed for optoelectronic pplictions.
MXene nd noble metl (Ag, Au, Pd) nnoprticle hybrids hve been fbricted for SERS pplic-
tion (Stheeshkumr et al., 2016).

1.4.3 BIOMEDICAL APPLICATIONS

The unique physicochemicl properties of MXene mke it convenient for its use in pplictions,
such s phototherml therpy, nticncer tretment, nd drug delivery. The min fctors tht must
be considered when nnomterils interct with living tissues re its biocomptibility nd colloidl
stbility. It is impertive to gin  deeper understnding bout neurl dynmics, which would the
pve wy to treting brin diseses nd injuries more effectively, nd this is being mde esier with
the use of implntble microelectrodes. Simple nd sclble exible microelectrode rrys using
MXene-bsed conductive inks hve been developed for in vivo micro-electrocorticogrphy record-
ing nd possessed remrkbly high volumetric cpcitnce of 1500 F/cm3 (Driscoll et al., 2020). A
multifunctionl thernostic gent comprising of MnOx/Ti3C2 composite MXene is developed nd
surfce engineered with soyben phospholipid for efcient mgnetic resonnce (MR) nd photo-
coustic imging-guided phototherml therpy (PTT) ginst cncer (Di et al., 2017). When Ti3C2
is loded with doxorubicin (DOX),  uorescent drug, nd hyluronic cid (HA), n effective tumor
trgeting nnomteril is formed (Liu et al., 2017). Ti3C2MXeneQDs re prepred, nd it is seen
tht the photoluminescence emission mximum shifts from blue to red, nd these could be used
for in vitro bioimging (Xue et al., 2017). Another MXene tht shows good promise in CT imging
is T4C3 due to their excellent biocomptibility nd eco-friendly synthesis (Lin et al., 2018; Z. Liu
et al., 2018). Similrly, MnOx/Ti3C2 (Di et al., 2017) composites re lso good cndidtes for MR
imging techniques.
Another importnt ppliction is in the development of sensors to ensure environment nd
humn sfety. The mjor chrcteristics of n effective sensor re short response time, low limit
of detection (LOD), high sensitivity, selectivity, low cost of production nd wide liner rnge. A
meditor-free nitrte biosensor with hemoglobin (Hb) immobilized on Ti3C2 MXenes s  protein-
binding pltform is reported (Liu et al., 2015). They obtined direct energy trnsfer of Hb on the
12 MXene-Filled Polymer Nanocomposites

bre substrte nd re used to detect the presence of nitrite in environmentl wter smples. There
hve been reports of  pH-sensitive Ti3C2QDs used to monitor intrcellulr pH nd developed wer-
ble uorescent nno-sensors (Chen et al., 2018). An Au/MXene composite biosensor is developed
to detect enzymtic glucose (Rkhi et al., 2016). A nonenzymtic glucose sensor using  porous
nickel–coblt-lyered double hydroxide nnocomposite hs been developed with  wide linerity
rnge nd low limit of detection (Menghui Li et al., 2019). An MXene-bsed nnocomposite ws
used to detect dopmine from  conductive mtrix of Pd/Pt nnoprticles with  DNA-dsorbed
MXene surfce exhibited excellent linerity nd high selectivity ginst scorbic cid, uric cid, nd
glucose (Zheng et al., 2018). Hb immobilized on the MXene surfce is lso used to develop H2O2
meditor-free biosensor (Wng et al., 2014). A Ti3C2-bsed FET biosensor for dopmine detection
nd neurl ctivity monitoring is developed nd hd low LOD, nd  wide liner rnge (Xu et al.,
2016). A werble voltile orgnic compound sensor cpble of detecting biomrkers (e.g., mmo-
ni in lung diseses) re lso developed by  group of reserchers using MXene-bsed devices (Lee
et al., 2017). There re reports stting the use of MXene for removing from wter bodies pollutnts
like hevy metl dsorption (Guo et al., 2015, 2016; Ying et al., 2015; Shhzd et al., 2017), dye
removl (Mshtlir et al., 2014; Wong et al., 2018), nd biologicl sorption of bcteri (Xio et al.,
2009; Jstrzebsk et al., 2017).

1.4.4 ELECTROCHEMICAL AND ENERGY STORAGE APPLICATIONS

Due to its role in developing sustinble energy, the engineering of efcient electrochemicl energy
storge is vitl. To chieve this, the serch for new mterils nd improvement of electrode rchitec-
ture hve been  reserch priority in recent yers (Mthis et al., 2019). However, conventionlly seen
chrge storge mechnisms (ion intercltion nd electric double-lyer [EDL] cpcitnce) seen in
electrochemicl energy storge devices re not ble to keep up with the demnds of energy storge
needs (Mthis et al., 2019). Intercltion pseudo-cpcitnce tht occurs vi bulk redox rections
with ultrfst ion diffusion is emerging s n lterntive mechnism in electrochemicl energy
(Mthis et al., 2019; Okubo et al., 2018). MXenes re promising intercltion pseudo-cpcitor
electrode mterils due to their high electricl conductivity for  high current chrge,  lyered
structure for ion intercltion, nd complementry bttery performnce for lrge specic cpcity
(Okubo et al., 2018). Other properties of MXenes like their bility for redox ctivity, high pseudo-
cpcitnce rte, electrochemicl stbility in cidic nd corrosive electrolytes, nd good cycling
stbility mke them preferble over other 2D mterils (Okubo et al., 2018). MXenes hve lredy
been demonstrted in vrious energy storge devices like btteries, fuel cells, nd electrochemicl
cpcitors (Luktsky et al., 2013; Mshtlir et al., 2013; Fei et al., 2018; Hung et al., 2019; Come
et al., 2012).
With the ever-incresing demnd for energy nd n urgency for implementing sustinble, green,
nd clen energy, renewble energy from sources like wind nd sun re becoming vitl. Since these
energy sources re spordic in nture, the role of energy storge devices is indispensble (Dusstre,
2010). High efciency in energy conversion, comprtively long life-spn, nd low cost mke elec-
trochemicl methods importnt technology for energy storge. The concept hs been lredy dem-
onstrted vi lithium–ion btteries, lithium–sulfur btteries, sodium–ion btteries, potssium–ion
btteries, nd multivlent–ion btteries in mny pplictions, such s portble devices nd electric
storge.
Two-dimensionl lyered mterils (grphite, LiCoO2, TiS2), with their high nisotropic
2D structure for fst chrge trnsfer nd lrge interlyer spce tht llows fst ion intercltion/
deintercltion, hve proved to be good electrode mterils in btteries (Aurbch et al., 1999;
Okumur et al., 2020; Oh et al., 2016). 2D MXenes possess tunbility, high spect rtio, high con-
ductivity (9880 S/cm for Ti3C2Tx), nd hydrophilicity (with contct ngle in the rnge 21.5° to 35°),
which mkes them not only good electrodes but lso  protective lyer for metl nodes to prevent
dendrite growth (Ansoriet al., 2019; Nguib et al., 2014; Nguib et al., 2021). MXene ws initilly
Introduction: MXene—A Novel Two-Dimensional Material 13

used s  mteril for negtive electrodes in Li–ion btteries (Nguib et al., 2012). Nondelminted
Ti2CTx in 1M LiPF6/ethylene crbonte (EC)–diethyl crbonte (DEC), delivered  specic cpcity
of 150–200 mAh/g t bout 20 mA/g with good cpcity retention (Nguib et al., 2012). Similrly,
nondelminted Nb2CTx nd V2CTxin  no-queous Li+ electrolyte gve the specic cpcities of
210–220 mAh/g (Nguib et al., 2013).
Lithium-sulfur bttery, with sulfur s ctive mterils in cthode exhibits high specic cpcity
of round 1675 mAh/g (Ji et al., 2009). But sulde dissolution nd deposition in electrolyte cuses
loss of sulfur nd destroys specic density nd cycle property of the bttery (Bruce et al., 2012;
Ling et al., 2015). In order to improve the performnce of these btteries, new strtegies re being
developed, nd one of them is nding the best mteril for building the node of lithium–sulfur
bttery (Ji et al., 2009; Ling et al., 2015; D. W. Wng et al., 2013). MXene sheets hve been tested
for the sme, nd sulfur toms re seen to be bonding well with Mxenes (Luktsky et al., 2013;
Nguib et al., 2012). Additionlly, the high specic re of 2D MXenes provide sufcient re
for electrochemicl ction nd ccommodtion of sulfur (Ling et al., 2015; Png et al., 2014;
To et al., 2014). It hs been demonstrted tht when  sulfur cthode is composited with Ti2C or
Ti3C2MXenes, it exhibits high performnce (Zho et al., 2015). Additionlly, considering the role
of surfce termintion, it hs been found tht –OH-terminted MXene nd its defective species re
found to be efcient in trpping sulfur in lithium–sulfur btteries (Ling et al., 2017).
High-power sodium–ion btteries hve gret potentil in lrge-scle pplictions, nd owing to
the bundnce nd low cost of sodium, sodium–ion btteries re in focus (Wng et al., 2015). The
negtive electrodes tht re currently used in these btteries re mde of mterils such s hrd
crbon, TiO2, phosphorous, nd P2-N0.66[Li0.22Ti0.78]O2 suffer from trde-off between energy nd
power densities (Ponrouch nd Goib, 2013; Oh et al., 2014; Qin et al., 2013; Y. Wng et al.,
2013). Additionlly,  lrge volume chnge due to its rection with lrge sodium ion leds to low
cycle stbility. New mterils like MXenes with pseudocpcitive behvior s negtive electrodes in
sodium–ion btteries is found to resolve these problems (Wng et al., 2015). Ti3C2Tx MXene in non-
queous N+electrolyte does not undergo ny substntil structurl chnge during the electrochemi-
cl rection nd hs good cpcity retention over 100 cycles (Kjiym et al., 2016). V2CTx hs
been demonstrted s positive electrode for sodium–ion cpcitor. Electrochemicl testing proved
tht both pseudocpcitive nd diffusion-limited redox rections occur in V2CTx. V2CTx/hrd cr-
bon sodium–ion cpcitor is built, nd it showed  mximum cell voltge of 3.5 V nd  cpcity
of 50 mAh/g (Dll’Agnese et al., 2015). In ddition to Li–ion nd sodium–ion btteries, MXenes
re tested for potssium–ion btteries, multivlent–ion btteries, nd others (Wu et al., 2021; Ming
et al., 2021).
MXene-bsed electrodes hve been tested for supercpcitors operting in queous electro-
lytes nd nonqueous electrolytes, s well s in hybrid, ll-solid-stte, nd micro-supercpcitors
(Ansori et al., 2019). Other thn pristine MXene electrodes, their composites hve lso been
investigted to further enhnce their electrochemicl nd mechnicl performnces (Dll’Agnese
et al., 2016; Ling et al., 2014). Ti3C2Tx electrodes re found to reversibly interclte vrious ctions
like N+, K+, NH4+, Mg2+, nd Al3+ with  cpcitnce vlue of 440 Fcm−3. Its performnce over 
wide rnge of chrging rte in vrious lkline nd neutrl electrolytes show cpcitive-like elec-
trochemicl behvior (Luktsky et al., 2013; Levi et al., 2015). Menwhile, in cidic electrolyte
(1 M of H2SO4), n MXene cly electrode exhibited  higher cpcitnce of 900 Fcm−3 (Ghidiu
et al., 2014). Such  high vlue of cpcitnce is possible only with pseudocpcitive contribu-
tions from Ti toms (Thoms et al., 2021; Luktsky et al., 2015). However, the limited potentil
rnge of MXene electrodes in queous electrolytes re  disdvntge (Ansori et al., 2019). Using
microporous electrode rchitecture,  cpcitnce of 210 Fg−1t 10 Vs−1nd 100 Fg−1 t 40 Vs−1 rte
nd using MXene hydrogel by incorporting H2SO4 electrolyte in between MXene lyers enbled
cpcitnce of bout 1500 Fcm−3 (Luktsky et al., 2017). MXene electrodes hve lso been tested
using crbon current collectors nd potentil window could be incresed to 1V in 3M H2SO4
(Luktsky et al., 2017).
14 MXene-Filled Polymer Nanocomposites

Due to the bsence of wter electrolysis rection, non-queous electrolytes offer higher potentil
window for MXene electrodes. A composite of MXene/crbon nnotube electrodes in 1 M of ethyl-
methylimidzole–triouro-sulfonylimide gve  potentil window of 1.8 V nd  cpcitnce of
245 Fcm−3 (Dll’Agnese et al., 2016; Figure 1.6). MXene electrodes, when used in net ionic liquid
electrolyte, showed  cell voltge of 3 V nd cpcitnce of 75 Fg−1with good power performnce
(Lin et al., 2016). The key issue with MXene electrodes in  nonqueous electrolyte is tht it exhibits
low cpcitnce, only in the rnge of 80 to 100 Fg−1. These vlues, which re much less thn wht
is seen in cidic electrolytes, is due to the bsence of hydronium ions or protons of wter molecules
tht fcilitte redox pseudo-cpcitnce in trnsition metl (Conwy et al., 1997).
All-solid-stte supercpcitors nd micro-supercpcitors (MSCs), which re sfer energy stor-
ge systems, re being developed for implementtion in pplictions such s werble devices nd
exible displys (Lu et al., 2014; Penget al., 2016; Hu et al., 2017; Kurr et al., 2016; Li et al., 2016).
MXene-bsed electrodes re used in ll-solid-stte MSCs for on-chip energy storge, which deliv-
ered n rel cpcitnce of 28 mFcm−2 (Peng et al., 2016). Ti3C2Tx MXene ink is used for stmping
coplnr MSCs on  exible substrte, nd this method of fbriction cn result in low-cost, scl-
ble, nd fst mnufcturing of MSCs (C. J. Zhng et al., 2018; Figure 1.7).

FIGURE 1.6 () Cyclic voltmmetry plot nd (b) chrge storge mechnism of Ti3C3Tx electrode in EMI–
TFSI ionic liquid electrolyte.

FIGURE 1.7 Illustrtion of Ti3C2Tx micro supercpcitor fbriction (A) using spry coting: thin lyer
of Ti3C2Tx is formed t the bottom s the current collector; (B) coting of n electroctive Ti3C2Tx lm; (C)
lser cutting to obtin interdigitl electrodes; nd (D) pinting of PVA/H2SO4 get electrolyte into interdigitl
Ti3C2Tx to fbricte MSCs.
Introduction: MXene—A Novel Two-Dimensional Material 15

FIGURE 1.8 Schemtic depiction of the most importnt properties nd pplictions of MXenes.

These demonstrtions show tht MXene with its pseudocpcitive behvior cn be used for
energy hrvesting nd storge. Further study on optimiztion of MXenes using methods such s
building nnocomposites or developing better electrode rchitecture cn open exciting results in
energy hrvesting, conversion, nd storge using electrochemicl methods (Luktsky et al., 2017;
Figure 1.8).

1.5 CONCLUSION
The lrge fmily of MXenes hs been found to hve immense potentil in vrious pplictions nd
is being extensively reserched for the possibility of new properties, sfer etching methods, nd
new functionlities. The outstnding electrochemicl properties of MXenes like their bility for ion
dsorption nd diffusion hve given these mterils extr leverge in energy storge pplictions
compred to other 2D mterils. The biomedicl pplictions of MXenes prove tht they re bio-
comptible s well. MXetronics is n evolving eld owing to the potentil electronic nd photonic
pplictions of MXenes. While the reserch on its ppliction in vrious pplictions is dvncing,
there re  few chllenges tht need to be overcome for its reliztion into sclble industril ppli-
ctions. An environmentlly friendly, sfer, nd sclble etching method is something tht must be
worked on since current methods involve concentrted cids nd other chemicls. Understnding
the surfce chemistry, relizing new surfce termintions, nd the bility to control surfce termi-
ntions cn led to vrious tunble properties nd functionlities. Additionlly, the possibility of
MXene synthesis without surfce termintion is to be devised. Even though more thn 60 MXenes
hve been predicted, Ti3C2 is the MXene tht is widely studied for vrious pplictions. The need
for extending studies to understnd the stble etching, stbility, properties, nd functionlities of
other MXenes re necessry for further dvncement in MXenes. Other chllenges like understnd-
ing mgnetic properties of MXenes, defect engineering for better control of properties, improve-
ment of chemicl nd therml stbility of MXenes, etching of MXenes from non-Al MAX phses,
nd lerning the electromgnetic ttenution properties of MXenes re open to reserch for these
mterils, which hve gretly progressed within  decde of its discovery.
16 MXene-Filled Polymer Nanocomposites

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24 MXene-Filled Polymer Nanocomposites

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Introduction: MXene—A Novel Two-Dimensional Material 25

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26 MXene-Filled Polymer Nanocomposites

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 2 Overview of MXene-Based
Polymer Nanocomposites
State of the Art and
New Challenges
Prajitha V, Jibin K P, Sisanth K S, Abitha V K,
Hanna J Maria, and Sabu Thomas

CONTENTS
2.1 Introduction ............................................................................................................................. 27
2.2 Synthesis of MXene/Polymer Nnocomposites ...................................................................... 29
2.2.1 Solution Blending........................................................................................................ 30
2.2.2 Ltex Compounding .................................................................................................... 31
2.2.3 Melt Blending.............................................................................................................. 33
2.2.4 In Situ Polymeriztion ................................................................................................. 33
2.3 Properties................................................................................................................................. 33
2.4 Applictions ............................................................................................................................ 37
2.5 Conclusion............................................................................................................................... 38
References........................................................................................................................................ 39

2.1 INTRODUCTION
Novel two-dimensionl (2D) MXene nnomteril discovered t Drexel University in 2011 hs gr-
nered signicnt interest mong reserchers due to its 2D morphology nd high therml, electricl,
nd mechnicl properties. MXene is generted through  prticulr drwing of mss ternry cr-
bide MAX-stge forerunners. The generl representtion of MXene is Mn+1XnTx, where M denotes
trnsition metl, including Sc, Y, Ti, Zr, Hf, V, Nb, T, Cr, Mo, or W X, represents crbon or nitro-
gen, nd n lies between 1–3 (Nguib et al., 2012). Figure 2.1 shows the different elements tht re
used for the formtion of the MAX phse. The MAX phse is exfolited by the creful engrving
of the A-phse using hydrouoric (HF) cid.
Compred to the solid M–X bond, the bond between M–A b is wek nd rective. It is possible
to remove the A lyer with  suitble etching regent nd forms MXene denoted s Mn+1XnTx,Tx
(oxygen [=O], hydroxyl [–OH] nd uorine [–F]) is the surfce-terminting functionl groups forms
during the etching process, nd the thickness of the MXene lyers be governed by the n vlue
(Lipton et al., 2019).
The HF-etching route to disssocite the bond between M–A in the compound Mn+1AXn with Al
cn be explined with the following chemicl chnges.
Ti3C2Tz, the most frequently investigted MXene to dte, ws combined to polydillyldimeth-
ylmmonium chloride (PDDA) nd polyvinyl lcohol (PVA), eqully hydrophilic polymers, in
the rst-ever report of MXene polymer nnocomposites in 2014 (Ling et al., 2014). Ti3C2Tz ws
mde by etching Ti3AlC2 in 50% HF for 18 hours t room temperture (RT) with constnt stir-
ring. The MXene multiple lyered sheets were rinsed using wter in nticiption tht  pH of 6 ws
mesured fter etching. These ne prticles were then dried out t room temperture for 24 hours
DOI: 10.1201/9781003164975-2 27
28 MXene-Filled Polymer Nanocomposites

in dvnce being immersed in dimethyl sulfoxide (DMSO) for 18 hours t RT nd subsequently iso-
lted by dding H2O nd centrifugtion. To this set prt, DMSO interpolted ML MXene residue,
300:1 wter ws dded, nd the solution ws sonicted in owing rgon (Ar) for bout 5 hours. From
2014 to 2021, there were bout 150 ppers published in this re. Ech yer, the number of mnu-
scripts in MXene polymer nnocomposites doubles compred to the previous yer, s depicted in
Figure 2.1. The incresed number of published rticles shows how importnt these mterils re to
the polymer eld. The cittion in Figure 2.2 revels the interest mong other reserchers in this re

FIGURE 2.1 MXene nnocomposites publictions nd cittions over the yers strting from 2014.
Source: Web of Science.

FIGURE 2.2 Cittion report of MXene polymer nnocomposites rticles.

Source: Web of Science.
Overview of MXene-Based Polymer Nanocomposites 29

FIGURE 2.3 Top 25 institutions engged in MXene polymer nnocomposites reserch.

nd the potentility of MAX phse mterils in ll elds of science, including electronic, environ-
mentl, energy storge, nd wter puriction pplictions. We cn see from Figure 2.2 tht fter
2019,  drstic chnge in cittion nd number of ppers published becuse the difculty in synthesis
procedure of MAX phse mterils is somewht optimized in these yers nd more cceptble nd
reproducible synthetic production route is estblished.
MXene nnoprticles reinforced in the polymer mtrix re hot res where reserchers re nd-
ing exciting results due to the extrordinry surfce region, therml, mechnicl, nd electricl
pplictions of MXene (Chen et al., 2021). MXene hs unique properties due to its 2D structure, like
one of them is high mechnicl strength, nd MXene hs  330 ± 30 GP Young’s modulus vlue.
Becuse of the high electromgnetic shielding properties, the composites hve been studied for elec-
tromgnetic interference (EMI) shielding pplictions. MXene/polymer composite hs pplictions
in innumerble rens, such s energy expedients, membrnes, rdition shielding, drug delivery,
biosensors, nd others (Zhng et al., 2007; Crey et al., 2019; Shi et al., 2019; Guo et al., 2020; Xio
et al., 2020).

2.2 SYNTHESIS OF MXene/POLYMER NANOCOMPOSITES

The polymers re reinforced with  lrge vriety of nnomterils to improve mechnicl strength,
therml, electricl, opticl, brrier, nd more. Lyered MXene mterils with high mechnicl
strength nd conductivity, s  potentil ller in polymers, llow the dispersion of nnomterils,
which hs  signicnt role in improving the properties in polymer nnocomposites. There re sev-
erl preprtion techniques re used by scientists to improve distribution s well s properties. The
interfcil thickness; secondry interctions, such s hydrogen bonding, electrosttic interction,
vn der Wls forces; nd others, even covlent bonding with polymer nd MXene, re successfully
synthesized by reserchers. The synthesis techniques opted for re bsed on the type of polymers,
wter-soluble thermoplstic PVA, nd MXene composites re synthesized by solution blending,
solution csting, nd other methods. The thermoplstic mterils, like ultr-high moleculr weight
polyethene nd polylctic cid polypropylene (PP), mong others, re synthesized vi melt blending
(Ling et al., 2014; Zhng et al., 2016; Shi et al., 2019; Hung et al., 2020; Xue et al., 2020; Tn et al.,
2021). Elstomeric/MXene nnocomposites re synthesized minly vi ltex compounding nd
vcuum impregntion techniques used for the thermoset mterils (Akyiiret al., 2021). Synthesis
30 MXene-Filled Polymer Nanocomposites

techniques lso depend on the ppliction of the prepred nnocomposites. Vrious methods re
used for the synthesis of MXene/polymer nnocomposites:

• Solution blending
• Ltex compounding
• Melt blending
• In situ polymeriztion

2.2.1 SOLUTION BLENDING

Solution csting is  mjorly used technique for MXene/polymer synthesis. The superior hydrophi-
licity of the MXene mteril simplies the processing method for esily soluble polr polymers,
such s polyvinylidene uoride, polyurethne, nd others, dissolved minly in  dimethylformmide
(DMF) or  PDDA wter-soluble polymer like PVA. Esily dispersed MXene in such solvents mixed
with the polymer solution nd the composite prepred either vi solution csting or vcuum ltr-
tion method. Vrious scientists lso tried spin coting nd dip coting of the dispersion. Among
the solution blending process, PVA is more explored by scientists due to its solubility in wter.
Ling et l. fbricted PVA/MXene lms vi  vcuum-ssisted ltrtion technique s the potentil
electronic ppliction (Ling et al., 2014), nd Tn et l. explored the opticl properties of drop cst
PVA/MXene composites. They hve theoreticlly clculted the opticl bsorption coefcient nd
extinction coefcient. They hve  very high increse in conductivity, 30,000% higher thn the net
PVA owing to hydrogen bond formtion of MXene nd PVA (Tn et al., 2021). Wng et al. success-
fully cst Ti3C2Tx/epoxy compounds nd reveled the EMI protective ppliction for synthesized
composites. The highest EMI shielding vlue is found in the 15 wt% compositions, with n idel
electricl conductivity of 105 S/m nd n EMI shielding effectiveness of 41 dB (Wng et al., 2019).
Even though MXene is hydrophilic, getting good dispersion is  chllenge, nd to improve the distri-
bution surfce modiction of MXene is opted by reserchers using cetyltrimethylmmonium bro-
mide nd n SiO2 coting (Yu et al., 2019; Wn et al., 2020). Figure 2.4 shows the MXene/polymer

FIGURE 2.4 Schemtic digrm of PVA/MXene solution before csting (Mirkhniet al., 2019).
Overview of MXene-Based Polymer Nanocomposites 31

TABLE 2.1
Solvent-Blended MXene/Polymer Composites
Mxene/Polymer Preparation Method/ Applications/
Sl. No Composites Solvents Properties References
1 Ti3C2Tx/PVA Vcuum ltrtion Wter supercpcitor electrodes (Ling et al., 2014)
2 MXene/P(VDF-TrFE- Solution csting DMF Improved dielectric constnt (Tu et al., 2018)
CFE)
3 PVA/MXene Vcuum-ssisted Dielectric properties (ε′ = (Mirkhni et al., 2019)
nnocomposites ltrtion 370.5, tn δ = 0.11)
Electronic devices
4 MXene/Polypyrrole/ Solvent csting enhnced dielectric (Sho et al., 2019)
crylic resin elstomer Wter nd DMF permittivity (493 t 100 Hz)
composite
5 MXene/PVA hydrogel Geltiniztion Werble (Zhng et al., 2019)
Wter Cpcitive sensors
6 MXene-PDMS Dip-coting Werble smrt devices (Song et al., 2019)
composites
7 PVA/MXene Solution csting Wter Improved mechnicl (Pn et al., 2020)
nnocomposites strength
8 MXene/polyniline ber Coting Strin sensor (Cho et al., 2020)
9 MXene/P(VDF-TrFE) Spin coting Pressure sensor (Li et al., 2020)
DMF
10 Ti3C2Tx MXene@SiO2/ Solution coting Wter Dielectric constnt of 27.2 (Wn et al., 2020)
PVA composite Electronic ppliction
11 MXene/PVDF Solvent-ssisted mixing 48.47 ± 3.5 dB (Rjvel et al., 2020)
nnocomposites nd compression Loding concentrtion 22.55
molding Ethnol vol%
EMI shielding
12 SiC-nnowire/MXene Solution csting EMI shielding (M et al., 2021)
PVDF poly(dillyl
dimethylmmonium
chloride, PDDA)
13 PVA/MXene lms Vcuum-ssisted Pressure-sensing (Zho et al., 2021)
ltrtion Articil electronic skin

vi solution blending, nd Tble 2.1 shows the vrious polymer/MXene composites synthesized vi
the solution blending process.

2.2.2 LATEX COMPOUNDING

Akyiir et l. synthesized MXene/nitrile butdiene rubber (NBR) composites vi the emulsion-com-
pounding technique nd obtined good dispersion nd n increse in mechnicl strength. Using
14 vol% MXene, they got  570% increse in Young’s modulus (Akyiiret al., 2020). NBR/MXene
nnocomposites were synthesized vi the ltex-stge-compounding method. The MXene suspension
ws mixed with NBR ltex nd cogulted using hydrochloric cid. The vulcnizing gents re com-
bined with the rubber composite vi two-roll mill mixing nd compression molding with excellent
electricl conductivity with  potentil EMI shielding ppliction (Akyiir et al., 2021).
Guo et l. used  sponiction process between hydroxyl nd crboxyl groups on serine to
modify MXene nnokes nd crete nnostructured Ti3C2MXenes/rubber-bsed suprmoleculr
elstomer (NMSE) with outstnding sensing cpbility (Guo et al., 2020).
 32

FIGURE 2.5 () The esteriction rection modies the surfce of MXene nnosheets by dding serine. (b) Using the ltex ssembly method, design  nnostructured
MXene network in NMSE.(Guo et al., 2020)
MXene-Filled Polymer Nanocomposites
Overview of MXene-Based Polymer Nanocomposites 33

2.2.3 MELT BLENDING

In  twin-screw extruder, Go et l. melt blended the polyethene glycol pretreted MXene/thermo-
plstic polyurethne (TPU) nd extensively studied the ller dispersion, mechnicl strength, nd
ller polymer interction using rheologicl nlysis. They hve observed  strong hydrogen bonding
interction between PEG pretreted MXene nd TPU chins, which results from good ller disper-
sion, nd the morphologicl studies show no gglomertion t lower concentrtion of MXene, but t
1 wt%m smll gglomertes re observed; t 0.5 wt% MXene, the tensile strength is incresed upto
41.2% compred to net TPU (Q. Go et al., 2020). Shi et al. (2019) successfully developedultr-thin
2D titnium crbide
(Ti3C2Tx)/PP nnocomposites with high mechnicl strength vi  melt blending technique.
First, the MA-g-PP/Ti3C2Tx nnosheet powder is synthesized by using mechnicl stirring of
MXene powder nd PP ltex with the ssistnce of n oxygen-free fst ertiontctic. Then the
MA-g-PP/Ti3C2Tx nnosheet powder melt blended with the PP grnules to obtin better disper-
sion. The synthesis of the PP/MXene composites is shown in the Figure 2.6, nd the trnsmission
electron microscopy (TEM) imge of the composites shows the interclted nd exfolited lyers of
MXene in the PP mtrix nd the scnning electron microscopy (SEM) imges of surfce frctured
PP/MXene composite, which indicting interfcil solid dhesion with the composite shown in
Figures 2.6bnd 2.6c, respectively. The excellent dispersion nd the hydrogen bond interction with
the PP nd theMA-g-PP/Ti3C2Tx nnosheet powder re responsible for the improved mechnicl
strength. The nnoconnement by the hydrogen bond restricts the mcromoleculr chin movement
nd mechnicl brekge nd improves the mechnicl strength, ductility, nd modulus by 35.3%,
674.6%, nd 102.2%, respectively; Figure 2.6d shows the model of mechnicl filure process (Shi
et al., 2019).

2.2.4 IN SITU POLYMERIZATION

In situ polymeriztion technique is  robust fbriction method in which the smll monomers, nd
the MXene re dispersed together nd llow the polymeriztion of the monomer with pproprite
conditions. Polyniline is  polymer tht hs gined signicnt interest in situ polymeriztion. The
smll molecule niline nd MXene dispersed in HCl re primrily mixed nd polymerized with 
suitble property for  potentil gs sensor mteril (Zho et al., 2019). Ul Hq et l. synthesized
PMMA/MXene/ZnO ternry compound vi in situ bulk polymeriztion technique. Here, the MAX
phse is Ti3C2Tx, which is dded to the methyl methcrylte (MMA) monomer for the in situ bulk
polymeriztion (Ul Hq et al., 2020). The in situ click polymeriztion technique ws explored by
McDniel et l. to synthesize uniformly dispersed in urethne/MXene composites. They creted
nnocomposite smples with  5 wt% ller Ti3C2Tzconcerning monomer nd  polymer mtrix
with 1:1 composition of thiol nd isocynte groups ([SH]/[NCO] = 1). They lso studied the rec-
tions of synthesized MXene with urethne nd prepred the composites. Figure 2.7 represents the
complete synthetic route followed for the preprtion of nnocomposite using urethne (McDniel
et al., 2021)

2.3 PROPERTIES
Due to the 2D structure of the MXene mteril nd its excellent surfce properties with good
conductivity nd mechnicl strength, incorporting this potentil ller into the polymer
mtrix will improve its properties, which shows  prospective clim in energy storge, EMI
shielding, membrne, sensors, nd biomedicl pplictions (Fenget al., 2018; Ci et al., 2020;
Krhn et al., 2020; Li et al., 2020; Zhng et al., 2020, 2021; Zheng et al., 2021; Jy Prksh
nd Kndsubrmnin, 2021; Kim et al., 2021; Kshetri et al., 2021; Rizi, Tghizdeh nd
Soroush, 2021)
 34

FIGURE 2.6 () Preprtion of PP-g/MXene nnocomposites; (b) trnsmission electron microscopic imges of PP-g/MXene nnocomposites 0.5 (, b) nd 2.0
(c, d); (c) SEM imges of  frctured surfce of PP-g/Ti3C2Tx NS-2.0, (d) digrms of the mechnicl filure process models of PP-g/Ti3C2Tx NS-2.0 (Shi et al., 2019).
MXene-Filled Polymer Nanocomposites
 Overview of MXene-Based Polymer Nanocomposites

FIGURE 2.7 MXene thio urethne nnocomposites re mde by (i) covlent functionliztion nd ugmenttion of multilyer Ti3C2Tz sheets vi  rection with
dodecyl isocynte, (ii) dispersion of customized Ti3C2Tz lyers within  tetrfunctionl thiol monomer, nd (iii) in situ polymeriztion nd nnocomposite estblish-
ment vi the ddition of  diisocynte monomer (McDniel et al., 2021).
35
36 MXene-Filled Polymer Nanocomposites

The increse in interfcil contct between the kes nd the surrounding polymer mtrix is
often ttributed to the reinforcing effect on MXene nnocomposites. However, this interction
is rrely dened, nd mteril qulities re often evidence of improved interfcil interctions/
strength. The yield stress of nnocomposites rises when the ller loding of 2D mterils, such s
grphene, MXene, nd lyered silictes, mong others, increses. This yield stress is  result of the
ller’s nd hosts interfcil contct.
The mechnicl strength of  polymer composite is very much crucil in every ppliction.
Ling et al. mdeup the principl MXene/PVA nnocomposite, which improves mechnicl
properties nd conductivity. The high elstic modulus (500 GP) of MXene sheets cn ct s 
sound reinforcement in the polymer mtrix, nd here the strength of the PVA/MXene compos-
ite improved to 91 ± 10 MP. The enhnced mechnicl strength indictes tht effective stress
trnsfer between the MXene lyer, nd the polymer mtrix is tking ction; lso, the interfcil
bonding between the mtrix nd MXene sheets re involved in the improvement in the mechni-
cl strength of these nnocomposites (Ling et al., 2014). Akyiir et al. fbricted  stretchble
mteril with  high electromgnetic shielding effectiveness of 49dB nd elongtion t  brek
of 170 ± 5.6%.
The MXene forms  good dispersion in the NBR mtrix due to the surfce modiction of
MXene with lkylmine nd dispersed vi ltex compounding. The composite shows more bil-
ity to store electricl energy thn the mgnetic signls, so there is  rpid increse in permittivity.
The electromgnetic shielding depends on the conductivity of the mteril here. The shielding
mechnism depends on the bsorption, nd n increse in dielectric loss with the rise in MXene
content is observed (Akyiir et al., 2021). The interfcil dhesion between the MXene nd the
polymer mtrix meliortes mechnicl strength by effective lod trnsfer to the MXene sheets.
The surfce energy nd the hydrophilic functionl groups present of the surfce of MXene
conrm good dhesion in the ller–mtrix interfce. TheMXene/epoxy coting showed high
surfce energy properties, nd the interfcil dhesion is very high, which results in incresed
mechnicl strength (Zukiene et al., 2021). Biocomptibility is  signicnt concern in bio-
medicl pplictions like rticil skin nd pressure sensing pplictions. The hydrogen bond
interction between MXene nd PVA provides  potentilly conductive biomteril for these
pplictions. To monitor the signls, pressure sensors re plced ner the tissue; for exmple,
to observe the gstric peristlsis, the sensor is put to the stomch wll, so in vitro nd in vivo
studies re inevitble, nd Zho et l. fbricted the mteril cn monitor crdic motion lso
gstric peristlsis (Zho et al., 2021).Q. Song et l. constructed very exibleFe3O 4@Ti3C2Tx/
DENR nnocomposites with excellent electric conductivity. Here, the conductive MXene lyers
disply excellent interfcil dhesion with the nturl rubber ltex prticles nd form  segre-
gted network structure tht imprts high mechnicl strength nd conductivity nd  58-dB
shielding efciency (Song et al., 2021). Tble 2.2 shows some of the properties nd pplictions
of MXene/polymer composites.
MXenes’ impermeble feture mkes them idel for incresing the brrier qulities of poly-
mers, preventing gses nd tiny molecules from pssing through. When compred to their
clen polymer equivlents, nnocomposites lled with lyered silictes, nd grphene hve
signicntly enhnced brrier chrcteristics (Crey nd Brsoum, 2021; Tn nd Thoms,
2016; Wng et al., 2018; Choudlkis nd Gotsis, 2009). The improved brrier properties cn
be explined bsed on tortuous pth cretion. As  result of increses in volume frction or
spect rtio of ller, the permebility will be decresed. Liu et l. studied the Ti 2CTz MXene
membrnes for isopropnol wter mixture dehydrtion (Liu et al., 2019), nd Shmsbdi et al.
studied the H 2 , CO2 , CH4 N2 gs permetion usingTi 2CTz/polyurethne/Pebx(copolymer of
polymide nd pole ether). They found good selectivity of CO2/N2 due to the solubility prm-
eter vlues contributed by the functionl group present in MXene sheets (Liu et al., 2020; Yng
et al., 2020).
Overview of MXene-Based Polymer Nanocomposites 37

TABLE 2.2
MXene/Polymer Composites and Their Properties
Sl No Polymer Mxene Properties/Applications References
1 Thermoplstic Ti3C2Tx At n MXene loding vlue of 0.5 wt. (Go et al., 2020)
polyurethne (TPU) %, tensile strength nd elongtion t
brek escltion by 41.2 wt%, nd15.4
wt%, respectively.
2 Polyvinylidene uoride Ti3C2Tx Therml conductivity is0.767 ± 0.034 (Rjvel et al., 2020)
(PVDF) W/mKnd22.55 vol% ller
concentrtion. 48.47 ± 3.5 dB EMI
shielding effectiveness
3 Epoxy Ti3C2Tx The electricl conductivity vlue of 105 (Wng et al., 2019)
S/m nd EMI shielding effectiveness of
41 dB is the idel vlues.
4.32 GP Young’s modulus nd 0.29
GP hrdness
4 Epoxy Ti3C2Tx Increse in young’s modulus (Sliozberg et al., 2020)
5 Poly vinyl lcohol Ti3C2Tx Electricl conductivity of 1.4 × 106 S/m (Tn et al., 2021)
6 Nitrile butdiene rubber Ti3C2Tx Electricl conductivity incresed from (Akyiir et al., 2020)
(NBR) ltex 1.84 × 10−16 S.cm−1 to 9.0 × 10−05 S.cm−1.
7 Nturl rubber ltex Ti3C2Tx Electricl conductivity vlue is6.18 × (Yng et al., 2021)
10−4 S/m
8 Polyurethne Ti3C2Tx PU/MX-0 hs n electricl conductivity (Liu et al., 2020)
of 5983.5 203.6 S cm−1, wheres PU/
MX-20 hs n SSEt of 33771.92 dB
cm2 g−1.
9 TPU Ti3C2Tx-rGO hybrid Excellent Flme retrdnt property (Liu et al., 2020)
10 P(VDF-TrFE-CFE) Ti3C2Tx Improved dielectric constnt (Tu et al., 2018)

2.4 APPLICATIONS
The verstile surfce chemistry of MXene nd its exceptionlly high electricl conductivity,
mechnicl strength, nd therml properties mke MXene n incredibly suitble mteril tht
cn be used in countless pplictions such s sensors, EMI shielding mterils, nd different
pplictions in the biomedicl eld (Chen et al., 2021). High electro-conductivity, extrordinry
sensitivity, short detection limit, truncted hysteresis, nd fst recovery fter repeted usge
re crucil properties for  potentil sensor. The concentrtion of the surfce group present in
the MXene determines the performnce of MXene/polymer composites (Rizi, Tghizdeh nd
Soroush, 2021).
MXene elstomer composites hve potentil use in self-heling exible sensor pplictions.
Guo et al. developed MXene/nturl rubber nnocomposites with excellent self-heling properties.
The serine-modied MXene developed n outstnding conductive network. The surfce nchoring
ssemblies of MXene engge with the serine-grfted epoxidized nturl rubber, forming interfcil
suprmoleculr hydrogen bond interctions. They hve developed  sensor tht cn sense minute
humn physiologicl motions nd externl moisture vritions (Guo et al., 2020). Luo et al. creted
n MXene/nturl rubber composite tht is highly conductive (1400 Sm−1) nd cceptble for EMI
shielding (SE = 53.6 dB). Nturl rubber’s crosslinking improves reproducibility nd stbility, mk-
ing it  vible cndidte for use in foldble electronics (Luo et al., 2019). The ppliction of MXene/
polymer composites, nd the pplictions re tbulted in Tble 2.3.
38 MXene-Filled Polymer Nanocomposites

TABLE 2.3
Application of MXene/Polymer Nanocomposites
Sl. No Mxene/Polymer Nanocomposite Applications References
1 PANI/Ti3C2Tx nnocomposites Gs sensor (Zho et al., 2019)
2 MXene/nturl rubber nnocomposite EMI shielding (Luo et al., 2019)
53.6 dB
6.71 vol%
3 Ti3C2Tx MXene/Epoxy nnocomposites EMI shielding (Wng et al., 2019)
41 dB 15 wt%
4 Serine-modied MXene/Epoxidized Electronic sensor (Guo et al., 2020)
nturl rubber Speech, fcil expression
recognition, nd pulse detection
5 The hydrogel of modied polycrylmide Electronic skin sensors (Ci et al., 2020)
polymer nd MXene-vinyl hybrid silic
nnoprticle
6 Composite of Ti3C2Tx MXene nd PVDF EMI shielding (Rjvel et al., 2020)
polymer At  thickness of 2 mm, 48.47 ± 3.5
dB corresponding to 22.55 vol %
ller quntity
7 MXene/Au/PET nnocomposite Pressure sensor, werble gdget (Go et al., 2020)
For biologicl signl recognition
Flexible piezoresistive sensor
8 Cellulose EMI shielding (Wng et al., 2020)
Nnobers/Ti3C2Tx MXene Aerogels/ 74 dB, 1.38 vol%,
Epoxy Nnocomposites
9 Ti3C2Tx nd P(VDF-TrFE) lm Piezoresistive (Li et al., 2020)
Pressure sensors
10 MXene/polynilineber nnocomposites Ultrsensitive sensing (Cho et al., 2020)
11 MXene/EPDM rubber EMI shielding (Lu et al., 2020)
48 dB 2.7 wt%
12 MXene/PU sensors Werble pressure sensor (Zukiene et al., 2021)
13 PDMS/MXene composite E-skin triboelectric tctile sensor (Ci et al., 2021)

2.5 CONCLUSION
MXene is  verstile lyered mteril tht cn be prepred from selective etching using strong
cids, shows high mechnicl strength nd high electro conductive properties, nd hs potentil
pplictions in electromgnetic interference shielding, biomedicl ppliction, pressure sens-
ing pplictions, nd energy storge pplictions, mong others. But the primry concern nd
difculty in MXene reserch is its production on n industril scle. If it fils in the industril
scle-up of synthesis, the pplicbility will lso be  question mrk, nd its fte will be simi-
lr to grphene. Another foremost concern is its hindrnce to oxidtion; the ongoing reserch
focuses on preventing the oxidtion of MXene sheets. The cost nd vilbility of MXene pow-
ders lso limit its ppliction potentil to  greter extent. It is vitl to nd n lterntive route
for synthesizing the MAX phse mterils without using hzrdous HF cid. While compring
to grphene nd crbon nnotube, the production cost of MAX phse mterils is lmost similr
or slightly lower. One of the chepest nnollers vilble to mke polymer composite is cly.
MXene reserch in the future should focus on reducing the production cost of MXenes, nd if the
price of MXene is lower thn tht of cly, one cn produce mterils with high-end properties in
 low-budget scheme.
Overview of MXene-Based Polymer Nanocomposites 39

We expect tht s the plying ren of MXene polymer nnocomposites progresses nd  count-
less emphsis is plced on sclble mnufcturing pproches, the expnsions will contribute the
wys nd mens of mking the MXene-bsed reserch nd development more vibrnt.

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Yng, K. et al. (2020) ‘Trizine-bsed two-dimensionl orgnic polymer for selective NO2 sensing with
excellent performnce’, ACS Applied Materials and Interfaces, 12(3), pp. 3919–3927. doi: 10.1021/
csmi.9b17450.
Yng, Y. D. et al. (2021) ‘Nturl rubber ltex/MXene fom with robust nd multifunctionl properties’,
E-Polymers, 21(1), pp. 179–185. doi: 10.1515/epoly-2021-0017.
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 3 Processing, Morphology,
Mechanical, and Electrical
Properties, and Applications
of Thermoplastic Polymer/
MXenes Nanocomposites
Pallishree Sahoo, Lipsa Shubhadarshinee,
Pooja Mohapatra, Patitapaban Mohanty, Bigyan Ranjan Jali,
Priyaranjan Mohapatra, and Aruna Kumar Barick

CONTENTS
3.1 Introduction ............................................................................................................................. 43
3.2 Thermoplstic Polymer/MXene Nnocomposites .................................................................. 45
3.2.1 Processing of Thermoplstic Polymer/MXene Nnocomposites................................ 46
3.2.1.1 Solution Blending ........................................................................................ 46
3.2.1.2 In Situ Method.............................................................................................. 47
3.2.1.3 Melt Blending .............................................................................................. 48
3.2.2 Chrcteriztion of Thermoplstic Polymer/MXene Nnocomposites....................... 48
3.2.3 Properties of Thermoplstic Polymer/MXene Nnocomposites................................. 51
3.2.3.1 Mechnicl Properties of Thermoplstic Polymer/MXene
Nnocomposites........................................................................................... 51
3.2.3.2 Electricl Properties of Thermoplstic Polymer/MXene
Nnocomposites........................................................................................... 54
3.2.4 Appliction of Thermoplstic Polymer/MXene Nnocomposites .............................. 55
3.2.4.1 Sensing Applictions.................................................................................... 55
3.2.4.2 Biomedicl Applictions.............................................................................. 56
3.2.4.3 Energy Storge Applictions........................................................................ 56
3.2.4.4 Electromgnetic Interference Shielding nd Absorption Applictions........ 57
3.2.4.5 Filtrtion Applictions ................................................................................. 58
3.2.4.6 Other Applictions ....................................................................................... 58
3.3 Future Perspectives nd Chllenges........................................................................................ 58
References........................................................................................................................................ 59

3.1 INTRODUCTION
Owing to the excellent exfolition of grphene nd its superior properties, two-dimensionl (2D)
nnomterils hve ttrcted  wide ttention for interdisciplinry reserch in science nd engineer-
ing s compred to the 3D nnomterils [1]. These mterils re  big fmily, including elementl
substnces (e.g., grphene, silicene, borophene, nd blck phosphorus) nd compounds (e.g., trnsi-
tion metl suldes, trnsition metl oxides, lyered double hydroxide [LDH], nd MXene) [2,3].

DOI: 10.1201/9781003164975-3 43
44 MXene-Filled Polymer Nanocomposites

Recently, novel types of 2D nnomterils, nmely, “MXenes,” hve been surfced nd produced
immense interest in the reserch community becuse of their unique nnostructured morphology
nd electronic fetures tht brodening their exercise in vrious promising pplictions. MXenes
re rst discovered by the Gogotsi nd Brsoum groups in 2011 [4]. They re n exceptionl clss of
hydrophilic, electriclly conducting 2D nnomterils, nd rchitecturlly, they re 2D nnosheets
of trnsition metl (Ti, V, Cr, Nb, etc.) crbides, nitrides, or crbonitrides [5–8]. MXenes re
obtined by selectively chemicl etching of the lyers of s- nd p-block elements (Al, Si, Sn, In,
etc.) from their equivlent 3D MAX phses consist of lyered ternry metl crbides, nitrides, nd
crbonitrides with  typicl chemicl composition of Mn+1AXn(n: 1, 2, 3, 4), where M, A, nd X
symbolize d-block trnsition metls (such s Mo, Ti, Zr, Cr, etc.), min-group s- nd p-block ele-
ments (minly IIIA/IVA), nd either C/N or both C nd N toms, respectively. More thn 70 kinds
of MAX phses hve been reported in literture [9,10]; however, the well-known MXene forms only
involved Ti3C2, Ti2C, (Ti0.5, Nb0.5)2C, (V0.5, Cr0.5)3C2, Ti3CN, T4C3 [11], Nb2C, V2C [12], nd Nb4C3
stoichiometric compositions [13]. Prticulrly, the exterior surfces of the dispersed single sheets
re usully functionlized with uoride (–F), hydroxyl (–OH), nd –O– polr functionl groups t
the time of chemicl etching tretments.
MXenes hve ttrcted tremendous ttention from reserchers due to their both outstnding
physicl nd chemicl properties [7], electricl conductivity [14], hydrophilicity, nd exible sur-
fce chemistry [15,16]. These properties mke MXene  potentil mteril for utilized for electrodes
in energy storge devices [17,18], electrochemicl supercpcitors [19,20], ctlytic promoters
[21,22], bsorbents for hevy metl ions, mterils for the photodegrdtion of dyes [23], biosensors
[24,25], nd nti-biofouling membrnes [26,27]. Among the synthetic mterils, MXene hs shown
the highest level of electromgnetic shielding (92 dB of electromgnetic interference [EMI] shield-
ing effectiveness [SE]) nd hs fr surpssed tht of silver nd copper [28] nd higher chrge storge
cpbility compred to grphene supercpcitors [29].
Vrious MXene-bsed polymer nnocomposites hve been investigted becuse of their supe-
rior physicl properties like mechnicl strength, electricl conductivity, nd therml conductivity.
Until now,  number of review rticles hve been published regrding recent dvnces of MXenes
covering their synthesis nd modictions together with preprtion, properties nd ppliction of
polymer/MXene nnocomposites [30–40]. Jimmy nd Kndsubrmnin presented severl poly-
mer nnocomposites of MXene with  focus on their fbriction methods nd future pplictions
[30]. Go et al. discussed the synthesis nd properties of the MXenes nd polymer/MXene nno-
composite membrnes together with promising pplictions in vrious res like ltrtion, EMI
shielding, energy storge nd conversion devices, werble devices, nd so on. [31]. Chen et al.
reviewed the clssiction, preprtion methods, performnce, nd pplictions such s biomedicl,
sensing, energy storge, conversion, nd supply, electromgnetic bsorption nd shielding, ctly-
sis, chemisorption, sewge puriction, me retrdnce, seprtion membrnes, nd other res
of polymer/MXene nnocomposites [32]. George nd Kndsubrmnin deliberted the exciting
potentil biomedicl pplictions speciclly ntibcteril ctivity, phototherml cncer therpy,
drug delivery, bioimging, biosensing, nd bone regenertion of polymer/MXene nnocomposites
[33]. Aghmohmmdi et al. ssessed the mechnicl, tribologicl, therml, corrosion, nd electri-
cl properties of both thermoset nd thermoplstic polymer/MXene nnocomposites [34]. Recently,
He et al., Gong et al., nd Kusr reviewed the preprtion, properties, nd ppliction of polymer/
MXene nnocomposites [35–37]. Crey nd Brsoum pprised the production methods nd prop-
erties prticulrly conductivity, mechnicl behvior, interfcil strength, gs permebility, nd the
dimensionl nd therml stbility of polymer/MXene nnocomposites [38]. Rizi et al. investigted
the reported dvnced pplictions of polymer/MXene nnocomposites [39]. Song et al. evluted
the fbriction nd progress of polymer/MXene nnocomposites for EMI shielding pplictions
[40]. Nevertheless,  lrge number of rticles re published on the polymer/MXene nnocomposites,
the reserch dvnces re even in the initil stges nd emerging performnces need to be elbo-
rtely investigted for ultimte pplictions.
Processing, Morphology, Mechanical, and Electrical Properties 45

Severl uthors hve reported tht the mechnicl, therml, nd electricl properties of polymer/
MXene nnocomposites noticebly increse with MXene loding. Feng et al. synthesized MXene-
bsed polyvinylidene uoride (PVDF) nnocomposites nd demonstrted enhnced electricl prop-
erties, such s the permittivity, AC conductivity, nd brekdown strength of bout 26 t 100 Hz,
10 −11 Scm−1, nd pproximtely 350 MVm−1 t 100 Hz, respectively [41]. PVDF/MXene nnocom-
posites showed n pproximtely one fold improvement in therml conductivity in comprison with
the pristine PVDF, ttended by  prominent improvement in the dynmic mechnicl properties of
the PVDF, for exmple, incresed storge modulus, nd shifting of the glss trnsition temperture
(Tg) towrd higher temperture t higher MXene loding [42]. Ling et al. prepred MXene-bsed
polyvinyl lcohol (PVA) nnocomposite tht could support 15,000 times its own weight [43]. Boot
et al. dded 8 wt.% polypyrrole (PPy) to MXene nd found tht the volumetric cpcitnce density
ws of 1000 Fcm−3, which is twice tht of the only MXene electrode [44], nd by dding 0.15 wt.%
MXene, Xu et al. reched 28 dB of EMI SE in  wve trnsprent PVA mtrix [45]. The mechni-
cl properties of ultr-high moleculr weight polyethylene (UHMWPE)/MXene nnocomposites
exhibited better mechnicl properties, especilly the surfce hrdness nd creep behvior [46].
PVA/MXene nnocomposite nnobers with low Ti3C2Tx (0.14 wt%) loding exhibited  DC con-
ductivity of 0.8 ×10 −3 Scm−1 [47].
The min objective of the recent book chpter dels with the processing, chrcteriztion,
properties, nd ppliction of thermoplstic polymer/MXene nnocomposites. The processing of
thermoplstic polymer/MXene nnocomposites using solution blending, in situ method, nd melt
mixing re discussed, long with  description of the synthesized mterils by mens of different
chrcteriztion techniques. In ddition, the mechnicl nd electricl properties of the fbricted
mterils re highlighted with  depiction of different pplictions such s sensing, biomedicl,
energy storge, EMI shielding, ltrtion, nd other elds to review the sttus of the thermoplstic
polymer/MXene nnocomposites. Finlly, this book chpter illustrtes the chllenges confronted
by thermoplstic polymer/MXene nnocomposites nd their future spects, which is importnt for
further reserch nd development of thermoplstic polymer/MXene nnocomposites with outstnd-
ing mteril properties.

3.2 THERMOPLASTIC POLYMER/MXene NANOCOMPOSITES

Nnomterils, such s nnoclys nd vrious 2D nnomterils, disply more benets in com-
prison with their 3D counterprts owing to their exceptionlly lrge specic surfce re nd
spect rtios. The mteril performnces such s mechnicl, electricl, therml, rheologicl, nd
brrier properties cn be substntilly improved by incorporting smll mount of nnollers t 
concentrtion less thn 2 wt% owing to the homogeneous dispersion of MXene nnosheets within
the polymer mtrix [48]. Excellent nnomterils cn extend noticeble improvements in electricl
conductivity, ctlytic ctivity, nd sensing behvior. Reported polymer/MXene nnocomposites
re typiclly mde up of lled composites nd complexes. The single-lyered MXenes exhibit more
vilble hydrophilic surfces nd superior comptibility with vrious polymers s compred to
the multilyered MXenes. Hence, MXenes re normlly delminted tht cn be esily dispersed
within the polymer mtrix. Prticulrly, polymer/MXene complex re clssied into lminted com-
posite nd structure [49–51], MXene-coted polymeric ber or fbric composite [52,53], polymer/
MXene composite ber or fbric [54–56], nd polymer/MXene composite erogel, fom, or sponge
[45,57,58]. The most studied re the lled composites, tht is, thermoplstic [43,46,59,60] nd ther-
mosetting polymer [61,62] mtrix, compred to the complexes. For exmple,  spin-coted MXene
dispersed onto polycprolctone (PCL) electrospun ber membrnes, which is  lyered composite
structure ws reported by Zhou et al. [63]. The rst-ever MXene-lled polymer nnocomposites
ws published in 2014 in which the Ti3C2Tx MXenes were incorported into the hydrophilic polyd-
illyl dimethyl mmonium chloride (PDDA) nd PVA [43]. Different polymer/MXene nnocom-
posites re studied, which consist of hydrophilic polymers like PVA [43, 64–66], polycrylic cid
46 MXene-Filled Polymer Nanocomposites

(PAA) [67,68], nd biopolymers [69,70], long with hydrophobic polymers like polyethylene (PE)
[71], polyethylene oxide (PEO) [72], polypropylene (PP) [73], polystyrene (PS) [74], polymide (PA)
[75], nd epoxies [76], mong others. However, current literture focuses on the conductive poly-
mers such s polyniline (PANI) [77,78], polyvinyl pyrrolidone (PVP) [79,80], polypyrrole (PPy)
[81], poly3,4-ethylenedioxy thiophene (PEDOT) [82], polystyrene sulfonte (PSS) [83], polyvinyli-
dene diuoride (PVDF) [84], nd polyvinylidene uoride–triuoroethylene (PVDF-TrFE) [85], nd
others.

3.2.1 PROCESSING OF THERMOPLASTIC POLYMER/MXENE NANOCOMPOSITES

Polymer/MXene nnocomposites or complexes cn be synthesized by using vrious methods, such
s solution blending, melt blending, dry mixing/therml pressing, emulsion mixing, in situ polym-
eriztion, ultrsonic mixing, nd lmintion stcking. Mostly MXene is prepred by solutions
consisting of uoride; the resulting MXene possess –F, –OH, nd –O-terminted polr functionl
groups on its surfce tht provide good hydrophilicity, but dried MXene hs poor hydrophilicity,
nd redispersion is lso difcult [86]. Solution blending is the most widely used technology for the
preprtion of polymer/MXene composite. Usully, wter is the most frequently used, nd in some
cses, polr solvents could lso be used.

3.2.1.1 Solution Blending

Solution blending tkes dvntge of the excellent hydrophilicity of MXene nd is esy to oper-
te. It exibly modultes the rtio of the components in the composites. In this method, rst the
dispersion of MXene nd hydrophilic polymer mtrix re crried out in  suitble common solvent
in seprte continers [87,88]. Then, both the solutions re blended together followed by evpor-
tion to remove the solvents. Generlly, this method is suitble for polymer either soluble in wter
or orgnic solvents such s PVA [89], polyvinyl chloride (PVC) [90], polyurethne (PU) [91], PEO
[92], polyuorene (PFS) [93], polycrylmide (PAM) [94], PVDF [42], polycryltes [95], cellulose
[96], chitosn (CS) [97], polylctic cid (PLA) [98], etc. To disperse MXene, the suitble polr
dispersnt used re N,N-dimethyl formmide (DMF) [42], wter [45], dimethylsulfoxide (DMSO)
[99] or dimethylcetmide (DMAc) [100]. The MXene nd polymer cn be mixed in the sme
dispersnt becuse the dispersnt cn lso dissolve the polymer s well. Solution blending could
lso be crried out in different dispersnts, but these dispersnts need to be mutully soluble. Ling
et al. hve explored the preprtion of  single-lyer MXene-bsed PVA nnocomposite by blend-
ing the queous solution of MXenes nd PVA [43]. For instnce, Nguib et al. dispersed MXene
with DMSO nd dissolved PAM with wter nd then mixed the two mixtures or solutions to obtin
the corresponding PAM/MXene nnocomposites [94]. At the moleculr level, solution blending
cnnot chieve  true dispersion of MXene nd polymer mtrix, which is minly shown in the
cse of wekly polr or nonpolr polymers. Therefore, some surfce modiction ws dopted
to enhnce the dispersibility of MXene in dispersnts, further incresing its uniform distribution
throughout the polymer mtrix. Before the fbriction of Ti3C2Tx-bsed UHMWPE nnocompos-
ites, rst the surfce modiction of MXenes is crried out. The surfce modiction cn enhnce
the comptibility nd dispersibility of Ti3C2Tx in  UHMWPE mtrix. Si et al. modied the sur-
fce of Ti3C2using long-chin ctionic bromide, which improved its dispersibility in DMF, thereby
improving the dispersion of Ti3C2 in PS [101]. However, Yu et al. used cetyl trimethyl mmonium
bromide (CTAB) to modify the surfce of Ti3C2 nd, thus, improve the dispersion of Ti3C2 in TPU
mtrix [91]. Figure 3.1 shows the procedure for the synthesis of the PVC/MXene nnocomposites
using  solution blending technique [90]. Some disdvntges such s substntil wste, difculty
of evporting the solvent, environmentl pollution, esy wrinkling during lm csting, poor t-
ness, nd insufcient mechnicl strength in lms re produced by solution blending, which hinder
the prcticl ppliction of this method.
Processing, Morphology, Mechanical, and Electrical Properties 47

FIGURE 3.1 Schemtic representtion of solution blending technique for synthesis of PVC/MXene
nnocomposites.

3.2.1.2 In Situ Method

The in situ method refers to the mixing of MXene nnosheets with smll molecules, such s mono-
mers, inititors, or curing gents, in presence of  ller, nd then smll molecules re in situ polym-
erized into mcromolecules. Consequently, MXene is well distributed in the polymer hosts. The
blending cn signicntly enhnce the homogeneous distribution of MXene nnosheets within
the polymer mtrix. In this method, the polymer moleculr chins re originted on the surfces
of the MXene nnosheets, which is n dvntgeous spect for lyered nnomterils becuse
the intercltion of monomers into nnolyers followed by  polymeriztion procedure to crete
enlrgement nd delmintion into individul nnolyers. This type of blending is widely used to
produce MXene-contined polymer nnocomposites, in the composites the polymers re thermo-
setting polymers contining cyclic or heterocyclic units, or liner mcromolecules, which cn be
polymerized in mild conditions [75,102,103]. Epoxides, polydimethyl siloxne (PDMS), PPy, PANI,
polydopmine (PDA), PAM, PAM/PVA, PEDOT, nd further complex cyclopolymers cn lso
be synthesized by in situ for prepring polymer/MXene nnocomposites to be used s electrodes,
ctlysis, shielding functionl mterils, nd other purposes. Qin et al. successfully obtined PPy/
MXene nnocomposites with 3D porous nnostructure vi in situ electrodeposition method in pyr-
role nd MXene mixes [104]. Wng et al. synthesized PDA/Ti3C2Tx composite lm electrodes by
single-step in situ technique [105]. Boot et al. nd Tong et al. prepred PPy/Ti3C2Tx composites
by in situ polymeriztion s shown in Figure 3.2 [44,106]. All the previously mentioned pproches
del with the utiliztion of different solvents, while Crey et al. described the in situ bulk polymer-
iztion of polycprolctm (ε-PCL) under inert conditions [75]. Here, 12-minoluric cid nd mul-
tilyer Ti3C2Tx were interclted with the ε-cprolctm monomer, which leds to the ring-opening
polymeriztion of ε-cprolctm to prepre melt-blended nnocomposites, with 94% decrese in
wter vpor permebility. Liner polymers cpble of being polymerized under mild conditions,
such s crylic monomers, olenic monomers, polyesters, nd polymide precursor monomers, cn
lso be polymerized in situ to prepre the corresponding nnocomposites.
48 MXene-Filled Polymer Nanocomposites

FIGURE 3.2 Schemtic representtion of in situ polymeriztion technique for synthesis of PPy/MXene
nnocomposites.

3.2.1.3 Melt Blending

As compred to solution blending or in situ polymeriztion, which utilize  lrge mount of orgnic
solvent, melt blending is considered more exible for formultion, more economicl, nd more envi-
ronmentlly friendly. In this method, MXene dded to the thermoplstic polymer mtrix is usully
done in the molten condition. This method includes extrusion, hot pressing, nd injection molding
of the polymer/MXene nnocomposites for uniform dispersion nd directionl orienttion of the
MXenes nnosheets within the polymer mtrix. This method is especilly ppeling for industril
mnufcturing of polymer/MXene nnocomposites for developing end-use products. MXenes cn
be esily supplied into the vrious methods of melt blending due to the stisfctorily high density
of the MXenes of bout 4.26 g/cm3 [107] but only restricted to the thermoplstic polymers bove
the melting point. However, the melt processing needs to be crefully crried out t higher temper-
tures; otherwise, both polymers nd MXenes undergo oxidtive therml degrdtion. Melt blending
is discussed in the literture with regrd to the fbriction of MXene-reinforced nonpolr thermo-
plstic polymers such s PP, UHMWPE [46], PS [73], PCL [67], liner low-density polyethylene
(LLDPE) [71,108], nd TPU [109,110]. The stepwise synthesis of melt blending of TPU/MXene
composites is shown in Figure 3.3[110].

3.2.2 CHARACTERIZATION OF THERMOPLASTIC POLYMER/MXENE NANOCOMPOSITES

Tn et al. studied the Fourier trnsform infrred (FTIR) spectroscopy of net PVA nd PVA/MXene
nnocomposites. The FTIR spectr of pure PVA nd PVA/MXene nnocomposite with vrious con-
centrtion of MXene illustrtes lmost the sme peks, nd no new peks re observed s  result
of the physicl interctions existing between PVA nd MXene nnosheets [111].
Figure 3.4 shows the scnning electron microscopy (SEM) morphology of the net UHMWPE
nd UHMWPE/MXene nnocomposites, which displys severl MXene nnosheets with lmellr
Processing, Morphology, Mechanical, and Electrical Properties 49

FIGURE 3.3 Schemtic representtion of melt blending for synthesis of TPU/MXene nnocomposites.

FIGURE 3.4 SEM microphotogrphs of the frctured surfce of the UHMWPE/MXene nnocomposites:
(a) 0, (b) 0.25, (c) 0.5, (d) 0.75, (e) 1, nd (f) 2 wt.% of MXene lodings t 300 nd 50 μm resolutions.
50 MXene-Filled Polymer Nanocomposites

structures nlogous to grphitic lyers or lyered silicte clys. The SEM surfce shows the growth
of spherulite structures of round 150–200 μm sizes with MXene t the nucleus. At higher loding
of MXene, the cretion of spherulites re more distinct becuse MXene cts s  nucletion center
for UHMWPE to develop numerous mount of spherulites [30,46].
Lu et al. reported cross-sectionl SEM microgrphs of the pristine TPU nd TPU/MXene nno-
composites. The pristine TPU displys  smooth nd uniform surfce morphology. The surfce
roughness of the TPU/MXene composites grdully improved with n increse in MXene concen-
trtion, which reveled n effective encompssing of the MXene nnosheets by the TPU mtrix
tht developed nlogic-segregted microstructures [112]. Moreover, the energy dispersive X-ry
(EDX) spectroscopy for element mpping of O, Ti, N, nd S distributions of MXene nnosheets
within TPU phse in the designted re of the SEM imge reveled tht the MXene nnosheets re
uniformly dispersed within the TPU mtrix, conrming the commencement of the interconnected
conductive network microstructures.
Figure 3.5 shows the SEM nd trnsmission electron microscopy (TEM) morphology of the
pristine PVDF nd PVDF/MXene nnocomposites. The microstructure of the cryo-frctured sur-
fce of the net PVDF exhibits  smooth surfce (Figure 3.5), wheres the surfce roughness of
the CTAB-modied MXene-bsed PVDF nnocomposites increses with increse in MXene lod-
ing s shown in Figure 3.5b–d, which informs the strong interfcil dhesion mong MXene nd
PVDF mtrix. The TEM imges illustrte  little lyer of the MXene nnosheets, which re homo-
geneously dispersed in the PVDF mtrix s displyed in Figure 3.5e–h. At  higher MXene lod-
ing, few gglomertions re observed tht implying the origintion of the interconnected network
structure [113].
Figure 3.6 shows the nnostructure morphology of pristine TPU nd TPU/MXene nnocompos-
ites using both SEM nd TEM. Figures 3.6 nd 3.6b show the SEM microgrphs of cryo-frctured
surfce of net TPU nd 1.0 wt.% MXene-bsed TPU composites, respectively. Figure 3.6b show
the distribution of the few lyers of MXene nnosheets within the TPU mtrix, which re well
coted with TPU mtrix, leding to the conclusion tht the strong interphse interction exists
mong the O nd OH groups on the surfce of the MXene, with  polr functionl group present on
the moleculr bckbone chin of the TPU mtrix [110]. Figure 3.6c–f represent the low-nd high-
resolution TEM imges of 1.0 wt.% MXene-loded TPU composites. The low-mgniction TEM
imge s shown in Figure 3.6c shows the blck spots corresponds to the MXene nnolyers, which

FIGURE 3.5 SEM imges of cryo-frctured surfce of PVDF/MXene nnocomposites: (a) 0, (b) 3, (c) 7, nd
(d) 10 wt.% of MXene lodings nd TEM microphotogrphs of PVDF/MXene nnocomposites: (e) 3, (f) 5, (g)
7, nd (h) 10 wt.% of MXene lodings.
Processing, Morphology, Mechanical, and Electrical Properties 51

FIGURE 3.6 SEM microgrphs of (a) net TPU nd (b) 1 wt.% MXene bsed TPU nnocomposites, nd
(c–f) TEM microgrphs of 1 wt.% MXene bsed TPU nnocomposites.

re homogeneously dispersed throughout the TPU mtrix without ny lrge ggregtion. The inter-
lyer spcing of the MXene nnosheets is bout 2.0 nm s observed from Figure 3.6f.
Figure 3.7 represents the polrized light microscope (PLM) photogrphs of net PEO nd PEO/
MXene nnocomposites. The spherulites formed in PEO nd 1 wt% MXene-bsed PEO nnocom-
posite re distinct nd lrge in size wheres the size of the spherulites signicntly decreses with
n increse in MXene contents due to the improvement in the number of nucletion sites [92].

3.2.3 PROPERTIES OF THERMOPLASTIC POLYMER/MXENE NANOCOMPOSITES

3.2.3.1 Mechanical Properties of Thermoplastic Polymer/MXene Nanocomposites
The mechnicl properties of the MXenes were theoreticlly evluted by considering the thick-
ness, surfce termintion, nd composite effects through DFT [114,115] nd MDs [116]. Figure 3.8
represents the moleculr congurtions of Ti2C, Ti3C2, nd Ti4C3 MXenes fter equilibrium t 300
K. From Figure 3.8b, the in plne elstic modulus of Ti2C, Ti3C2, nd Ti4C3 MXenes re clculted
s 597, 502, nd 534 GP, respectively, using moleculr dynmics, which is noticebly higher thn
tht of the grphene [116,31]. Moreover, the MXenes re inorgnic llers with good rigidity [114]
nd exurl properties [117].
52 MXene-Filled Polymer Nanocomposites

FIGURE 3.7 PLM imges of PEO/MXene nnocomposites: (a) 0, (b) 1, (c) 2, (d) 3, nd (e) 4 wt.% of MXene
lodings.

FIGURE 3.8 Modelling of mechnicl behviour of MXenes using DFT: (a) orgniztions of the different
MXenes fter equilibrtion t room temperture nd (b) typicl stress-strin curves of MXenes computed vi
MDs.
Processing, Morphology, Mechanical, and Electrical Properties 53

Some polymers hving polr functionl groups strongly interct with the MXenes becuse of the
existence of terminl groups on the surfce of MXenes. Consequently, the mechnicl behviors
such s yield strength, elstic modulus, ultimte tensile strength, elongtion t brek, nd hrd-
ness of the polymer mtrix might be enhnced signicntly. Ling et al. reported tht the MXene
nnosheets rolled with 10 wt% PVA cn withstnd bout 15,000 times thn the individul mss
[43]. Hu et al. hve shown tht the mechnicl properties of the MXene nnolms substntilly
improved by the incorportion of 14 wt% chitosn [97]. Zhi et al. reported tht the incorportion of
MXene into the PU mtrix improved the yield stress, hrdness, nd tensile strength by70%, 13%,
nd 20%, respectively, t 0.5 wt% MXene loding [118]. Sheng et al. reported tht the mechnicl
strength nd modulus of the 0.5 wt.% Ti3C2 MXene-bsed TPU were enhnced by 47.1% nd 39.8%,
respectively, in comprison with the net TPU due to the homogeneous dispersion of the MXene in
the TPU mtrix long with strong chemicl interctions mong MXene nd TPU moleculr chins
[110]. Zhng et al. reported tht the tensile strength nd modulus of UHMWPE were enhnced by
the incorportion of Ti3C2 MXene. The ultimte tensile strength of the nnocomposite is incresed
by 8.6% with ddition of 0.75 wt% Ti3C2 s shown in Figure 3.9. The mechnism for the trnsfer of
stress from UHMWPE to Ti3C2 MXene is displyed in Figure 3.9b, which cts s  vitl fctor for
enhncement of the mechnicl properties [46]. Liu et al. shown tht the Young’s modulus of Non
lm is improved bout 23% by the ddition of 2 wt.% of Ti3C2Tx MXene [119]. Yi et al. developed
0.5 wt% steric cid–modied Ti3C2Tx-bsed PLA nnocomposites with 131.6% improvement in

FIGURE 3.9 (a) Stress-strin curves for Ti3C2 MXene bsed UHMWPE nnocomposites with different
MXene loding nd (b) schemtic representtion of the mechnism for enhncement of the mechnicl
properties.
54 MXene-Filled Polymer Nanocomposites

the elongtion t brek in comprison with the pristine PLA mtrix [98]. Zhng et al. chieved tht
the incorportion of 0.3 wt% MXene into PMMA mtrix improves the tensile strength nd modulus
of 89% nd 397%, respectively [120]. Go et al. hve elborted the vrious prmeters of mechni-
cl properties of different kinds of MXene-bsed polymer nnocomposites in tbulr form [31].

3.2.3.2 Electrical Properties of Thermoplastic Polymer/MXene Nanocomposites

MXene shows excellent electricl conductivity (σ) of 9880 S/cm equl to tht of grphene [121,122]
nd the conductivity were pprecibly improved by the incorportion of MXene into the polymer
mtrices, which cn be employed for electromgnetic interference shielding, stretchble strin sen-
sors, humidity nd voltile orgnic compounds (VOCs) sensors long with energy storge devices
[38]. Myerberger et al. obtined tht the electricl conductivity of PEO/Ti3C2Tx nnocomposites
ws enhnced by bout 73.6% thn tht of pristine PEO [68]. Ling et al. observed tht the conduc-
tivity of the PVA/MXene nnocomposites signicntly increses with n increse in Ti3C2 loding
[43]. Sobolčik et l. studied the frequency dependence of the dc conductivity of MXene-bsed
PVA nnobers [47]. Nguib et al. synthesized Ti3C2Tx MXene bsed PAM nnocomposites with
signicnt improvement in electricl conductivity s shown in Figure 3.10 [94]. Sun et al. syn-
thesized highly conducting PS/MXene nnocomposites with  percoltion limit of 0.26 vol.% nd
conductivity of 1081 S/m [123]. Xu et l. prepred conductive PP/MXene nnocomposites with low
percoltion limit s represented in Figure 3.10b [124].

FIGURE 3.10 Vrition of conductivity of (a) PAM nd (b) PP nnocomposites with MXene loding.
Processing, Morphology, Mechanical, and Electrical Properties 55

Tu et al. perceived tht the dielectric permittivity of the polyvinylidene uoridetriuoro-ethyl-

ene-chlorouoroethylene (PVDF-TrFE-CFE) ws signicntly improved by the ddition of MXene
with  percoltion limit of 15 wt% [125]. In ddition, Mirkhni et al. exmined tht the dielec-
tric constnt of PVA/MXene nnocomposites prepred by vcuum-ssisted ltrtion is noticebly
higher in comprison with the solution csting methods [126].
Liu et al. reported tht the proton conductivity of the Non/MXene nnocomposites is incresed
due to improvement in proton trnsporttions by the incorportion of the MXene [119]. Fei et al.
noted tht the proton conductivity of the polybenzimidzole (PBI) is improved twofold in presence
of the MXene [100]. The proton conductivity of the polymer/MXene nnocomposites is effectively
improved due to the formtion of long-rnge interconnected routes nd enrichment of polr func-
tionl groups resulted from the interfcil interctions between the polymer mtrix nd MXene,
which provides  lrge proton trnsfer rte nd rpid mobility of protons with low resistnce.

3.2.4 APPLICATION OF THERMOPLASTIC POLYMER/MXENE NANOCOMPOSITES

3.2.4.1 Sensing Applications
MXene is  suitble mteril for  brod rnge of highly sensitive nd highly selective sensor
pplictions [127–129] becuse of its superior conductivity [121,122,130], low bndgp [2], esy
chemicl modiction [131], nd rich ctive sites [132]. The polymer/MXene nnocomposites cn
be employed for both chemicl (humidity [50,133,134] nd VOCs [135]) nd mechnicl (strin
[50,136] nd pressure [58,129,137–140) sensors due to the effective synergistic effect imprted by
high exibility of the polymer nd good sensing chrcteristics of the MXene. Kim et al. developed
PAM/MXene sensor with improved liner nd humidity sensing ctivities t both low nd high
humidity concentrtion [133]. Sjid et al. prepred PVA/MXene nnocomposites with humidity-
sensing behvior [134]. An et al. described the ultr-fst humidity-sensing recovery nd repetbil-
ity of MXene bsed polydillyl dimethyl mmonium chloride (PDAC) nnocomposites [50]. Wng
et al. fbricted  moisture sensor from PVA/MXene nnocomposites with response nd recovery
time of 0.9 nd 6.3s, respectively [141].
Yun et al. studied VOCs’ sensing behvior of MXene-bsed PVA/polyethylene imine (PEI)
nnocomposites. It exhibits low response nd recovery times to detect different VOCs t concentr-
tions rnging from prts per billion (ppb) to sturted levels becuse of the chemicl dsorption of
polr gses on the surfce of the MXene through hydrogen bonding tht is further supported by
the lrge specic surfce re of the highly porous PVA/PEI mtrix [135]. Wng et al. developed 
PANI/MXene nnocomposites bsed self-powered NH3 gs sensor in rel-time monitoring of the
NH3 concentrtion [142].
Shi et al. fbricted  bionic strin sensor with good sensitivity, high dynmic durbility, nd
huge deformtion from MXene-bsed PDA nnocomposites [136]. Yng et al. creted n elstic
strin sensor of MXene-bsed PU nnocomposite with excellent sensing rnge nd ultr-sensitivity
[139]. Zhng et al. reported  strin sensor of PVA/MXene nnocomposite hydrogel [60]. Cho
et al. synthesized PANI/MXene nnocomposites bsed stretchble strin sensor with sensing rnge
of 80% strin, sensitivity of 2369.1 for guge fctor, nd detection limit of 0.1538% strin to monitor
movements [143].
Guo et al. formed MXene bsed PLA nnocomposites with werble pressure sensing proper-
ties of 11- nd 25-ms response nd recovery time, respectively. The PLA/MXene nnocomposites
exhibit relible response fter 1000 compression cycles with  smll detection limit, low power
utiliztion, high sensitivity, nd bord detection rnge [129]. Hu et al. developed  werble pressure
sensor by using CS/MXene nnocomposite erogels [137]. Li et al. constructed n excellent pres-
sure sensor using PU/MXene nnocomposite fom [58]. Li et al. developed MXene-bsed PVDF-
TrFE nnocomposites s  highly sensitive piezoresistive pressure sensor with response time of
16 ms [85]. Wng et al. lso reported PVDF-TrFE/MXene nnocomposites with superior liner
pressure sensors to detect the regulr ctions of  humn [144]. Zho et al. represented  very
56 MXene-Filled Polymer Nanocomposites

sensitive piezoelectricsensor bsed on PVDF/MXene nnocomposites with  high voltge sensitiv-

ity of 0.0480 V/N,  low recovery time of 3.1 ms, nd  good stbility of 10,000 s [145].

3.2.4.2 Biomedical Applications

Polymer/MXene nnocomposites cn be suitble for vrious biomedicl pplictions, such s drug
delivery, ntimicrobil ctivity, nticncer therpy, biosensing, bioimging, nd bone regenertion
due to their good phototherml conversion efciency (PCE), high selectivity, nd fst stimuli sen-
sitivity to tumor cells, electron sensitivity, higher ntibcteril properties, unique surfce rectivity,
excellent hydrophilicity, good biocomptibility, nd remrkble electricl nd opticl properties
[33]. Rsool et al. illustrted tht the PVDF/MXene nnocomposites membrne exhibit remrkble
ntibcteril ction to both grm-positive B. subtilis nd grm-negtive E. coli bcteril strins nd
growth inhibition of 73% nd 67%, respectively, long with  drstic fll in cell vibility of the bc-
teri in comprison with the pristine PVDF [146]. Myerberg et al. demonstrted the ntibcteril
behvior of the CS/MXene nnocomposites to grm-positive S. aureus nd grm-negtive E. coli
bcteri hving growth reduction of 62% nd 95%, respectively [54].
Lin et al. reported phototherml therpy (PTT) of the polylctic-co-glycolic cid (PLGA)/
MXene nnocomposites, with the destruction of tumorous cells hppening t nerly 80°C in ner-
infrred (NIR) lser within 300 s [147]. Szuplewsk et al. demonstrted the NIR lser-ssisted nni-
hiltion of the cncerous cells using PEG-coted MXene nnokes with resonble PTT efciency
nd notble biocomptibility t brod spn of mesured concentrtions of up to 37.5 μg/ml [148].
Feng et al. shown the PTT of the PVA/MXene nnokes t wide rnge of bsorptions within NIR
region hving PCE of nerly 24.5% nd 43.3% t 808 nm nd 1064nm, respectively [149]. Lin et al.
employed PVP/MXene nnosheets to study the in vivo PTT tumor tretment utilizing NIR lser
sources, reporting n pprecible heling of the tumor cells within two dys without reppernce
nd hving  surviving period of 16 dys [150].
Xing et al. evluted the sustined nd controlled relese of the nticncer DOX drug by cel-
lulose/MXene nnocomposite hydrogels, reveling  signicnt DOX relesing cpbility, which is
further ccelerted by irrdition of 808-nm light [151].
Rkhi et al. constructed  Non/MXene nnocomposites-bsed enzymtic glucose biosensor,
which exhibited  liner mperometric response t concentrtions of 0.1–18 mM, including sensi-
tivity nd detection limit of 4.2 μAmM−1cm−2nd 5.9 μM (S/N = 3), respectively [152]. Chen et al.
introduced biocomptible PLA/MXene nnocomposites for guided bone regenertion (GBR), which
encourged preosteoblst dhesion, prolifertion, nd osteogenic differentition [153].

3.2.4.3 Energy Storage Applications

Polymer/MXene nnocomposites re extensively utilized for the fbriction of energy storge sys-
tems, for exmple, supercpcitors, rechrgeble btteries, nd energy conversions [30–32,35–38].
The conductive polymers, for exmple, polyuorene (PF) derivtives [93], poly(3,4-ethylenedioxy-
thiophene) (PEDOT) nd its derivtives [102,154,155], PPy [44,104,156,157], PANI [78,158–162],
PVA [43], PDAC [43], PDVF [41,163], nd others, re generlly used for energy storge devices.
Boot et al. reported pseudocpcitnce of the polr, nonpolr, nd chrged nitrogen functionlized
PF derivtives, which displyed improvement in both volumetric nd grvimetric cpcitnce with
pprecible retention of cpcitnce both low nd high scn rte long with good cycling stbil-
ity up to 104 cycles tht cn be utilized for effective prolonged energy storge devices [93]. The
cpcitnce of the PF derivtives is signicntly high compred to both PVA/MXene [43] nd PPy/
MXene nnocomposites [44]. Chen et al. prepred PEDOT/MXene nnocomposites with good spe-
cic cpcitnce nd brodened potentil rnge of bout1.8 V, long with promising supercpcitor
properties [154]. Wu et al. prepred PPy/MXene nnocomposites tht demonstrted n ultimte
grvimetric cpcitnce of 184.36 Fg−1t 2.0 mVs−1nd dmirble cycling longevity to mintin the
cpcitnce retention of 83.33% following 4 ×103 chrging/dischrging cycles t  current density
Processing, Morphology, Mechanical, and Electrical Properties 57

of 1.0 Ag−1 [156]. Li et al. demonstrted pseudocpcitor obtined from conducting PANI/MXene
nnocomposites with  specic cpcitnce of 1632 Fcm−3nd  rte cpcity of 827 Fcm−3t
5×103mVs−1 [159]. Vhid Mohmmdi et al. discussed the PANI/MXene nnocomposite electrodes
with excellent specic nd volumetric cpcitnce of 503 Fg−1nd 1682 Fcm−3, respectively, s well
s cpcitnce retention of 98.3% fter 104 cycles [160]. Li et al. emphsized n electrochemicl
electrode bsed on PANI/MXene nnocomposites, showing volumetric cpcitnce of 563Fg−1t
0.5Ag−1nd retention cpcity of 84.72% nd 95.15% by chnging current density from 0.5–20Ag−1
nd fter 104 cycles, respectively. An symmetric supercpcitor is developed by tking of PANI/
MXene nnocomposites nd ctivted crbon (AC) s positive nd negtive electrodes, respectively
tht chieved 22.67Wh/kg energy density t 0.217kW/kg power density [161].

3.2.4.4 Electromagnetic Interference Shielding and Absorption Applications

Polymer/MXene nnocomposites cn be pplied for EMI shielding due to  synergistic effect exhib-
ited by highly conductive, hydrophilic, nd chemicl ctive MXene nd good elstic, corrosion
resistive, eco-friendly, nd lightweight polymers [40,164]. Different polymer/MXene nnocom-
posites, such s PS [123], PP [124], elstomer [165], PEDOT:PSS [166–168], PVA [66,169], PAT–
PANI–PpAP copolymer [170], PU [171–173], TPU [174], PVDF [175,178], nd others, re tken to
investigte the EMI shielding performnce. Sun et al. developed PS/MXene nnocomposites chiev-
ing  superior EMI SE bove 54 dB throughout the entire x-bnd frequency region, for exmple,
the highest EMI SE of 62 dB t 1.9 vol.% MXene concentrtion, which is stted s the mximum
reported vlue for conducting polymer nnocomposites [123]. Xu et al. explored the EMI shielding
performnce of the PP/MXene nnocomposites exhibiting EMI SE exceeding 60 dB throughout
the complete X-bnd frequency rnge with the highest vlue of 66 dB t thickness of 1.93 mm for
2.12 vol.% MXene loding [124]. Akyiir et al. reported highly exible nd mechniclly tough
elstomer/MXene nnocomposites with high EMI SE of 49 dB for  lm 1 mm thick with  density
of 1.25 gcm−3 t 19.6 vol.% of MXene loding. The high conductivity of MXene of 4350 ± 125 Scm−1
deliver spontneous chrge crriers in the polymer to tke in EMI rditions [165]. Wn et al. nd
Liu et al. reported PEDOT:PSS/MXene nnocomposite lms exhibiting EMI SE of 40.5 dB nd
42.1 dB t bout specimen thickness of 6.6 μm nd 11.1 μm, respectively, nd the former shows 
specic EMI SE (SSEt) of 19 497.8 dBcm2g–1. The totl EMI SE (SET), long with both bsorption
(SEA) nd reection (SER) components, is signicntly incresed with n increse in MXene lod-
ing [166,167]. Jin et al. studied the EMI shielding of 19.5 wt% MXene-lled PVA nnocomposite
lm, which showed 44.4 dB EMI SE t  27.0-μm specimen thickness nd 9343 dBcm2g−1specic
EMI SE (SSEt) [66]. Rguln et al. synthesized MXene-loded PAT–poly(p-minophenol)–
polyniline (PAT–PANI–PpAP) copolymer nnocomposites nd climed 99.99% blocking of the
incident rditions, with highest EMI SE rnge from 45.18 to 39.33 dB, but SSEt, bsolute effective-
ness (SSE/t), nd SE/trnges re 27.99–40.49 dBcm3g−1, 236.45–721.25 dBcm2g−1, nd 1.393–1.6
dBmm−1, respectively [170]. Wng et al. investigted the EMI shielding properties of the PU/MXene
nnocomposite erogels nd reported n EMI SE bove 64.7 dB t  specimen thickness of 2 mm
nd  density of bout 38.2 mgcm−3. The typicl SET nd SEA vlues enhnced from 32.5 dB to 64.7
dB nd 23.6 dB to 55.6 dB with improvement in thickness from 0.5 to 2.0 mm, respectively [171].
Go et al. conveyed remrkbly high 50.7 dB EMI SE t  52-µm specimen thickness nd n SSE/t
of 7276dBcm2g−1 [174]. Li et al. mnufctured PVDF/MXene nnocomposite lms with  mxi-
mum 19504.8dBcm2g−1 SSE/t t  17-μm specimen thickness [175].
Wei et al. exmined the microwve bsorption behvior of the PANI/MXene nnocomposites,
which showed the highest reection loss of −56.30 dB t 13.80 GHz frequency nd  1.8-mm thick-
ness s well s  relevnt bsorption bndwidth (>90%) extending from the X-bnd to the Ku-bnd
GHz frequency region with the vrition of thickness from 1.5 to 2.6 mm. The dependence of reec-
tion loss on both frequency nd thickness of the PANI/MXene nnocomposites nd the suggested
mechnism of microwve bsorption [177].
58 MXene-Filled Polymer Nanocomposites

3.2.4.5 Filtration Applications

Hn et al. devised the ltrtion performnce of the polyether sulfone (PES)/MXene nnocomposite
membrnes with superior ux vlue with  remrkble rejection of both orgnic dyes nd inorgnic
slts t low pplied pressure [99]. Ren et al. prepred PVDF/MXene nnocomposite membrnes exhib-
ited excellent wter ux chrcteristic nd considerble selective ltering of metl ctions subjected to
both dimension nd chrge. The wter ux of the PVDF/MXene nnocomposites drsticlly decresed
nd ltrtion time rpidly incresed with increse in thickness of the membrne. Moreover, the selectiv-
ity bout the metl ction of sizes less thn 4.5 Å nd oxidtion sttes between +2 to +4 [179].
Hn et al. developed polyimide (PI)/MXene nnocomposite membrnes with n outstnd-
ing rejection rte of the orgnic dyes t both mbient pressure nd temperture [180]. Wu et al.
reported the successful lcohol uxes in both PEI/MXene nd PDMS/MXene nnocomposites
[181]. Moreover, Ho et al. demonstrted polr (mine (–NH2) nd crboxyl (–COOH) nd nonpolr
liner hydrocrbon chin (−C6H6 nd −C12H26) functionl groups in modied MXene-bsed poly-
crylonitrile (PAN)/PEI nd PAN/PDMS nnocomposite membrnes with signicnt improvement
in ux of orgnic solvents such s ethyl cette, isopropnol, n-heptne, nd toluene [182]. Xu et al.
formulted chitosn/MXene nnocomposite membrnes for pervportion dehydrtion of orgnic
solvents such s ethnol, ethyl cette, nd dimethyl crbonte [183]. Shen et al. investigted the
CO2 gs seprtion performnce of the PEI/MXene nnocomposite membrnes with permetion
selectivity of 15.3 nd 1.4 for CO2/CH4 nd CO2/H2 gs mixtures, respectively [184].

3.2.4.6 Other Applications

In ddition to the ppliction of the polymer/MXene nnocomposites in the discussed elds, the
novel nnostructures nd excellent properties of the sme cn be suitble for vrious promising
purposes, for exmple, rechrgeble btteries [72,185], fuel cells [100,186,187], nnogenertors
[52,188], me retrdncy [169, 189–193], nd mny more [34,194,195]. Luo et al. reported tht the
me retrdncy behvior of the TPU/PCS-MXene nnocomposites ws pprecibly improved, nd
the smoke emission cpbility ws signicntly reduced s the presence of the MXene endorses
the lbyrinth effect, which develops  compctness nd concentrtion of residues through unevenly
 nonggregted distribution of MXenes within the TPU mtrix. The time to ignition, pek het
relese rte, totl het relese, totl smoke production, pek CO production rte, nd pek CO2 pro-
duction rte of the 3wt% PCS-MXene-lled TPU nnocomposite ws reduced by 35.13%, 66.66%,
21.01%, 27.72%, 52.24%, nd 60.65%, respectively, in comprison with net TPU [192].

3.3 FUTURE PERSPECTIVES AND CHALLENGES

This book chpter dels with the processing, morphology, mechnicl nd electricl properties, nd
ppliction of polymer/MXene nnocomposites. This chpter discussed the importnt results of the
current rticles nd proposed mechnisms for the inuence of MXene on the properties of polymer
nnocomposites. Reinforcement of MXene within the polymer substntilly enhnce the mechni-
cl, electricl, nd therml properties due to the synergistic effect of the superior electricl con-
ductivity, high specic surfce re, exceptionl nnostructured morphology, nd distinct surfce
chemistry of the MXene nnosheets nd superior exibility, good mechnicl strength, nd esy
processibility of the polymer mtrices. Polymer/MXene nnocomposites cn be successfully pre-
pred through solution csting, melt blending, nd in situ polymeriztion processes. The polymer/
MXene nnocomposites hs exhibited vst ppeling projections tht cn be emerged s  potentil
substitute for sensor, biomedicl, energy storge nd conversion, EMI shielding nd bsorption,
ltrtion, nd mny other pplictions.
Nonetheless, the reserch nd development work on polymer/MXene nnocomposites re in
their erly stges, so industril mnufcturing nd successive endue cnnot be explored due to
following two min chllenges. Initilly, exfolition of the MXene nnolyers into single-lyer
Processing, Morphology, Mechanical, and Electrical Properties 59

nnosheets involves hzrdous chemicl methods, nd chieving  homogeneous dispersion of the
hydrophilic MXene nnosheets within the hydrophobic polymer mtrix is  chotic tsk. In spite
of the tough chllenges, the fbricted polymer/MXene nnocomposites cn be suitble for vrious
promising pplictions. Therefore, the reserch work on polymer/MXene nnocomposites cn be
further ccelerted to ccomplish with fruitful implementtions in different ppliction res. A key
drwbck of MXene to be used for fbriction of polymer/MXene nnocomposites is its vulnerbil-
ity to oxidtion, which most ffect the EMI shielding performnce. Furthermore, immense ttention
cn be given to the lrge-scle production of polymer/MXene nnocomposites using economiclly
vible nd environmentlly friendly methodologies.
Advnce reserch on polymer/MXene nnocomposites cn be performed bsed on the follow-
ing importnt pproches: (1) investigtion of industrilly fesible, cost effective, nd eco-friendly
techniques for fbriction of MXene nnosheets; (2) reducing the oxidtion of MXene nnosheets
for enhncing their chemicl stbility; (3) exmining the origins for interphse dhesive interctions
mong polymer mtrix nd MXenes; nd (4) dvncement of multiperformnce polymer/MXene
nnocomposites.

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 4 MXene–Elastomer
Nanocomposites
Jeeshma R, Swapna V.P, and Ranimol Stephen

CONTENTS
4.1 Introduction ............................................................................................................................. 71
4.2 Preprtion Methods of MXene/Elstomer Nnocomposites ................................................. 72
4.2.1 Ltex Compounding Method ...................................................................................... 72
4.2.2 Freeze-Drying Method ................................................................................................ 72
4.2.3 Solvent Mixing–Melt Blending Method ..................................................................... 73
4.2.4 Melt Blending Method ................................................................................................ 73
4.2.5 Lyer-by-Lyer Deposition Method............................................................................ 73
4.2.6 Spin-Coting Method .................................................................................................. 74
4.2.7 Solution Csting Method............................................................................................. 74
4.2.8 Vcuum-Assisted Filtrtion Method or Suction Filtrtion Method............................. 75
4.2.9 Emulsion Method ........................................................................................................ 76
4.3 Properties of MXene/Elstomer Nnocomposites .................................................................. 76
4.3.1 Conductivity ................................................................................................................ 76
4.3.2 Dielectric Properties.................................................................................................... 77
4.3.3 Mechnicl Properties................................................................................................. 77
4.3.4 Therml Stbility......................................................................................................... 78
4.3.5 Flme Retrdncy........................................................................................................ 79
4.3.6 Brrier Properties ........................................................................................................ 79
4.4 Applictions ............................................................................................................................ 80
4.4.1 Sensors ........................................................................................................................ 80
4.4.2 Electromgnetic Interference Shielding Mterils...................................................... 83
4.4.3 Other Applictions ...................................................................................................... 83
4.5 Conclusion............................................................................................................................... 83
References........................................................................................................................................ 84

4.1 INTRODUCTION
Two-dimensionl (2D) trnsition metl crbides, nitrides nd crbonitrides re generlly clled s
MXenes. It is synthesized from  precursor MAX, where M is the erly trnsition metl, A is group
IIIA or IVA element nd X is crbon nd or nitrogen. Recently, mteril scientists hve shown
gret interest in the study of different Mxenes nd MXene-bsed nnocomposites becuse of their
properties like electricl nd therml conductivity, high specic surfce re nd comptibility
with polymer systems. The ne-tuning of size, surfce chemistry nd morphology of MXenes re
possible, which mkes it  promising nnomteril for vrious pplictions. Moreover, the MXene
surfce is hydrophilic nd cn esily be dispersed in wide rnge of solvents. Introduced to the sci-
entic community in 2011, MXene/polymer nnocomposite reserch is in n erly stge [1]. Two-
dimensionl MXenes hve good electricl conductivity nd cn be used in the electronic industry.
The importnce of conductive elstomers rose from the demnd for stretchble nd exible
electronics. Elstomers cn be mde conductive by incorporting some conductive llers such s

DOI: 10.1201/9781003164975-4 71
72 MXene-Filled Polymer Nanocomposites

crbon nnotube, grphene, grphite, MXene nd so on. Elstomer/MXene nnocomposites re
promising mterils for electromgnetic interference (EMI) shielding owing to the exceptionl elec-
tricl conductivity of MXene [2]. Properties of nnocomposites gretly depend on the group present
on the MXene surfce, its dispersion in the polymer mtrix nd the processing conditions. MXene/
polymer nnocomposite membrnes exhibited high degree of wter permetion nd rejection of ions
[3]. It cn ct s  me retrdnt lso, nd its incorportion decreses the mmbility of poly-
meric membrnes [4]. The electricl conductivity of poly(vinyl lcohol) (PVA) is found to be 3000
times greter thn pristine PVA in the presence of this nnomteril [5]. MXene/poly(propylene)
nnocomposites showed excellent EMI shielding [6]. From studies, it is reveled tht MXene is n
interesting nnomteril for the fbriction of conductive exible nnocomposites. This chpter
focuses on the preprtion, properties nd pplictions of MXene/elstomer nnocomposites. It
provides n insight into the different processing techniques, properties nd pplictions of MXene/
elstomer nnocomposites.

4.2 PREPARATION METHODS OF MXene/ELASTOMER

NANOCOMPOSITES
4.2.1 LATEX COMPOUNDING METHOD
Ltex compounding is one of the effective nd widely used methods to prepre MXene/elstomer
nnocomposites. This method llows the preprtion of nnocomposite t mbient conditions. In
this method, the unmodied MXene (or modied MXene) solution is trnsferred to the net els-
tomer ltex of  specied mount, nd it is mechniclly stirred for to get uniform dispersion of
MXene in the elstomer ltex. Then the cogultion of MXene–elstomer ltex is initited by dd-
ing cid, nd the resulting cogulnt is wshed thoroughly to remove the impurities nd obtin pH
7. The wet product is llowed to dry in  ventilted oven followed by compounding using  two-
roll mill. The composite is then vulcnized using  preheted-hydrulic press [7]. The preprtion
method of MXene/elstomer nnocomposite by ltex compounding is summrized in Figure 4.1.

4.2.2 FREEZE-DRYING METHOD

MXene/elstomer nnocomposites cn lso be prepred by green nd fcile freeze-drying methods.
The specied mount of MXene (Ti3C2) dispersion is grdully dded to the elstomer ltex con-
tining dditives nd stirred mechniclly t room temperture. The uniform MXene/elstomer sus-
pension is directly dried vi freeze-drying. It is then mixed in  two-roll mill, nd the nl rubber

MXene

Elastomer latex Mechanical mixing

Co-coagulation

Two-roll milling

Vulcanization

FIGURE 4.1 Schemtics of MXene/elstomer nnocomposite preprtion by ltex compounding method.

MXene–Elastomer Nanocomposites 73

SBR/Ti3C2
SBR latex nanocomposite

Vulcanization &
Mechanical mixing

Freeze-drying

Ti3C2 (MXene)

FIGURE 4.2 Schemtics of styrene butdiene rubber (SBR)/MXene nnocomposite preprtion by freeze-
drying method [8].
Source: Reproduced with permission from RSC.

nnocomposite is obtined by compressing the compound t  specic temperture with  plten

press for the optimum curing time. The preprtion method of  styrene butdiene rubber (SBR)/
MXene nnocomposite is shown in Figure 4.2 [8].

4.2.3 SOLVENT MIXING–MELT BLENDING METHOD

MXene/elstomer nnocomposite cn be fbricted using the solvent mixing–melt blending method.
One of the exmples is the preprtion of polyurethne/MXene-hybrid nnocomposite [9]. In this
method, polymer is dissolved in  suitble solvent nd ultrsonicted to get  homogeneous solution.
MXene dispersed in ethyl lcohol is dded to the polymer solution nd sonicted. The prepred
nnocomposite is precipitted in  nonsolvent nd dried. It is then mixed using two-roll mill nd
hot-pressed to obtin elstomer/MXene nnocomposites.

4.2.4 MELT BLENDING METHOD

The melt blending method is lso n effective method used to prepre MXene (Ti3C2TX)/elstomer
nnocomposite. The modied or unmodied MXene is blended with elstomer in  twin-screw
extruder, where the extruder cts s  dispersion tool. The temperture nd screw speed of the
extruder hve been optimized for the even dispersion of MXene in the elstomer. The extruded
smple is then hot-pressed for further nlysis [10,11].

4.2.5 LAYER-BY-LAYER DEPOSITION METHOD

MXene (Ti3C2)-coted elstomer cn be synthesized by the lyer-by-lyer (LBL) deposition method,
which involves the synthesis of Ti3C2 ultr-thin nnosheets nd the coting solutions nd the LBL
deposition. The fundmentl principle of the LBL deposition method includes the lignment of
oppositely chrged mterils s multiple bilyers by utilizing the vrious interctive forces includ-
ing vn der Wls, hydrogen bonding, nd electrosttic bonds. Lin nd coworkers [12] successfully
synthesized the Ti3C2/chitosn coted polyurethne foms (PUFs) by LBL deposition method for
me retrdnt ppliction nd the scheme is presented in Figure 4.3. They used Ti3C2 ultr-thin
74 MXene-Filled Polymer Nanocomposites

FIGURE 4.3 Schemtic of the lyer-by-lyer ssembled pproch for construction of the Ti3C2/chitosn
nnocoting on PUF [12].
Source: Reproduced with permission from Elsevier.

nnosheets, which re negtively chrged, s the min component to prepre the re retrdnt cot-
ing for PUF, nd the chitosn is used s the positively chrged prtner combined with Ti3C2. The
chitosn powder is dissolved in deionized wter, nd n queous suspension of MXene nd sodium
polycrylte (PAAN) solution is djusted by the diluted hydrochloric cid solution to pH 5 nd
pH 3, respectively. The LBL deposition is chieved by immersing the PUF into PAAN solution
followed by the chitosn solution nd MXene solution until the required numbers of bilyers re
formed. This method is helpful to conserve the porous structure of elstomer fom, which is dm-
ged during the loding of nnollers.

4.2.6 SPIN-COATING METHOD

The spin-coting method is effectively used for the synthesis of MXene/elstomer nnocomposites.
First, the MXene dispersion in ethnol is prepred using n ultrsoniction method. The MXene
dispersion in ethnol is then dropped into the elstomer solution nd mixed thoroughly by ultr-
soniction for 30 minutes to obtin uniform suspension. Next, the curing gents re dded into the
suspension, where the curing gent dded should be one tenth of the elstomer mss, nd the smple
is stirred to produce  uniform dispersion. The produced mixture is spin-coted onto  nylon textile
coted with Cu–Ni lloys substrte nd cured in n oven t 80°C for lmost 2 hours. This method
ws successively used for the fbriction of MXene/elstomer nnocomposites used for sensing
pplictions [13].

4.2.7 SOLUTION CASTING METHOD

The solution csting is one of the simplest methods, which is used for the fbriction of MXene/
elstomer nnocomposites. First,  homogeneous mixture of elstomer nd MXene is prepred by
tking the required mss frction of elstomer nd MXene nd then dding  10-wt% curing gent
into the solution. The obtined mixture is poured onto the glss substrte with  required thick-
ness nd heted t 80°C for 2 hours. Finlly, the MXene/elstomer composite lm is detched
from the glss surfce nd cn be used for further pplictions. One of the exmples is the form-
tion of MXene/polydimethylsiloxne (PDMS) nnocomposite lm by the csting method [14].
Figure 4.4 shows the fbriction procedures of the MXene/elstomer nnocomposite lm by the
csting method.
MXene–Elastomer Nanocomposites 75

Stir

Elastomer latex MXene MXene/elastomer mixture

Casting

80°C

2 hours

Elastomer/MXene nanocomposite film

FIGURE 4.4 Schemtic digrm for the fbriction of the elstomer/MXene nnocomposite lm.

FIGURE 4.5 Schemtic digrm of the preprtion of MXene/NR nnocomposite [16]

Source: Reproduced with permission from Elsevier.

4.2.8 VACUUM-ASSISTED FILTRATION METHOD OR SUCTION FILTRATION METHOD

MXene/elstomer nnocomposite lms re lso synthesized by  simple nd cost-effective suction
(vcuum-ssisted) ltrtion method. In this method, the electrosttic repulsion forces between the
similrly chrged MXene nd elstomer ltex (both re negtively chrged) ensure the distribution
of the MXene sheets between the elstomer prticles, which gives n interconnected 3D network
[14,15]. First,  colloidl suspension of MXene of required concentrtion is prepred. Then, the
MXene (Ti3C2Tx) suspension is mixed with elstomer ltex under rpid stirring t room temper-
ture, nd then the mixture is sonicted for 10 minutes to obtin  uniform suspension. The prepred
suspension is subjected to vcuum ltrtion to generte MXene/elstomer composite lm. The lms
so obtined re then removed nd llowed to ir-dry t room temperture. The fbriction of the
MXene/nturl rubber nnocomposite [16] is illustrted in Figure 4.5.
76 MXene-Filled Polymer Nanocomposites

4.2.9 EMULSION METHOD

The emulsion method is n importnt method used to prepre MXene/elstomer nnocomposite.
For this, rst, n MXene/ethnol dispersion is prepred by mixing the required quntity of MXene
(Ti3C2Tx), ethnol nd zirconi beds in  plnetry milling continer. The mixture is milled t
400r/min for 10 hours followed by sonicting t 25°C for 1 hour nd centrifuged t 10,000r/min for
10 minutes. The obtined superntnt (MXene dispersion) is then dded to the queous emulsion of
elstomer (functionlized or nonfunctionlized), which cn be prepred by stirring. The mixture is
then sonicted to obtin uniform dispersion. Afterwrd, the MXene/elstomer emulsion is poured
into  glss plte nd dried for 2dys t mbient temperture to obtin the composite lm. One of
the exmples is the fbriction of MXene/polyurethne composite lm using wterborne polyure-
thne nd MXene dispersion in ethnol [17].

4.3 PROPERTIES OF MXene/ELASTOMER NANOCOMPOSITES

The crystls of MXenes possess overll  hexgonl closely pcked structure, where M toms re
in closely pcked rrys nd X toms reside in the octhedrl interstitil sites [18–20]. To keep up
structurl stbility the ordering of M toms in MXenes could vry between M2X, M3X2 nd M4X3
[21]. The properties of MXene cn be ltered by vrying its surfce functionlities such s –O, –OH,
–F s well s tuning the rtios of M or X elements. Due to the intriguing properties of MXene, it
esily ctches the ttention of reserchers for the improvement of vrious properties of polymers
[22]. In this section, we discuss the properties of MXene/polymer composites, including electri-
cl nd therml conductivity, dielectric properties, mechnicl properties, therml stbility, me
retrdncy nd brrier properties

4.3.1 CONDUCTIVITY
The electricl nd therml conductivity of pure elstomers re found to be lower. This drwbck of
the elstomers cn be overwhelmed by fbricting their composite with conductive nnomterils
[23–25].
Conductive elstomer nnocomposites hve ttrcted gret ttention in exible sensors, elec-
trosttic dischrge environments nd therml interfce mngement. Compred to other nno-
mterils, MXenes hve good electricl conductivity nd hve been incresingly used in exible
electronic devices (Tble 4.1)[26]. Metllic conductivities of Ti3C2Tz MXenes re reported on the

TABLE 4.1
Electrical Conductivity of MXene and Other Materials
Nanomaterial Electrical conductivity [S/m]
Crbon mteril ≈ 106 crbon nnotube (CNT)
≈ 108 (grphene)
1.6 ×105 (reduced grphene oxide [rGO] lm)
Metl mteril 4.10 × 107 (Au bulk)
6.3 × 107 (Ag bulk)
5.96 × 107 (Cu bulk)
Conductive polymers ≈ 105
MXene fmily 2.4 × 106 (Ti3C2Tx lm)
2.7 × 105 (Ti3CNTx lm)
1.6 × 105 (Ti2CTx lm)
9 × 104 (V2CTx lm)
MXene–Elastomer Nanocomposites 77

order of pproximtely 10,000 S/cm [27] nd electricl conductivity in the rnge of pproximtely
2,000–6,500 S/cm [28]. The conductive MXene-bsed polymer nnocomposites re widely used s
electromgnetic interference shielding mterils [29], trnsprent conductors [28], energy storge
nd conversion pplictions [30–31], wter puriction [32] nd sensors such s exible strin sen-
sors, pressure sensors, gs nd selective molecule sensors [33–35].
Nitrile butdiene rubber (NBR) exhibits  therml conductivity of 0.23 W.m−1K−1, while upon the
dispersion of Ti3C2TxMXene nd llylmine-modied MXene (m-MXene) t 19.6 vol% in NBR, the
therml conductivity increses to 0.69 W.m−1K−1 nd 1.01 W.m−1K−1, respectively, which is observed
to be higher thn the other reported elstomer nnocomposite system contining lumin, boron
nitride, grphene nd zinc oxide nnoprticle t the sme or higher ller frction. NBR/MXene nd
NBR/m-MXene nnocomposites, whose electricl conductivity incresed upto 8.82 × 10 −5 nd 6.67
× 10 −3 S.cm−1, respectively, t 20.9 vol% ller lodings compred to the unlled elstomer [7, 36].
SBR/Ti3C2Tx MXene nnocomposites exhibited  therml conductivity of 0.477 W.m−1K−1, which is
much higher thn tht of n SBR/reduced grphene oxide (3wt%) nnocomposite system (0. 265W.
m−1K−1)[8]. Nturl rubber ltex (NRL)/MXene nnocomposite fom exhibits the electricl conduc-
tivity of 6.18 × 10−4 Sm−1, which is two orders of mgnitude higher thn tht of pure NRF [37].

4.3.2 DIELECTRIC PROPERTIES

Elstomers with excellent dielectric properties re most suitble in the eld of electromechni-
cl trnsducers. Hyper-brnched polysiloxne (HPSi)-modied Ti3C2TX sheets (HPSi-d-Ti3C2TX)
incorported poly (dimethyl siloxne) (PDMS) composite system holds excellent dielectric proper-
ties. PDMS contining 1.40 vol.% HPSi-d-Ti3C2TX system exhibit  dielectric constnt of 23.7 t
102 Hz, which is 8.5 times higher thn tht of net PDMS [38]. Jen et l. fbricted Ti3C2Tx MXene
incorported ethylene–vinyl cette (EVA) nnocomposites nd they found tht n 8 wt% MXene-
ller-incorported EVA showed greter dielectric properties with low dielectric loss compred to ll
other weight percentges owing to their high electricl conductivity, good interction between ller
nd mtrix nd well dispersion of Ti3C2Tx in EVA mtrix [39].

4.3.3 MECHANICAL PROPERTIES

Ti3C2 MXene possesses  higher Young’s modulus mong solution-processble 2D mterils nd
hs been observed to be 333 ± 30 GP by the tomic force microscopy indenttion technique [40],
which is much higher thn those of grphene with similr thickness [41]. These demonstrted
tht MXene mterils re good reinforcements for polymeric composites. Theoreticl moleculr
dynmic simultion study reports 502 GP Young’s modulus for MXene, but the experimentl vlue
is found to be lower owing to the surfce functionliztion nd defect [42]. The good mechnicl
property of MXene fcilittes their ppliction in portble nd werble microelectronic systems
like supercpcitors. The incorportion ofTi3C2Tx MXene (t 14.0 vol%) in elstomer, nitrile but-
diene rubber, leds to 570% increse in Young’s modulus. While both elongtion t brek nd
tensile strength record  640% nd 180% improvement t 3.9vol% nd 7.5 vol% MXene, respec-
tively, nd then decresed [35]. NBR/MXene nnocomposites fbricted vi ltex compounding
exhibited remrkble mechnicl properties. At 14.0 vol% MXene-incorported NBR exhibited 
tensile strength of 25.94 ± 0.81 MP, elongtion t brek of 170 ± 5.6% nd Young’s modulus of
15.85 ± 0.75 MP [2]. MXene provides signicnt reinforcement to the nturl rubber (NR) mtrix.
NR/Ti3C2 nnocomposite fbricted by vcuum-ssisted ltrtion exhibited modulus nd tensile
strength 150 times nd 7 times higher, respectively, thn those of pure NR, t 6.71 vol%Ti3C2. Ti3C2-
reinforcedNR by forming n interconnected network due to the electrosttic repulsion between NR
nd negtively chrged Ti3C2 [15]. Compred with net nturl rubber ltex fom (NRF), 2 nd 3
phr of MXene contining NRF showed  171% nd 157% increse in tensile strength, respectively
[37]. Polyurethne (PU)/MXene nnocomposites fbricted vi n emulsion method showed  70%,
78 MXene-Filled Polymer Nanocomposites

20% nd 13% improvement in yield stress, tensile strength nd hrdness, respectively, thn pure PU
t 0.5 wt% MXene loding [17]. It is interesting to observe tht incorportion of MXene, increses
rigidity nd toughness of the polymer simultneously. Sheng et l. prepred thermoplstic polyure-
thne (TPU)/MXene nnocomposites by  melt blending method nd exmined their properties.
Their ndings demonstrted tht t 0.5 wt% MXene incorportion, the tensile strength nd elong-
tion t the brek of TPU were incresed by 47.1% (from 14 MP of TPU to 20 MP) nd 17.5% (from
1580% of TPU to 1857%), respectively [11]. 3wt% MXene nd melmine-cynurte (Ti3C2Tx@
MCA) nnohybrid-integrted TPU nnocomposites exhibit 61.5 MP of tensile strength, 175.4 ± 7.9
MJ m−3 of toughness nd 588% of strin t filure [43]. Li et l. reported tht in the presence of 2
phr Ti3C2, SBR nnocomposites showed higher tensile strength, which is higher thn tht observed
in SBR nnocomposites with 2 phrgrphene [8]. Ti3C2MXenes/PDMS composite system modied
by biomolecule exhibited  higher tensile strength t 10 wt% of ller loding, while elongtion t the
brek decresed with the increse of ller loding from 2 wt% to 10 wt% [44].

4.3.4 THERMAL STABILITY

Generlly, the therml stbility nd the dimensionl stbility of the nnocomposite re closely
relted to the therml conductivity, therml expnsion, degrdtion nd brrier properties of dded
nnollers. MXenes possess good therml conductivity compred to those of most semiconduct-
ing low-dimensionl mterils nd metls. For exmple, 2.5 wt% of Ti3C2Tz MXene–incorported
PDMS nnocomposite showed  threefold improvement in therml conductivity compred with
pure PDMS [46]. SBR/Ti3C2nnocomposites fbricted by freeze-drying, nd the mechnicl mix-
ing process showed higher therml stbility thn net SBR. In the presence of 4 phr Ti3C2, SBR

TABLE 4.2
Mechanical Properties of MXene/Elastomer Composites
Tensile Young’s
Thickness Strength Modulus
MXene/Elastomer Method wt (%) (μm) (MPa) Strain (%) (GPa) Ref
Ti3C2/NR Vcuum- 0.58 v – 3.11 935 0.4e 15
ssisted 1.18 v 244 5.69 843 1.1 e
ltrtion 1.80 v 247 7.01 801 1.31 e
2.44 v 243 10.02 789 1.98 e
3.10 v 248 11.86 771 2.3 e
4.83 v 245 13.32 765 64.2 e
6.71 v 251 18.25 761 87.8 e
Ti3C2/TPU Hot press 0.125 250~300 17.3 ±1 1780 ±130 11
0.25 250~300 18.0 ±1.2 1700 ±120
0.5 250~300 20.6 ±1.2 1850 ±100
1.0 250~300 17.3 ±0.8 1820 ±120
A-MXenes/D- Solution 2 1000 0.64 ±0.12 117 ±12 0.00130 ±0.0002 44
PDMS blending 6 1000 0.79 ±0.14 113 ±12 0.00151 ±0.0002
10 1000 1.81 ±0.22 81 ±6 0.004 ±0.0007
CTAB-Ti3C2/TPU Hot press 0.5 1000 ±300 50.8 ±1.1 599 ±45 45
2.0 1000 ±300 50.1±0.8 614 ±18
TBPC-Ti3C2/TPU Hot press 0.5 1000 ±300 55.9 ±4.6 605 ±22 45
2.0 1000 ±300 54.3 ±2.3 632 ±9

Note: e nd v, respectively, refer to elstic modulus (MP) nd vol% of MXene/elstomer nnocomposites.
MXene–Elastomer Nanocomposites 79

nnocomposites showed initil decomposition t 150°C nd mximum decomposition temper-

ture of 160°C [8]. Thermoplstic polyurethne (TPU)/MXene nnocomposites fbricted vi melt
blending method exhibited n incresed mximum degrdtion temperture of 20.3°C nd the onset
degrdtion temperture of 13.1°C t 0.5 wt% MXene loding [11].

4.3.5 FLAME RETARDANCY

TPUs re extensively pplied s lightweight mterils in electronic device csings, footwer soles
nd shielding for wirings. Nevertheless, it is  highly mmble mteril nd emits  lot of toxic gs
(i.e., CO nd HCN) nd hevy smoke during combustion, which remins  mjor concern in indus-
tril ppliction. Thus, it is impertive to enhnce the re sfety of TPU mteril. The introduction of
me retrdnts to TPU mteril is n effective wy to improve its re sfety performnce. MXene
is  very promising me retrdnt, nd it reduces smoke nd toxicity hzrds in TPU signicntly.
Liu et l. prepred  titnium crbide–reduced grphene oxide (Ti3C2Tx-rGO) hybrid nd found
tht its ddition in  TPU elstomer improve the therml nd re-sfe performnces of TPU nno-
composite signicntly. Incorporting 2.0wt% Ti3C2Tx-rGO led to  signicnt decrese in totl
smoke relese nd the smoke production rte of TPU nnocomposite by 54.0% nd 81.2%, respec-
tively. Moreover, this nnocomposite exhibited 46.2% nd 54.1% distinct reductions in the totl cr-
bon monoxide yield nd crbon monoxide production rte, respectively [9]. MXene nd melmine
cynurte (Ti3C2Tx@MCA) nnohybrid integrted TPU nnocomposite exhibit 40% reduction in
the pek-of-het-relese rte (PHRR) [43].
CTAB-modied Ti3C2 (MXene)–incorported TPU exhibited reduction in PHRR by 51.2%
nd the production of smoke, CO2 nd CO by 57.1%, 49.7% nd 39.4%, respectively [15]. TBPC-
modied Ti3C2 (MXene)–incorported TPU exhibited  reduction in PHRR by 52.2% nd produc-
tion of smoke, CO2 nd CO by 57.4%, 51.7% nd 41.6%, respectively [45].
Ti3C2/chitosn-hybrid-coted PUF reduced the mmbility nd smoke relese of PUF signi-
cntly. With respect to pure PUF, eight different number of bilyers (BL) coting decresed the
PHRR by 57.2%, reduced the totl het relese by 65.5%, reduced the smoke relese by 71.1% nd
reduced the pek of CO2 nd CO production by 68.6% nd 70.8%, respectively [12].

4.3.6 BARRIER PROPERTIES

MXenes re impermeble prticles, nd their ddition into polymers increses the gs brrier prop-
erties of polymers nd resists the trnsport of gs molecules. Generlly, impermeble nnopr-
ticles in  polymer my limit the diffusion of lrger gs molecules cross the membrne due to the
increse in the tortuous pth of the gs molecule in the polymer mtrix. A schemtic representtion
of the tortuous pth is presented in Figure 4.6. Shpe, dispersion stte, orienttion nd volume

(a) Gas molecule (b) Gas molecule

FIGURE 4.6 () Diffusion of gs molecule in pure polymeric lm nd (b) diffusion of gs molecule in poly-
mer nnocomposites through the tortuous pth.
80 MXene-Filled Polymer Nanocomposites

frction of nnollers re the fctors tht determine the tortuosity of the pth. Tortuosity (τ = L1/L2)
is the rtio of the diffusion pth length of the permeting molecule in the nnocomposite membrne
(L1) to the diffusion pth length of the permeting molecule in the pristine polymer (L2) [47].
A nnoprticle-embedded polymer mtrix either increses or decreses the gs brrier proper-
ties of  polymer, which depend on the nture of  nnoller nd the polymer–ller interction.
After introducing nnoprticles, polymers often exhibit high brrier properties by reducing free vol-
ume, constructing  tortuous pth for permeting molecules nd minimizing the permetion cross
section in polymers. Here, nnollers ct s brrier, reducing the trnsport of gs molecules. In the
reverse cse, introducing prticles such s silic nd metl oxide decreses the gs brrier property
of polymers by disrupting the polymer chin pcking nd cretes voids t the polymer–prticle
interfce or free volume pockets [48]. In 2020, Shmsbdi nd coworkers crried out  gs perme-
bility study onTi3C2Tz/Pebx/PU membrne using H2, CO2, N2, nd CH4 gses, nd they observed
incresed CO2/N2 selectivity due to the good dsorption of CO2by the functionl group (especilly
the hydroxyl group) on the Ti3C2Tz surfce [49].

4.4 APPLICATIONS
4.4.1 SENSORS
Elstomer/MXene nnocomposites exhibit excellent stretchbility nd high conductivity due to
synergistic effects. Hence, elstomer/MXene nnocomposites hve ttrcted incresing interests in
sensor fbriction. Becuse of the properties such s high conductivity, verstile surfce chemistry
nd high spect-rtio MXene nnomterils hve been used for sensor fbriction. These elstomer/
MXene nnocomposite–bsed sensors hve found ppliction in electronic skin, electronic dis-
ply equipment, humn helth nd humn body movements, werble electronics nd new gen-
ertion robots [50–56]. High sensitivity, low fbriction prices, good stbility, low detection limit,
quick recovery for repetitive use, energy-efcient nd  quick nd preferbly liner response re the
importnt properties simultneously required for  sensor for its prcticl ppliction.
Flexible werble sensors cn detect n extensive rnge of humn ctivities such s nger bend-
ing [57], rteril pulses [58], rm nd leg movement [59] nd vocl-muscle vibrtions [60].
MXenes re highly promising cndidtes for the ppliction of pressure nd strin sensors.
Pressure sensors re widely pplied in the eld of sports [61], electronic skin [62], helthcre mon-
itoring [63] nd speech recognition [64]. Most of the reported MXene/elstomer-bsed pressure
sensors re observed to be piezoresistive type. Piezoresistive pressure sensors re lwys in high
demnd for werble smrt devices nd humn motion detection.
In  piezoresistive strin sensors, n pplied pressure cuses  chnge in resistivity. In the chnge
in resistivity ΔR/R0, where ΔR indictes the difference between resistivity of the sensor’s mteril
before nd fter pplying the strin nd R is the resistivity of the sensor fbricted mteril t rest.
The guge fctor (GF) is used to nlyze sensitivity of strin sensors:

GF ˜ °R / R0 ,
°R / l0

Where L0 is the originl length of the sensor before pplying  strin nd ΔL is the bsolute chnge
in length. A high GF vlue indictes lrger chnge in resistivity. Ti3C2 MXenes/PDMS composite
system modied by biomolecule exhibit good potentil in werble sensing devices. It shows  GF
of 3.6 nd exhibits good tensile strength, conductivity nd self-heling properties [44]. There re
reports showing GF in the rnge 43–107 for elstomer/MXene-bsed sensors within the strin rnge
of 0–10%. Guo nd coworkers reported  good electronic sensor for intelligent sensing fbricted by
ssembling MXenenno-kes modied with serine nd  rubber-bsed suprmoleculr elstomer
(NMSE). This NMSE-bsed sensor could precisely monitor minute humn physiologicl motion
nd moisture vrition [64], it is shown in Figure 4.7. Piezo resistive pressure sensors fbricted
MXene–Elastomer Nanocomposites 81

FIGURE 4.7 Sensing properties of modied MXene/epoxidized NMSE–bsed electronic sensor [64].
Source: Reproduced with permission from ACS.

from hollow-structured MXene–PDMS composite system exhibit superior properties, including 

wide working rnge (0–180o), consistent performnce with excellent stbility (over 1000 cycles) nd
low detection limit (10 mg). Bsed on its excellent performnce, hollow-structured MXene–PDMS
composite sensors cn detect fcil muscle movement, swllowing, stereo sound nd ultrsonic
vibrtion monitoring, representing its potentil ppliction in werble smrt devices [65].
Li et l. prepred  exible, sensitive, relible nd piezoresistive pressure sensors by coting
PU/chitosn (CS) sponge with Ti3C2Tx (MXene) [66]. Recently, Zhng et l. developed s-MXene/
elstomer (elstomer [Ecoex series]) bilyer device hving ppille-like rrys, here s-MXene
is the 3D micro-structure composed of single-wlled crbon nnotube (SWCNT) nd Ti3C2Tx
titnium crbide (MXene). The bilyer device ws pplied in exible, high-precision nd high-
sensitivity (11.47 kP−1) piezoresistive pressure sensors, nd it ws further used to detect microdro-
plet mnipultion, s well s voice recognition [67].
It is chllenging to fbricte  multifunctionl, exible, highly sensitive strin sensors with ttrc-
tive properties, such s  wide sensing rnge nd low detection limits for prcticl pplictions in
physicl cre systems, smrt robotics nd werble electronics. Generlly, sensors would exhibit 
trde-off effect between high sensitivity nd wide sensing rnge during their ppliction. Recently,
MXene/polyurethne mt–bsed strin sensor were developed nd exhibited superior performnce
for sensing ppliction by chieving high sensitivity coupled with wide sensing rnge. MXene/poly-
urethne mts possess superior properties, including high sensitivity (GF upto 228), outstnding
82 MXene-Filled Polymer Nanocomposites

performnce (more thn 3200 cycles), sensing rnge upto 150%, low limit of detection (0.1%) nd
multifunctionl detection. MXene/polyurethne-bsed sensors cn hve gret potentil to monitor
subtle physiologicl signls (such s respirtion nd pulse wves), nd hence, it could be pplied for
werble helth detectors nd rticil electronic skin [68] (Figure 4.8).

TABLE 4.3
Elastomer/MXene-Based Sensors with Their Applications
Elastomer/MXenesystem Application Ref
Modied Ti3C2 MXenes/PDMS Elstomeric werble strin Sensors 44
Modied MXene/epoxidized nturl rubber Self-helble intelligent sensors nd monitor minute 64
(NMSE) humn physiologicl motion nd moisture vrition
Hollow-structured MXene/PDMS Pressure sensors nd pply in werble smrt devices 65
Ti3C2TxMXene/polyurethne (PU)/chitosn Piezoresistive pressure sensors 66
(CS) sponge
s-MXene (SWCNT nd Ti3C2Tx)/elstomer Pressure sensors nd detect microdroplet mnipultion 67
(Ecoex series) s well s voice recognition
MXene/polyurethne mt Strin sensors nd pply in werble helth detectors 68
nd rticil electronic skin
Ti3C2 nd polyurethne Stretchble strin-sensing fbric 69
Ti3C2 nd poly(dimethylsiloxne) Skin conforml sensors for helth Monitoring 70

FIGURE 4.8 Physiologicl signl monitoring nd physicl motion detection of  network-M/P mt
sensor [68].
Source: Reproduced with permission from RSC.
MXene–Elastomer Nanocomposites 83

4.4.2 ELECTROMAGNETIC INTERFERENCE SHIELDING MATERIALS

Globlly, electromgnetic wve pollution hs become one of the gret chllenges for the environ-
ment. Electromgnetic interference (EMI) shielding mterils minimize or prevent the relese of
EMI signls considerbly from electromgnetic devices into the environment. High-performnce
electromgnetic interference shielding mterils re essentil in exible, foldble nd werble
electronics. MXene sheets provide excellent EMI shielding performnces to the polymers s com-
pred with crbon nnomterils incorported into polymer nnocomposites. The chllenging issue
for the EMI shielding mterils is to combine high EMI shielding performnce together with excel-
lent stretchbility nd mechnicl robustness. Two-dimensionl lyered mteril hve been proved
to hve exceptionl EMI shielding performnce long with excellent mechnicl, electricl nd
therml properties. The incorportion of MXene into elstomer enhnces shielding performnce s
well s stretchbility nd mechnicl robustness. NBR/MXene nnocomposites fbricted vi ltex
compounding exhibited EMI shielding effectiveness of 49 dB t 19.6 vol%. Mechnicl properties
lso found to increse remrkbly by the ddition of MXene to elstomers. In the presence of 14.0
vol% of MXene, NBR exhibited  tensile strength of 25.94 ± 0.81 MP, elongtion t brek of 170
± 5.6% nd Young’s modulus of 15.85 ± 0.75 MP [2]. At 6.71 vol%,  Ti3C2Tx MXene-doped NR
nnocomposite system shows high exibility, excellent EMI shielding performnce of 53.6 dB nd
electricl conductivity of 1400 Sm−1[15] s shown in Figure 4.9.

4.4.3 OTHER APPLICATIONS

T.H. Chng nd coworkers reported highly stretchble MXene/elstomer bilyer composite-bsed
electrochemicl electrode for bendble, stretchble supercpcitors. Recently, MXene-bsed com-
posites hve demonstrted  high potentil for ppliction in werble nd trnsprent devices. A
2D MXene nnosheet is found to be potentil phototherml ller for vrious light-responsive ppli-
ctions. It possesses high therml conductivity nd 100% efciency for light-to-het conversion
[72]. In 2019, Fn et l. developed  werble, helble nd trnsprent composite by integrting
AgNP@MXene hybrid in PU. The AgNP@MXene–PU composite exhibits effective phototherml
conversion nd quick heling cpbilities, nd they pplied this composite in  trnsprent, skin-
mountble, nd sun-powered wrn coting to revel its potentil ppliction for werble nd trns-
prent devices [73].

4.5 CONCLUSION
Scientists re looking for promising mterils to develop exible electronic goods. Recently, Mxenes
re found to be  good dditive for polymers becuse of its distinctive properties. It is  2D mteril
with good electricl nd therml conductivity. Due to its lrge surfce re, it is considered to be 
good dsorbent nd cn be used for the removl of hevy metls. MXene/elstomer nnocomposites
exhibited excellent electricl nd therml conductivity thn crbon nnotube or grphene-lled
systems. Therefore, these mterils re considered to be fvorble mterils for EMI shielding nd
vrious sensor pplictions.

TABLE 4.4
EMI Shielding Effectiveness (SE) of Elastomer/MXene Nanocomposites
Elastomer/MXene System Filler Fraction Fabrication Method EMI SE (dB) Ref
1. NBR/MXene 19.6 Ltex compounding 49 2
2. NR/MXene 6.71 Vcuum-ssisted ltrtion 53.6 15
3. PDMS/MXene 1.1 Dip coting 43 71
84 MXene-Filled Polymer Nanocomposites

FIGURE 4.9 () Electricl conductivities nd (b) Electromgnetic interference shielding effectiveness of
different volume frction of MXene loded into MXene/rubber nnocomposites [15].
Source: Reproduced with permission from Elsevier.

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 5 Green Polymer
Nanocomposites
with MXenes
Nanoth Rasana, Karingamanna
Jayanarayanan, and P. Sarath Kumar

CONTENTS
5.1 Introduction ............................................................................................................................. 89
5.1.1 Green Biopolymer MXene Nnocomposites .............................................................. 89
5.2 Synthesis Methods of Green MXene Nnocomposites........................................................... 89
5.3 Chrcteriztion of Green MXene Nnocomposites............................................................... 91
5.4 Mechnicl Properties of Green Polymer Bsed MXene Nnocomposites ............................ 97
5.5 Applictions of Green Polymer Nnocomposites with MXenes ............................................ 98
5.6 Conclusion nd Future Direction .......................................................................................... 102
References...................................................................................................................................... 102

5.1 INTRODUCTION
5.1.1 GREEN BIOPOLYMER MXENE NANOCOMPOSITES
MXenes re  novel two-dimensionl (2D) nno-structured clss of mterils tht offers vrious
structurl compositions, exciting metllic conductivity, electricl, mechnicl, therml properties
nd dispersibility [1–3]. These properties of MXenes could be exploited nd used s nno-llers in
polymer nnocomposites [4]. Among these, MXene green polymer nnocomposites ply  signi-
cnt role owing to its biodegrdbility, nontoxicity, environmentl-friendliness nd low-cost synthe-
sis techniques. Since the discovery of grphene, ultrthin 2D nnomterils, such s phosphorene
[5], ntimonene [6–7] hexgonl boron nitride [8], lyered metl oxides, trnsition metl disuldes
[9] nd lyered double hydroxides [10], hve gined gret pplicbility owing to their compct,
ordered structure nd quntum connement effects [11]. Very few studies hve reported the incor-
portion of Ti3C2Tx (titnium crbide) MXenes in vrious bio/green polymer mtrices. The mjor
preprtion methodologies nd the chrcteriztion of biodegrdble polymers (poly(crylic cid)
(PAA) [12], poly (lctic cid) (PLA) [13], polyethylene oxide (PEO) [14], lginte/PEO nnobers
[12], poly(vinyl lcohol)(PVA) [12], cellulose [14], chitosn [15], polydopmine (PDA) [13], lignin
biopolymer (L-DEA) [16] nd reinforced MXenes were reported in literture. The mjor objec-
tive of this chpter is to investigte reported MXene-reinforced green nnocomposites synthesis,
processing methodology, prmeters, its sustinbility, cost-effectiveness, tunble properties nd
pplictions.

5.2 SYNTHESIS METHODS OF GREEN MXene NANOCOMPOSITES

Different synthesis routes were discussed in the literture, nd the method of exfolition of MAX
(M: erly-trnsition metl, A: A group element, X is C or N) phse (polycrystlline nno-lmintes
of ternry crbides nd nitrides) into MXene sheets, which mintin their properties nd crystl

DOI: 10.1201/9781003164975-5 89
90 MXene-Filled Polymer Nanocomposites

structure, is pplied in most of the studies [17–22]. In ddition to its dptbility, low-cost fcile
synthesis pproches using biodegrdble sustinble polymers mke it n obvious choice in vri-
ous elds of mterils reserch [23–29].
Elis et l. [12] reported the synthesis route of MXene-reinforced biodegrdble polymer nno-
composites. The uthors hve chosen sustinble biopolymers, such s PVA, PEO, PEO/lginte
nd PAA, for the reinforcement with MXenes. Initilly, the etching of Ti3AlC2 (MAX phse) with
lithium uoride/hydrochloric cid (LiF/HCl) solution ws crried out, nd the colloidl form of
MXene (Ti3C2) kes ws prepred by the soniction of Ti3C2 multilyers [30–31]. An mount of
bout 1 gm of Ti3AlC2 ws grdully dded into HCl solution (12M) long with 1 g of LiF nd
ws stirred continuously for 1dy t room temperture to obtin  colloidl solution. The obtined
solution ws then wshed repetedly with deionized wter followed by continuous gittion, cen-
trifugtion nd decnted till the blck superntnt ws visible (which shows n increse in the con-
centrtion of delminted MXene in solution). In the lst step of the rst phse of preprtion, the
solution ws sonicted in n ice bth under rgon gs ow, followed by centrifuge for 1hour. In the
second phse of preprtion, fully dissolved polymeric solutions (PAA +DMF/H2O, PEO +ethnol/
H2O, PVA + ethnol/H2O) were dded to 1 wt% of Ti3 C2Tx solutions nd stirred for 12 hours t
23°C to chieve complete dissolution. To prepre PEO/lginte/Ti3 C2Tx solution, Ti3 C2Tx/lginte
ws dissolved in glycerol/wter nd dded to  PEO polymer diluted in wter, nd lter, the Ti3
C2Tx/PEO/lginte ws further mixed for 24 hours. Then, Ti3 C2Tx/polymer solution ws electros-
pun to nnober mts by pumping t constnt ow rtes (250–750 μL/hr) under n pplied voltge
of (15–20kV) using  21-guge needle [12].
Hung et l. [32] explined the synthesis of MXene (Ti3C2)-reinforced biodegrdble PLA com-
posites. The uthors lso reported the production of crude Ti3C2 MXene using LiF/HCL solution.
The homogeneous hydrouoric cid solution ws prepred by stirring LiF/HCl solution for 10 min
nd then dded to powdered Ti3AlC2 MAX phse nd ws stirred t 38°C for 2dys. The pH of
superntnt ws mde neutrl by wshing the crude phse of Ti3C2 MXene multiple times with
HCl, LiCl nd deionized wter. The precipitte ws seprted by centrifuging nd sonicting in n
ice bth nd exfolited, single lyers of MXene under nitrogen ow, which ws further centrifuged
nd freeze-dried. PLA biopolymer ws kept in  vcuum oven t 80°C for 4 hours before melt
processing owing to its hygroscopic nture. The dried intumescent me retrdnt (IFR)/PLA bio-
polymer nd Ti3C2 MXene were melt-blended in  Brbender Plsticorder mintining the screw
speed t 60 rpm for 6 min nd chmber temperture t 180°C. The blended composite obtined
fter melt mixing is compression molded t 180°Cnd 10MP for 10 minutes [32]. Another work
[33] reported the production of Ti3C2Tx /polydillyl dimethyl mmonium chloride (PDDA) com-
posites by  dropwise ddition of n queous PDDA polymer solution into colloidl solution of
MXene, nd the mixture ws mgneticlly stirred for 24 hours nd then centrifuged t  high rpm
of 3500 for 1 hour. A similr procedure ws used to prepre PVA/MXene composites with PVA-
MXene weight rtios s 60:40, 40:60, 20:80 nd 10:90 [33]. Yi et l. [34] reported the modic-
tion of MXene sheets using steric cid (SA) nd proposed the synthesis route to prepre MXene/
PLA composite lms. The modiction of MXene sheets using SA (Ti3C2Tx-SA) ws prepred
by mixing 0.5 g of (Ti3C2Tx-N) with 2 g of SA in 80 ml of ethnol nd llowed to rect t 85°C
for 24 hours under continuous mgnetic gittion. After completion of the rection, the mixture
ws ultrsoniclly treted under nitrogen tmosphere, the rection product mixture ws seprted
by centrifugtion nd the precipittion ws wshed by ethnol to remove unttched trces of SA
from MXene–N nnosheets. The product is then dried in  vcuum oven t 80°C for 12 hours to
form Ti3C2Tx-grfted-SA nnosheets [34].
The SA-modied MXene (vried the content from 0.2–2 wt%) sheets re further embedded into
PLA mtrix by solution blending method (Figure 5.1). PLA grnules were dissolved in chloroform
to obtin PLA solution. Ti3C2Tx–SA suspension ws slowly dded to PLA solution, then mgneti-
clly stirred for 12 hours, nd ultrsoniclly treted for 20 min. The mixture ws llowed to evpo-
rte slowly from Petri dishes t room temperture for 24 hours to form thin composite lms [34].
Green Polymer Nanocomposites with MXenes 91

FIGURE 5.1 Synthesis method of steric cid (SA) modied MXene with green biopolymer PLA nnocom-
posites [34].

In nother work [35] on green/MXene composites, Ti3C2Tx MXenes were synthesized from
Ti3AlC2 MAX phse, nd the cellulose-bsed lter pper ws dipped in  colloidl solution of
MXene. The M-lter composite ppers with different dip-coting cycles (1,3,5,7 dip-coting cycle)
were prepred nd kept between PET pltes for curing t 100°C for 2 hours [35]. In nother study
[15] on chitosn/MXene composites, MXene etched from MAX phse ws mixed with ethnol, NH3
(mmoni) nd wter, nd the mixture ws ultr-sonicted with modied polystyrene nd wshed
nd dried to MXene. Then the MXenes were treted with vinylimidzole to obtin MXene with
imidzole brushes on the surfce (QMXene-NH2) nd by solution csting dispersed in the chitosn
mtrix [15]. By ltering the rection time nd cid content, diverse MXenes could be developed by
HF (hydrouoric cid) etching crried out from room temperture to vrious tempertures. The
MXene nnosheets with terminl functionl groups re then blended with green biopolymers using
vrious processing techniques (listed in Tble 5.1) like solution processing, melt blending, electro-
spinning, vcuum-ssisted ltrtion, dip coting, polymeriztion nd others [23,36–37]. Enhnced
exfolition, lrge-scle delmintion of 2D MXenes with tilored thickness could be chieved from
the previously mentioned synthesis routes.

5.3 CHARACTERIZATION OF GREEN MXene NANOCOMPOSITES

Severl studies hve reported the chrcteriztion techniques employed on MXene-reinforced bio-
polymer nnocomposites [38–41]. The reports reveled the relevnce of MXene-bsed biopolymer
nnocomposites nd their brod ppliction prospects in the eld of mteril science [42–44].
The viscosity nd conductivity of net biopolymers nd biopolymers loded with 1 wt% MXene
were investigted by Elis et l. [12]. In their work, since the polymer/MXene solutions were elec-
trospun viscosity ws  prime fctor in controlling the morphology of nnobers. Low viscous poly-
mer solutions could not produce uniform nd continuous bers nd high viscous polymer solutions
led to difculty in ejections while electrospinning [45–48]. With the ddition of 1 wt% of Ti3C2Tx
MXene in PAA biopolymer,  slight vrition in viscosity ws observed. The viscosities of PEO nd
PVA incremented by 11.7% nd 8.7%, respectively, with the incorportion of Ti3C2Tx. This enhnce-
ment in viscosity of PVA nd PEO biopolymers is relted to the presence of hydroxyl groups on
Ti3C2Tx nd the hydrogen bonding effect between the biopolymers, which decides the rheologicl
behvior of  polymer. On the other hnd, in the cse of Ti3C2Tx/lginte/PEO solutions,  decre-
ment in viscosity by 10% ws observed with regrd to net PEO, owing to the repulsive interctions
92 MXene-Filled Polymer Nanocomposites

TABLE 5.1
Processing Techniques, Characterizations and Applications of MXene-Based Green
Biopolymer Nanocomposites
Characterization
Polymer/MXene Synthesis/Processing Methods Applications References
PVA, PEO, PAA/Ti3C2 Electrospun MXene/ Morphology, Viscosity, Sensors, moleculr [12]
MXene polymer nnobers Conductivity electronics, tissue
mesurement, XRD, engineering
FTIR
PLA/Ti3C2 MXene Melt mixing in XRD, AFM, XPS, CCTs Flme retrdnt [32]
Brbender Plsticorder LOI, SEM pplictions
nd then compression
molded
PDDA/PVA/MXene Composite lms vi Electricl conductivity, Energy storge devices [33]
VAF (vcuum-ssisted TEM, SEM
ltrtion)
PLA/MXene-modied Solution csting XRD, FTIR, TEM Flme retrdnt nd [34]
steric cid (SA) structurl pplictions,
PDMS coted M-lter Dip coting nd curing TEM, SEM, XRD, Sensors, EMI (electro [35]
pper (cellulose)/Ti3C2Tx Electricl conductivity mgnetic Interference)
Cellulose nnober Vcuum ltrtion SEM, TEM, Mechnicl EMI Shielding mterils, [53]
(CNF)/MXene pproch properties werble electronics nd
mesurement personl heting
systems
Chitosn/MXene modied Solution csting TEM, SEM, XRD, TGA Anion exchnge [15]
with Imidzole nd Mechnicl membrnes
properties
PDA300 (Poly dopmine Solution csting XRD, SEM, TEM, Lithium–ion btteries [13]
het-treted t 300°C)/ lithium–ion diffusivity
MXene mesurement
Ti3C2TxMXene/Alginte Solution csting XRD, SEM, FTIR, XPS, Removl of hevy metl [54]
biopolymer Hg2+dsorption ions (mercuric ions)
mesurements
Ti3C2Tx MXene/Chitosn Electrospinning XRD, SEM, TEM, Wound heling [43]
nnobers ntibcteril ctivity pplictions
Polydopmine/MXene Polymeriztion TEM, SEM, XRD, High-performnce [14]
cycling stbility rechrgeble btteries

mong the polynionic lginte nd decresed interctions between PEO/lginte with the ddition
of MXenes [12]. Another mjor nding reported by this group of reserchers is enhncement in the
conductivity of polymers with the incorportion of MXenes. The enhncement in the conductiv-
ity of the polymeric solution could be chieved by dding ionic slt or by djusting solvent rtios,
which could produce low-dimeter bers due to the high number of chrge crriers tht incresed
the polymer jet stretching. The electricl conductivity of 1 wt% MXene in PEO solution enhnced
by 74%, 34.6% in Ti3C2Tx/lginte/PEO solution nd 6.2% increse in Ti3C2Tx/PVA solution with
regrd to net polymeric solutions. With the incorportion of MXene in PAA biopolymer, the con-
ductivity ws reduced, which shows wek interctions between the MXene nd PAA polymer. The
morphologicl results from their study reveled the vrition in the dimeter of electrospun nno-
bers with the incorportion of MXenes in polymers. The verge dimeter of PVA ber incresed
by 32.9%, wheres there ws  decrement in the verge dimeter of the PEO ber by 20% nd in
Green Polymer Nanocomposites with MXenes 93

the PAA nnobers by 38.9% with the incorportion of MXenes. The reduction in ber dimeter
suggests the pplicbility of such bers in moleculr electronics, sensors nd tissue engineering due
to the improvement in conductivity [49–52]. Fourier trnsform infrred (FTIR) nlysis of elec-
trospun bers reveled the functionl groups nd vibrtion bnd corresponding to O–H, C–H nd
C–O stretch in MXene-reinforced polymer composites. A decrese in crystllinity ws observed
in PVA polymer owing to the hydrogen bonding between surfce termintion groups (hydroxyl)
on MXene nd biopolymer PVA, which limits the crystl growth of PVA. An enhnced nucletion
rte nd crystlliztion were reported for PEO, nd the ppernce of  new pek ws observed in
PAA spectr (conrmed by X-ry powder diffrction [XRD] nlysis), which is indictive of the
delmintion of nnober mts [12].
Hung et l. [32] reported the tomic force microscopy nd XRD nlysis ofTi 3C 2 MXenes,
which shows the exfolited MXenes of  thickness of 1.55 nm nd  dimeter of 0.69 μm. The
high spect rtios nd lrger d spcing promoted  uniform distribution of MXene in the PLA
mtrix. The flme retrdncy of PLA mtrix could be enhnced by the incorportion of intu-
mescent flme retrdnts (IFRs) re mde up of piperzine pyrophosphte (C 4H14N2O7 P 2),
phosphoric cid (H 3PO 4) nd zinc oxide (ZnO). The uniform distribution of MXenes nd
flme retrdnts in PLA mtrix ws very well studied using SEM nlysis nd energy dis-
persive spectroscopy (EDS) mpping (elements Ti, P, N). The flmmbility of MXene/IFR/
PLA composites ws nlyzed using UL-94 tests nd LOI (limiting oxygen index) tests.
The higher vlue of LOI indictes  strong flme retrdnt effect. PLA hs low LOI vlue
of 21.5% nd is highly flmmble with no rting (NR). Figure 5.2 demonstrtes the LOI in
percentge with respect to increse in MXene content in PLA mtrix nd its flme retrdnt
effect [32].
The incorportion of 1 wt% of MXene in PLA/IFR (11 wt%) mtrix enhnced the LOI to 160%,
nd the mximum het relese rte reduced by 64.6% (obtined by cone clorimeter tests [CCTs]),
nd in UL-94 tests, the smple chieved V-0 rting (Figure 5.3).

FIGURE 5.2 LOI vlues of PLA nnocomposite with increse in MXene loding [32].
Source: Reprinted with permission from Elsevier.
94 MXene-Filled Polymer Nanocomposites

FIGURE 5.3 LOI of PLA nnocomposites incorported with me retrdnt nd MXene [32].
Source: Reprinted with permission from Elsevier.

FIGURE 5.4 The mechnism of synergism of me retrdncy of biodegrdble PLA composites incorpo-
rted with MXenes nd IFR dditive [32].
Source: Reprinted with permission from Elsevier.

Morphologicl results, CCT nlysis, XPS nd XRD nlysis of MXene/PLA/IFR composites
represented the nnosheet brrier effect of nno TiO2 ctlyst nd 2D MXene sheets. Hence, the
proposed PLA biopolymer composite system hs the bility to enhnce chr formtion nd resists
me nd re hzrd (Figure 5.4). It indictes tht the ddition of n IFR system cn lrgely reduce
Green Polymer Nanocomposites with MXenes 95

the me spred rte of composite system. This is lrgely due to the brrier effect of the chr
lyer formed from the IFR (dditive) system, which covers on MXene surfce nd decreses its
wicking ction. During the burning of the mtrix nd the genertion of the chr lyer, the high-
energy MXene surfce is trnsformed into  crbonized rough surfce, which leds to wekening
of the wetting, spred nd ow of interfcil PLA melt, thus reducing the ctul me spred rte.
Furthermore, IFR retrds the combustion of the composites through generting gret mount of
gses nd developing n intct intumescent chr shortly fter the ignition. When prt of IFR ws
substituted by MXene, there is  tremendous decline in the smoke production rte (SPR) nd totl
smoke-relese rte (TSR). The rndomly distributed 2D MXene nnosheets provides  tortuous
pth effect tht would effectively prolong the diffusion routes of degrded products during burning
nd hinder the relese of gses.
Yu et l. [55] reported tht nno-TiO2 in MXene sheets promotes chrring of polyurethne mtrix
during burning by blocking the relese of voltiles. The compctness of chr lyer nd degree of
residue chrring re improved owing to the crosslinking rection promoted by MXene nnoly-
ers [56]. The genertion of pores nd crcks during combustion could be obstructed, providing n
improved brrier effect for het nd mss trnsfer [57].
Moreover, the inclusion of MXene nnosheets in PLA biopolymer with crbide content in Ti3C2
develops self-chrring, promotes chr formtion nd nlly gets encpsulted in crbon residue.
Owing to the high spect rtio of MXene sheets like grphene [58] nd other 2D mterils, there
is  dely in the relese of mmble voltile products nd offers  brrier to the trnsport of
oxygen from the tmosphere. MXenes, long with IFR, exhibit excellent synergistic effects for
enhncing the me retrdncy of PLA [32, 59–63]. In nother study, MXene ws incorported
into poly(dillyldimethylmmonium) chloride (PDDA) nd in  PVA biopolymer, which re neutrl
electriclly [33, 64–65]. The uthors reported excellent electricl conductivity, exibility nd con-
trolled thicknesses [65]. XRD nlysis reveled the ordered stcking of Ti3C2Tx s evidenced by 
shrp pek t 4.7°. With respect to pure Ti3C2Tx lms, there ws  pek shift to lower ngle side from
6.5°, which demonstrtes the intercltion of PDDA molecules mong MXene kes. In the cse of
PDDA/MXene composites nd PVA/MXene composites, there ws  shrp decrese in electricl
conductivity, the lm thickness could be tilored with loding of the polymer nd the lms were
exible nd freestnding. With the incorportion of polymer in MXenes, the distnce between the
kes increses nd they become less uniform. It is reveled tht most of the Ti3C2Tx lms exist
s single lyers within the composite (veried by high-resolution trnsmission electron microscopy
[HRTEM]) nd the distnce between the lyers incremented with polymer loding. Furthermore,
the conductivity (electricl) of the composites could be vried in  brod rnge from 22430 S/m to
zero bsed on the composition of PVA [33]. Yi et l. [34] observed the chrcteristic X-ry diffrc-
tion peks (9.5°, 19.2°, 34.0°, 36.8°, 39.0°, 41.8°, 48.5°, 52.4°, 56.6° nd 60.2°) [66–68] of Ti3AlC2
crystlline MAX phse nd conrmed its purity. However, fter tretment with n HF solution, the
diffrction pek corresponding to Al (39ο) disppered due to the removl of Al lyer from MXene.
Furthermore, lowered pek positions of Ti3C2Tx indicted the lrger interlyer spcing in Ti3C2Tx
thn Ti3AlC2, nd scnning electron microscopy (SEM) imges reveled the lmellr structure of
MXene, with ech lyer pproximtely 70nm thick [34]. FTIR nlysis could conrm the presence
of symmetric nd symmetric vibrtions of C–H in –CH2, indicting tht the SA ws ttched to
MXene, nd the shift in diffrction peks to new positions suggest tht Ti3C2Tx ws successfully
interclted by SA nd incresed the spcing between the lyers. Even fter the strong wshing in
ethnol, it ws observed tht SA grfting remined on Ti3C2Tx, which due to the strong rection
between hydroxyl groups on MXene nd crboxyl groups on SA.
The trnsmission electron microscopy (TEM) imges of Ti3C2Tx reported by Hu et l. [35] indi-
ctes  t lmellr structure (verge size of 0.58 μm) with wrinkles tht could promote electricl
conductivity. The specil morphology [34] nd bility to promote electricl conductivity conforms
to nother report by Ling et l. [33]. The SEM imges of cellulose M-lter pper shows the pres-
ence of porous microstructure, which rnges from few to  dozen microns, tht forms the bsis for
96 MXene-Filled Polymer Nanocomposites

the electriclly conductive pthwys. With the incorportion of MXene in M-lter pper, cellulose
bers re coted with MXenes nd interconnected MXenes re lled in the pores. As the number
of dip-coting cycle increses, with rise in loding of Ti3C2Tx, MXene network becomes more nd
more compct nd dense in comprison with M-lter/MXene composites with fewer dip cycles.
This interconnected network of MXenes nd cellulose bers provides the ow pth for chrge
crriers, cusing n improvement in the electricl conductivity [69]. The morphology of PDMS-
coted M-lter/MXene composites explins the tight bonding of MXenes with cellulose bers [35].
This is  fcile pproch for the lrge-scle green production of M-lter/MXene green compos-
ites for the genertion of exible, multifunctionl electromgnetic interference (EMI) mterils.
Zhou et l. [53] lso reported tht the incorportion of MXene long with cellulose nnober lyers
genertes multilyered MXene/polymer lms rrnged lterntively tht could be used s EMI
lms. A simple nd efcient vcuum ltrtion pproch ws followed for the preprtion of ex-
ible, robust lms of cellulose nnober nd MXenes. SEM imges reveled highly ordered lmell
microstructure of crbon nnober nd MXenes, nd no gps nd exfolitions were observed t the
interfce of multilyered MXene nd CNF (cellulose nnober) which indictes the exibility nd
the reson for improved mechnicl properties of the lm. Cellulose nnobers ct s brriers tht
could prevent “zigzg” nno-crck growth [70] in MXene lyers nd show enhnced mechnicl
strength (112.5 MP) nd toughness of 2.7 MJ/m3 compred to homogeneous CNF/MXene lm
nd freestnding MXene lm [53]. It ws reported by Wng et l. [15] tht imidzole functionl-
ized MXene (QMXene-NH2) could be homogeneously distributed in the chitosn mtrix. This
constructs OH–conduction chnnels within the membrne nd enhnces mechnicl nd therml
stbility of prepred composites [15].
Biodegrdble modied PDA (polydopmine, PDA) biopolymers were prepred by Dong et l.
[13] nd then incorported with highly conductive MXenes, imprting excellent rte cpbility,
high cpcity nd good cycling stbility. PDA mterils were synthesized from polymeriztion
rection of dopmine monomers. Het tretment of PDA ws crried out t different tempertures
(200°C, 300°C nd 400°C). The uthors proposed  simple het tretment t 300°C, which pro-
motes the superior electrochemicl performnce of PDA. SEM photogrphs of PDA revels the
sphericl prticles with dimeters of 300–500 nm, nd the polymer ws treted t different tem-
pertures: 200°C, 300°C nd 400ºC. In FTIR studies, compred with untreted PDA, het treted
PDA t 300 οC shows the increse of crbonyl C toms. The peks tht corresponds to ctechol
C toms disppered suggesting their oxidtion. XRD nlysis shows diffrction peks from 9
to 6 ο for PDA/Ti3C2Tx which indictes the increment in interlyer distnce from 0.98 to 1.47 nm.
The SEM imges show tht PDA/Ti3C2Tx (het-treted t 300°C) composite exhibited  lyered
morphology. The EDS elementl imges revel tht PDA is uniformly distributed in Ti3C2Tx /
PDA300 composite. The Ti3C2Tx /PDA (t 300°C) composite portryed high specic cpcities of
1190 mAhg−1nd 552 mAhg−1 t 50 mA g−1 nd 5 A g−1, respectively, when used s n node. The
2D lyered lmell nnostructure nd unsturted crbon–crbon bonds in the PDA biopolymer,
long with Ti3C2Tx (conductive) MXenes, promote excellent lithium–ion storge cpbility [13].
A sndwich-structured composite ws prepred by in situ polymeriztion of dopmine on the
surfce of Ti3C2Tx MXenes to form ordered mesoporous polydopmine (MPDA)/Ti3C2Tx by Li
et l. [14]. The verticlly oriented ordered MPDA lyers with nnopores of pproximtely 20 nm
provide  continuous diffusion chnnel, while Ti3C2Tx lyers gurntee  continuous electron ow
pth. Li et l. [14] lso conrmed its high rte performnce, cyclbility nd reversible cpcity,
which re the key chrcteristic requirements for high-performnce rechrgeble btteries s
suggested by Dong et l. [13] in their work. Another study [71] reveled the lmellr lyers nd
hydrophilic surfce of MXenes functionlized with sulfonte polyelectrolyte brushes (Ti3C2Tx-
SO3H) vi  fcile precipittion-cum-polymeriztion pproch. Sulphonted MXenes were used
s nnollers in chitosn biopolymer nd sulfonted poly(ether ketone) (SPEEK). The report
reveled the efcient proton trnsfer pthwy, which connects with conduction chnnels in poly-
mer phse. The incorportion of 10 wt% sulfonted MXene in polymer mtrices enhnced the
Green Polymer Nanocomposites with MXenes 97

proton conductivity with respect to SPEEK nd chitosn membrne by 144% nd 66%, respec-
tively [71].
In nother study [54], Ti3C2Tx MXene ws prepred using  nontoxic fcile pproch by etching
with NH4F insted of HF cid. A novel green nnocomposite ws synthesized by incorporting 2-D
MXene nd sodium lginte (SAG) biopolymer spheres. The MXene/Alginte biopolymers exhibit
high dsorption behvior of Hg2+ (mercuric ions) owing to the porous nture of polymer spheres
nd functionl moieties on biopolymer lginte, which ws conrmed by FTIR, SEM, XRD nd
XPS nlysis [54]. In the work reported by Elis et l. [43] Ti3C2Tx MXene kes were incorpo-
rted within chitosn nno-biopolymer bers vi n electrospinning process. SEM microgrphs of
MXene/chitosn reveled the thick networks of uniform-dimeter nonwoven bers. The brnching
of bers ws not observed, which explins the proper blnce of the electricl nd surfce tension
forces of Ti3C2Tx/chitosn solution during electrospinning. The brodened nd reduced pek inten-
sity of XRD diffrction peks suggests the interction between the MXenes nd chitosn nno-
bers. TEM microgrphs reveled the simultneous visuliztion of chitosn nd MXene kes in
the composite nd suggest the two types of orienttion s the embodiment of Ti3C2Tx kes within
the ber nd the protrusion of MXene kes [43].

5.4 MECHANICAL PROPERTIES OF GREEN POLYMER

BASED MXene NANOCOMPOSITES
It ws reported tht Ti3C2Tx lms of pproximtely 3.3-μm thickness presented  Young’s modulus
of 3.5 ±0.01 GP nd tensile strength of 22 ± 2 MP [33], which re comprble with grphene
oxide (GO) [72] nd crbon nnotube–bsed bucky pper [73]. At the sme time, it ws observed
tht MXene lms possessed better conductivity. PVA lm of 13 μm exhibits  tensile strength of
30 ±5 MP. With the incorportion of 10 wt% of MXene in PVA, tensile strength enhnced by
34%. A further increse in MXene loding to 40 wt% in PVA/MXene lms enhnced the Young’s
modulus to 3.7 ±0.02 GP, the tensile strength to 91 ±10 MP nd  higher strin t brek of
4 ±0.5% in comprison with other lodings of MXene. The generl increse in strength nd stiff-
ness of these composite lms indictes the efcient stress trnsfer from the mtrix to MXene lyers
nd suggestive of strong interfcil bonding between the MXenes nd the PVA polymer [74]. The
hydroxyl groups, which re termintion groups on MXenes cts s  binder between the MXenes
nd PVA polymer. Reports suggested tht MXene/PVA lms rolled into cylinders by controlling
the PVA–MXene rtio demonstrte enough tensile nd compressive strength tht they could be
used for energy storge device pplictions [33,75]. The mechnicl properties of pure-PLA nd
SA-modied PLA composites with different contents of MXenes 0.2, 0.5, 1 nd 2 wt%) were
reported by Yi et l.[34]. At low loding of 0.5 wt% of MXene it is observed tht PLA composites
exhibited excellent toughness, wheres it decresed when the ller content incresed to 1 wt%.
The elongtion t brek incresed to 131.6%, pproximtely sixfold in comprison with pure PLA
biopolymer. This increse in elongtion t brek is owing to two fctors nd could be due to the
plsticizing effect of SA nd the incresed chin mobility of PLA or owing to the induced sher
yielding cused by the incorportion of rigid llers. Beyond 1 wt% of MXene toughness decresed
due to the formtion of ggregtes. MXene kes prevent the movement of polymer chins due to
lrge specic surfce re. The reported results indicte tht even with  smll wt% of MXenes
(Ti3C2Tx),  signicnt increse in mechnicl properties could be chieved. The percentge of
crystllinity nd the therml stbility of SA-modied MXene/PLA composites ws lso found
to be very prominent even t low lodings of MXene, which shows the pplicbility of PLA bio-
polymer in novel pplictions [34]. Mechnicl properties of chosen green polymer-bsed MXene
nnocomposites re reported in Tble 5.2.
It ws reported [53] tht freestnding MXene lm shows  low tensile strength (3.5 MP) nd
strin t the brek of 0.6%, owing to the wek interction between MXene sheets. For  uniform
stress distribution, polymer binders like PVA nd CNF were employed, which contribute to strong
98 MXene-Filled Polymer Nanocomposites

TABLE 5.2
Tensile Properties of Green Biopolymer/MXene-Reinforced Nanocomposites
Composite Nomenclature Mechanical Properties References
PVA/Ti3C2Tx Tensile strength: 91 ± 10 MP; [33]
Ti3C2Tx:40 wt% Young’s modulus: 3.7 ± 0.02MP; Elongtion t
PVA lm thickness: 12 μm brek: 4 ± 0.5MP
PLA/Ti3C2Tx-g-SA (Steric cid) Elongtion t brek: 131.6 ± 18%; Yield strength: [34]
Ti3C2Tx-g-SA: 0.5 wt% 56.7 ±1.4M P; Young’s modulus: 2.6 ± 0.1 GP
Alternting Cellulose nnober/MXene Tensile strength: 112.5MP, Toughness 2.7MJ/ [53]
CNF5@MXene4 lm m3, strin t brek 4.3%
Chitosn/MXene-NH2 Tensile strength: 41MP; Strin t brek: 0.045% [15]
MXene: 7.5 wt%
Chitosn/SPEEK (sulfonted (poly ether Tensile strength: 39MP 50% strin [71]
ketone))/Ti3C2Tx-SO3H-5 wt%

interction nd fcilitte stress trnsfer [76–78]. The homogeneous CNF-reinforced MXene lm
presented  tensile strength of 92.1 MP nd  strin t brek of 2.2%, which is lower thn free-
stnding pure CNF lm. Hence, the uthors proposed lternting  multilyered structure long
with CNF lyers. Multilyered CNF nd MXene lms with 50% CNF content undergo plstic yield-
ing, nd their strength nd toughness re comprble with tht of CNF lm. With the incorportion
of MXene lyers vrying from 1 to 5%, tensile strength, the toughness nd strin t brek were
enhnced in the rnge of 86.6 to 112.5 MP, 1.6 to. 2.7 MJ/m3 nd 3.1 to 4.3%, respectively. At
the optiml content of CNF 5 lyer nd MXene 4 lm, the chieved mechnicl properties ws
equivlent to pure CNF lm. It ws lso observed tht t this optiml content of CNF5MXene4
lm, it could withstnd  weight of 500 g without filure representing the exibility of lternte
multilyered composite lms [53]. It is found tht QMXene-NH2 (Imidzole-modied MXene) hs
 tensile strength of 27.5MP, Young’s modulus of 920.2MP nd strin t brek of 5.5%. With
the incorportion of QMXene-NH2 in semi-crystlline chitosn biopolymer tensile strength rised
to  mximum of 41 MP, but elongtion t brek ws slightly reduced [15]. The incorportion of
sulfonted MXenes in SPEEK nd chitosn–polymer mtrices enhnced the mechnicl strength
signicntly. It is reported tht the tensile strengths of hybrid membrnes obtined re greter thn
10.4 MP, which indictes the possibility to include sulfonted MXene in mtrices, prticulrly in
green biopolymers to enhnce its structurl stbility [71].

5.5 APPLICATIONS OF GREEN POLYMER NANOCOMPOSITES WITH MXenes

A bioderived electrode mteril ws mde from PDA, which is very cost-effective nd mintins
sustinbility by incorporting nnostructured Ti3C2Tx MXene nd could be used s n lterntive
in lithium–ion btteries. The electrochemicl performnce of biopolymer PDA could be improved
in synergism with MXene nd under  simple het tretment t 300°C. The prepred composite
exhibits enhnced rte cpbility (remining 552 mAh g−1 t 5A g−1) nd retined 82% cycling st-
bility even fter 1000cycles nd exhibited  high cpcity of 1190 mAh g−1, 50mA g−1). The super-
lithition of the C–C (unsturted) bonds in PDA in combintion with the conductive substrte
of MXene leds to the high performnce of biopolymer MXene composite [13]. Li et l. [14] lso
proposed the pplicbility of green MXene composites for energy storge device pplictions owing
to their cost-effectiveness, exibility nd environmentl friendliness. For enhnced electrochemicl
performnce the uthors proposed  sndwich-lyered composite structure of polystyrene-polyeth-
ylene oxide block copolymer, long with Ti3C2Tx MXene, which promotes nnopore chnnels for
Green Polymer Nanocomposites with MXenes 99

FIGURE 5.5 Ordered mesoporous structure of MXene nnosheets by direct polymeriztion nd het tret-
ment of polydopmine biopolymer [14].
Source: Reprinted with permission from ACS publictions.

diffusion of ions nd continuous electron ow pth. The ordered MPDA structure (Figure 5.5) with
MXenes in the composite fcilittes the ion trnsfer pth, enhnces the vilble surfce re for
lithium ions nd demonstrtes excellent rte performnce, reversible cpcity nd cycling life. The
ordered MPDA/Ti3C2Tx electrode chieved  specic cpcity of 1000 mA hg−1 t 50 mA g−1. A
high cpcity of 430 mA h g−1 ws lso mintined fter 600 cycles t 1A g−1. The electrochemicl
performnce of ordered MPDA/Ti3C2Tx ws evluted using cyclic voltmmetry (CV) vi hlf-cell
congurtion.
From the cyclic voltmetry nlysis of ordered (MPDA)/MXene composite, the pek t 1.5 nd
0.67 V is ttributed to the ddition of lithium to unsturted nitrogen nd enoliztion rection of
100 MXene-Filled Polymer Nanocomposites

lithium with crbonyl oxygen [79–80]. The intercltion of Li+ ions into C6romtic rings cor-
responds to the genertion of strong electrolyte interphse (SEI) lm t the interfce between the
electrode nd the electrolyte nd ws conrmed by voltmetry nlysis [81]. The redox properties
of ordered MPDA/Ti3C2Tx re highly reversible, which ws indicted by overlpping of peks in CV
curves. The chrge–dischrge curves show the Li+ de intercltion nd the low columbic efciency
t the initil cycles ws incresed to 95% from the third cycle. These observtions suggest tht gen-
ertion of mesoporous structure in PDA composite cn enhnce the overll reversibility of rections
nd cpcity with lithium ions. The heterostructure of ordered MPDA nd MXene corresponds to
high rte cpbility nd cpcity [14,82]. The recent progress nd dvnces in PDA/MXene com-
posites ws lso discussed by other group of reserchers [83–85].
In nother study, Myerberger et l. [12] reported the lignment of Ti3C2Tx kes within the ber
xis of biopolymer PVA nd PAA polymer nd observed the protruded kes from the bers. This
is importnt for biomedicl pplictions (ntibcteril wound heling), where protruded MXene
kes could hrm bcteril membrnes [12]. The uthors lso reported the ntibcteril proper-
ties of electrospun Ti3C2 MXene kes with chitosn nnobers for ntibcteril wound dressing
pplictions [43]. They demonstrted  reduction of 95% nd 62%, respectively, of bcteril colony
units ginst grm-negtive Escherichia coli (E.coli) nd grm-positive Staphylococcus aureus
(S.aureus) with 0.75 wt% Ti3C2Tx- loded nnobers for 4-hour tretment. Cytotoxicity studies
proves the nontoxicity of MXene/chitosn bers. The verge cell vribility reltive to the control
specimen ws bout 85% t different test concentrtions, which demonstrted the non-cytotoxicity
of MXene/chitosn composite mts to bcteril cells over n exposure time of 72 hours [43].
The mechnism of the ntibcteril nture of MXene kes is relted to the direct contct of
bcteril cells with MXene kes [43,86]. TEM nlysis reveled the penetrtion of MXene kes
through bcteril membrnes, cusing direct mechnicl destruction tht lso conforms with nti-
bcteril ctivity of GO [87–89]. In ddition, hydrophilic negtively chrged surfce termintion
functionl groups (–F,–O, –OH) on MXenes promotes the gglomertion of bcteri, cusing nti-
bcteril ctivity. About 200 μg mL−1 of colloidl suspension of Ti3C2Tx ginst E. coli indictes
99% bcteril inhibition zones [43,86,90–91]. Another study reveled the pplicbility of green
MXene composites for the cpture of hevy metl ions from wste wter, owing to its lrge spe-
cic surfce re, high porosities, oxygented functionl groups nd unique internl structure of
MXenes. The synthesized microspheres of MXene–SAG spheres (MX-SAG) composite under
extreme pH conditions (0.5–1.0M HNO3) demonstrted n dsorption cpcity of 932.84 mg/g for
the removl of mercuric ion (the highest mong the reported dsorbents) nd shows excellent repro-
ducible properties [54]. The Ti3C2Tx MXene is superior to GO, owing to the presence of termintion
surfce groups, hydrophilic nture nd chemicl stbility, where GO lcks functionl groups on the
surfce to dsorb metl ions [92].
The MX-SAG biopolymer composite microspheres possess  unique sphericl structure tht
entrps Hg2+ ions nd provides sufcient binding loctions [54, 93–95]. Figure 5.6 shows the com-
prtive performnce of MX-SAG biopolymer composite nd GO/SAG biopolymer composite
on the dsorption efciency of mercuric ions. Zhng et l. [96] lso reveled the pplicbility of
MXene-bsed green polymer composites to dsorb environmentl toxicnts like hevy metl ions,
rdionuclides, orgnic dyes nd gs molecules nd even its sensing cpbility [96–97].
The pplicbility of MXenes in supercpcitor pplictions ws discussed by Qin et l. [16].
The MXene/biopolymer composite pper electrodes re obtined by self-ssembly of negtively
chrged Mo1.33 CMXene nd mine ctions functionlized lignin. The intercltion of L-DEA
(lignin-diethnolmine), long with MXene, enhnced the interlyer spcing between MXene
sheets nd promotes improved chrge trnsfer nd the composite electrode possessed  mximum
cpcitnce of 503.7Fg−1. The mine-modied lignin-bsed biopolymer with MXene lso exhib-
ited excellent stbility nd rte performnce. The Mo1.33C/L-DEA/exfolited grphene/ruthenium
oxide nnoprticle composite device provides n energy density of 51.9 nd 27.8 Whkg−1 t  volt-
ge window of 1.35 V nd t power densities of 338.4nd 40095 Wkg−1 nd hence cn be utilized
Green Polymer Nanocomposites with MXenes 101

FIGURE 5.6 Adsorption efciency of SAG biopolymer spheres long with MXene on mercuric (Hg2+) ion
removl in comprison with GO [54].
Source: Reprinted with permission from Elsevier.

to design high-potentil supercpcitors with enhnced energy density [16]. The cellulose nno-
ber/MXene (CNF/MXene) composite lms could enhnce the electricl conductivity by 621 S
m−1[53]. The reection-bsorption zigzg reection mechnism of lternting multilyered CNF/
MXene lms demonstrted excellent EMI shielding effectiveness of pproximtely 40 dB. The
uthors [53] observed tht owing to the impednce mismtch lmost 90% of incident electromg-
netic (EM) wves re immeditely reected. When EM wves pss through the MXene lms, they
hit holes, dipoles nd electrons, cusing mssive polriztion nd losses t interfces. These losses
id the high ttenution of EM-wve energy, cusing EM-wve bsorption by these lms. This
mechnism of EMI reection nd bsorption of cellulose nnober/MXene lms could contribute
to EMI shielding performnce but hs reltively low electricl conductivity. This drwbck could
be circumvented by the presence of lternting multilyered CNF/MXene lm tht could rise the
impednce mismtch of the specimen–ir interfce nd thereby improve the reection of incident
electromgnetic wves t the interfce. Furthermore, EM wves trnsmit from one MXene to the
other MXene lyers, nd lternting lyered structures cuse  high-impednce mismtch between
the cellulose nnober biopolymer nd the MXene lyer. This promotes zigzg reection between
the biopolymer lyer nd the MXene lyer nd results in  high-bsorbing ttenution of EM wves
nd very little trnsmittnce [76, 98–100]. This mechnism of MXene incorported green nno-
composite ccounts for  signicnt increse in EMI shielding effectiveness [53,101].
Another study [15] disclosed the signicnce of MXene-bsed green chitosn biopolymer com-
posite s  conductive membrne enhncing OH− conduction up to 172% owing to continuous ion
conduction chnnels previling in the composite. This justies the potentil of MXene green nno-
composites in the development of nion exchnge membrnes for lkline fuel cell pplictions
[15]. The SPEEK/chitosn/Ti3C2Tx composites demonstrte the enhnced proton conductivities nd
t incorportion of 10 wt% of MXene, conductivity enhnced by 81% nd 146% under 120°C owing
to the proton trnsfer pthwys provided by sulfonted MXene interclted in the polymer phse
[71]. Wng et l. [102] proposed  green, exible nd efcient pproch for the development of
102 MXene-Filled Polymer Nanocomposites

3DMXene incorported with PDMS mtrix nd these composites exhibited  high electricl con-
ductivity of 5.5 S/cm. Even t low vol% of 2.5, MXene therml conductivity enhncement ws bout
220% nd decresed electricl resistnce. The composite system hs its relevnce in the develop-
ment of triboelectric nnogenertors with cpcitor structures nd could be pplied to sensors nd
energy hrvesters [33,37, 102–106]. Some other studies on MXene-bsed nnocomposites reveled
their ppliction in photoctlytic hydrogen production showing high ctlytic ctivity [44,107].

5.6 CONCLUSION AND FUTURE DIRECTION

The objective of this chpter ws to elucidte the most cost-effective, environmentlly friendly, fc-
ile pproch to synthesis strtegies for MXene/biopolymer composites. A review of the methodol-
ogy of preprtion of green polymer/MXene nnocomposites, its morphologicl structure, vrious
property enhncements demonstrting the relevnce of MXene-bsed green nnocomposites in vr-
ious sectors of mterils engineering ws presented. The percentge of enhncement of the proper-
ties of biopolymers, long with MXene, ws reported, nd the methods/lterntive pproches for
improving the properties of biopolymer were explicted. MXene/green biopolymer composites hve
received incresing ttention owing to their wide rnge of compositions, enhnced conductivity
nd dispersibility. Although different synthesis routes nd processing of MXene/biopolymer green
nnocomposites hve been reported in the pst decde, there re still chllenges nd hurdles in its
prcticl pplictions. Modulting the surfce functionl groups on MXenes is  mjor fctor tht
produces ctive binding sites nd improves the performnce of MXenes once they re incorported
in  biopolymer. Bsed on the size of specic surfce re, the porosity nd the type of functionl
group performnce of MXene green nnocomposites could be vried. The res like electromg-
netic shielding, ntibcteril pplictions nd electrochemicl energy storge device development,
mong others, will continue to be the focus of reserch in the future.

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 6 Thermoset/MXene
Nanocomposites
Benjamin Tawiah and Sarkodie Bismark

CONTENTS
6.1 Introduction ........................................................................................................................... 109
6.2 Thermoset Nnocomposites .................................................................................................. 110
6.3 Thermoset/MXene-Bsed Nnocomposites.......................................................................... 113
6.4 Thermoset/MXene Nnocomposites Fbriction.................................................................. 115
6.4.1 In Situ Polymeriztion Blending ............................................................................... 115
6.4.2 Solution Mixing/Blending......................................................................................... 116
6.4.3 Hot Press/Injection Molding ..................................................................................... 118
6.4.4 Vcuum-Assisted Filtrtion....................................................................................... 118
6.4.5 Resin Trnsfer Molding............................................................................................. 119
6.4.6 Templte-Assisted Fbriction.................................................................................. 119
6.4.7 Ionic Intercltion nd Soniction-Assisted Method ................................................ 122
6.5 Structure nd Morphology of Thermoset/MXene Nnocomposites ..................................... 123
6.6 Mechnics of Thermoset/MXene-Bsed Nnocomposites ................................................... 124
6.7 Appliction of Thermoset/MXene-Bsed Nnocomposites.................................................. 126
6.8 Chllenges in Thermoset/MXene Nnocomposites: Fbriction nd Applictions.............. 127
6.9 Conclusion............................................................................................................................. 128
References...................................................................................................................................... 128

6.1 INTRODUCTION
Polymers hve become n importnt nd ubiquitous prt of humn existence to the extent tht
one cnnot imgine life without them. The ppliction of polymers in recent yers hs expnded
to hitherto unimgined res thnks to the dvncement in polymer science nd engineering.
One importnt re in polymer reserch nd development sperheding the widespred pplic-
tion of polymers in mny elds is polymer nnocomposites (PNCs; Aghmohmmdi et l., 2021;
Krishnmoorti nd Vi, 2007). PNCs hve demonstrted distinctive physicochemicl properties
tht re fr distnt from their components cting lone. The functionlity of nnocomposites is
fundmentlly relted to the efcient properties of the constituents, composition, structure, nd
interfcil interctions t the nnoscle level. The unique nnoscle properties of the individul
components nd the good interction of the components s  result of their creful design results
in excellent PNC products with wide engineering pplictions (Sliozberg et l., 2020). Among the
vrious types of nnocomposites, thermoset/MXene nnocomposites hve gined more ttention
recently becuse these nnocomposites exhibit unique nd benecil properties compred to other
nnocomposites.
Thermoset/MXene nnocomposites re mostly  multicomponent solid products contining
nnoscle mteril(s) (100nm or smller in dimension) dispersed in  thermoset or thermoplstic
mtrix. These form  new group of nnocomposites possessing essentil properties, such s high
therml stbility, high mechnicl performnce, nd excellent brrier properties. Currently, poly-
mer nnocomposites re used in mny industries, including vehicles, trnsporttion, civil engineer-
ing, nd tools used in sports nd recretionl ctivities (Go et l., 2020).
DOI: 10.1201/9781003164975-6 109
110 MXene-Filled Polymer Nanocomposites

With the quest to expnd the usbility of thermoset nnocomposites, the meliortion of func-
tionlity of polymer nnocomposites via the introduction of llers hs received keen interest
recently (Aghmohmmdi et l., 2021). Due to the importnt chrcteristics of inorgnic nno-
mterils, they nd pplictions s llers to enhnce the performnce nd widen the pplictions
of polymer nnocomposites. These llers include bers from textiles wste, wood, nd MXene nd
other two-dimensionl (2D) mterils such s grphene, lyered double hydroxide (LDH), molyb-
denum disulde (MoS2), hexgonl boron nitride (HBN), phosphorene nd MXene. In recent
yers, the incorportion of MXene in polymer mtrix hs yielded numerous publictions in mny
different res of pplictions. MXene is  series of 2D compounds reveled to hve  promising
prospect for reinforcement of nnocomposites, due to their protble mechnicl nd conductive
behvior in het nd electricity. Stoichiometriclly, MXene is dened s Mn+1XnTx, in which n =
1, 2, or 3, “M” is  trnsition metl “d”, “X” is crbon nd/or nitrogen, nd the Tx is ssignble to
uorine, oxygen, nd/or hydroxyl termintions (F, O nd/or OH) (Mishr et l., 2017). The fbric-
tion strtegies used to produce MXene from the MAX phse re responsible for the termintions.
Experimentl studies reveled tht the M-A bonds re fril thn M-X bonds in the MAX phse. As
 result, the extrction of A elements from MAX phses by etchnt leds to the formtion of novel
mterils known s MXene (Alhbeb et l., 2017; Kim et l., 2021). In ddition, the development
of essentil ionic groups further mkes MXene  Verstile nnomteril (Come et l., 2015).
Resistnce to elstic deformtion, good conductivity to het nd electricity re mong the veri-
tble chrcteristic fetures of MAX phses. Also, the inherent functionl groups of MXene, good
mechnicl properties, self-lubricting, nd high therml conductivity re considered to be the
most preferble reinforcements for polymeric mterils (Aghmohmmdi et l., 2021). Moreover,
the hydrophilic properties of MXene enble good interction with polr polymeric constituents in
composites, which is not commonly shown in other 2D nnomterils. The hydrophilic properties
of MXene is due to the surfce terminting groups such s OH nd –O–nd F resulting from the
chemicl etching of Al. MXene hs been widely used in reserch for the production of stte-of-the-
rt energy mterils, lubricnt dditives, nd polymer-reinforced mterils (Song et l., 2021b; Go
et l., 2020; Tontini et l., 2020; Ming et l., 2021; Verger et l., 2019; Sun et l., 2021; Jy Prksh
nd Kndsubrmnin, 2021; Zhng et l., 2016). Also, the physicl nd electricl functionlities
of MXene hve been estblished tht the ddition of low MXene lodings into polymer systems
enhnces the tribologicl nd corrosion resistivity of nnocomposites.
Thermoset polymers hve been mixed with MXene using mny different mens of nno-
composite preprtion techniques to mutully benefit the finl product (nnocomposites).
Mny studies on thermoset/MXene nnocomposites hve been done with interesting results
(Wng et l., 2019; Ji et l., 2020; Liu et l., 2020; Crey nd Brsoum, 2021; Go et l., 2020;
Song et l., 2021b). Therefore, this chpter discusses thermoset polymer/MXene composites,
the impct of MXene on thermoset polymers’ mechnicl nd therml behvior, fbriction
strtegies nd the structurl morphology, chllenges, nd pplictions of thermoset/MXene
nnocomposites.

6.2 THERMOSET NANOCOMPOSITES

Thermosets re essentilly polymers possessing the bility to crosslink their inter-nd intrmolecu-
lr chins to form  solid polymer network (Dodiuk, 2013). Unlike thermoplstic polymers, ther-
moset polymers network covlently crosslinks nd become irreversible fter mnufcturing. This
implies tht thermoset polymers cnnot be reshped or remelted fter fbriction. Upon heting or
incorporting curing gents (such s mine hrdeners) from the resin stte to the nl solid stte, the
bsic polymeric constituents of thermosets undergo n irrevocble chnge in the chemicl structure.
The route through which the monomers re trnsformed into  solid, nonsoluble, nd nonfusible
mtrix, which is mostly the lst fbriction step of  polymeriztion rection is clled curing (Roller,
1986). Comprtively, the irreversible cross-linkge in thermosets grnts good mechnicl strength
Thermoset/MXene Nanocomposites 111

nd chemicl nd het resistnce thn thermoplstics. Additionlly, thermosetting resins possess
numerous benets over thermoplstic resins regrding their processbility, cost, dimensionl stbil-
ity, environmentl stress crcking resistnce, nd scope for modiction (Rtn, 2012). This mkes
thermoset polymer composites more preferble for protective cotings, erospce composites, com-
puter chip pckging, nd structurl pplictions.
Thermoset nnocomposites hve the potency in dvncing the utility of composites tht surpss
scientic discoveries in recent decdes regrding mterils employed in the production of nnocom-
posites. The nnostructure fbricted by  nno-phse in polymer mtrix represents n indispens-
ble booster to the structurl properties of the polymer in recent yers. As  result, the explortion
of  huge vriety of thermoset nnocomposites nd brod knowledge of the fbriction methods
nd their properties hve been studied extensively. Notbly, wht distinguishes thermoset nnocom-
posite from trditionl composites is the extent of control in their production, processbility, nd
functionlity in  specic eld of ppliction tht cn be chieved nerly down to the tomic scle.
Also, in the eld of dvnced technology, thermoset nnocomposites re used s substitutes for
wood nd steel, especilly in the erospce nd militry sectors due to the multiple functionlities
of the composites produced with the presence of thermosets reinforced with llers like crbon bers
nd glss. There re numerous types of thermosets possessing different properties, reltble to their
structure nd constituents. Thermoset polymers re clssied into phenolic resins, mino resins
(polyimides [dinhydride, dimine], nd bismleimides), polyester resins, silicon resins, epoxy res-
ins, vinyl esters, nd polyurethnes (Zferni, 2018). Among these, epoxy hs gined tremendous
pplictions in mny works due to its high performnce.
Thermoset epoxy exhibits unique properties such s  low tendency to shrink, good compt-
ibility, strong dielectric properties, long-term stbility, reltively low cost, nd so on. Epoxy resins
possess mny rective groups, which determine the functionlity of epoxy. The greter the number,
the higher the functionlity. Some of the commonly used epoxies include diglycidyl ether of bisphe-
nol-A (DGEBA) nd bisphenol-F (DGEBF), tetrglycidyl dimino diphenyl methne (TGDDM),
nd triglycidyl resin of p-minophenol (TGAP), Figure 6.1. However, the most widely used re the
DGEBA-bsed.
Curing s the nl step of polymeriztion tkes plce by the rection of rective groups of epoxy
nd  primry dimine or n nhydride commonly referred to s hrdeners.
In generl, unsturted polyesters compose of polymer units linked vi ester groups re mong the
erliest ctegories of thermoset polymers widely employed in ber-reinforced polymer composites.
Polyester resins re viscous, even with some being solids hving  low melting point nd  low molec-
ulr weight. The unsturted polyesters lso possess C=C bonds in the min chin which permits

N CH2 N

H3C CH3
Diglycidyl ether of bisphenol-A Tetraglycidyl dimino diphenyl methane

H
N
HO OH
H
4,4-dihydroxydiphenylmethane of bisphenol F Triglycidy resin of p-aminophenol

FIGURE 6.1 Chemicl structure of some commonly used epoxies.

112 MXene-Filled Polymer Nanocomposites

crosslinking rections of polymer units. One chrcteristic dvntge of unsturted polyesters is

their bility to rect with the monomeric vinyl group due to the presence of C=C bonds, which
fcilittes the crosslinking of the chins. Primrily, styrene nd α-methyl-styrene re employed s
co-monomers to ensure the occurrence of required cross-linkges. Crosslinked polyester products,
such s minoplst or phenol-ldehyde resins, tend not to be prticulrly rigid (Miskolczi, 2013).
Thermoset polyester composites re typiclly fbricted by polycondenstion rections.
Aside from epoxy nd unsturted polyesters, vinyl ester resins re other types of thermoset
polymers. These re  specil type of polyester used to fbricte high-performnce composites
with discrete mteril properties t  low cost compred to numerous unsturted polyesters. The
moleculr structure of vinyl esters re similr to polyesters but differs in the loction of their rec-
tive sites. Vinyl ester resins re primrily composed of mixtures of styrene nd methcrylte epoxy.
Unlike polyester, vinyl esters hve fewer cross-linked bonds owing to the cross-linking of C=C
double bonds t the end of the polymer chin (Miskolczi, 2013b). Styrene s  constituent of vinyl
ester hs one rective vinyl group, but vinyl ester monomer hs severl rective vinyl end groups.
The rective groups of vinyl ester provide crosslinking cpcity nd brnching while styrene revels
only liner chin extension. The polymeriztion of vinyl ester units tkes plce by free rdicl chin
growth (Chigwd et l., 2005). It hs been fbricted with mny different nnomterils (such s
nnocly) to improve its performnce nd broden its ppliction. Vinyl ester nds ppliction in
re retrdncy, wind turbine mnufcture, utomotive industries, nd constructions.
Another group of thermoset polymer system worth mentioning is those bsed on formldehydes.
Formldehydes re typiclly dhesive resins with severl merits in terms of cost, fst curing speeds,
low curing tempertures, good pnel performnce, nd, in most cses, colorless, which mkes them
idel cndidtes for composites fbriction despite their perceived dverse helth nd environmentl
effects. The formldehyde dhesive resins in this ctegory include phenolic resin, melmine forml-
dehyde resin, nd polyurethne (Mrtin et l., 2006; Singh nd Thkur, 2009). The thermosetting
formldehyde resin bsed on ure is prticulrly produced t lrge scle globlly, with production
exceeding 5 million metric tons (t) nnully due to its wide pplictions in plywood, berbord, nd
prticlebords (Song et l., 2021). The ppliction of the vrious thermoset formldehyde-bsed
resins in composites fbriction hs been explored. In  study conducted by Zheng nd coworkers,
grphene oxide–poly(ure–formldehyde) ws used to fbricte epoxy composite for corrosion pro-
tection in hrsh environments, nd excellent results were chieved (Zheng et l., 2018). Similrly,
 thermlly stble, lightweight, nd biodegrdble Sgo-ber prticle bord bonds were fbricted
using ure formldehyde to form  composite mteril ment for vrious pplictions (Ching et l.,
2016). Despite the wide pplictions of formldehydes in composite fbriction, there re no suf-
cient dt on the use of MXene with formldehyde-bsed resins for composite fbriction.
In this decde, polymeric mterils hve found considerble pplictions due to their unique proper-
ties, such s low cost, low density, corrosion resistnce, nd ese of processing. For instnce, polymeric
cotings re minly employed s protective cotings for metllic substrtes to hinder the corrosion of
the substrte. However, the low mechnicl, electricl, energy storge cpcity, nd tribologicl proper-
ties of polymeric mterils hve restricted their brod utiliztion. Therefore, vrious pproches hve
been introduced for improving the mechnicl, electricl, me retrdncy, tribologicl performnce,
nd so on of thermoset polymer composites. A prominent route for meliorting the performnce of
thermoset polymer composites is the incorportion of nnomterils into their mtrices. These mteri-
ls help improve the properties of thermoset such s electricl, het, mgnetic, mechnicl, wer prop-
erties, nd others, hence incresing their level of utility in mny other res nd widening their scope of
ppliction. Severl nnomterils in  form of 1D, 2D, nd 3D hve been used for elevting the proper-
ties of polymers. It hs been demonstrted tht the 2D nnomterils, such s grphene, molybdenum
disulde, nnocly, MXene, nd others, re promising reinforcements for the polymeric mtrices due to
their discrete morphology nd properties (Fu et l., 2019; Frigione nd Lettieri, 2020).
Thermoset/crbon nnotube (CNT) nnocomposites hve been successfully fbricted by resis-
tive heting–ssisted inltrtion followed by curing of the polymer mtrix resin (Kim et l., 2014).
Thermoset/MXene Nanocomposites 113

The improved wetting nd dhesion of the polymer resin to the CNT yielded  signicnt improve-
ment of the thermoset/CNT nnocomposite, including enhnced mechnicl properties (Kim et l.,
2014). Also, CNTs hve been incorported in nnocomposites to increse therml conductivity nd
therml stbility (Dong et l., 2018). Other usble llers include bers (crbon bers, glss bers,
rmid bers, etc.), strch, nd chitosn (Mtos Ruiz et l., 2000). These textiles wste in the form
of wste or technicl bers re incorported in thermoset to increses their mechnicl properties
s observed in  study by Zunjrro Kmble nd coworkers. Among ll the thermosets, epoxies
re one of the most verstile ctegories, with  wide rnge of ppliction elds owing to their good
rectivity, which enbles them to bond well to bers (Gibson, 2017).
In this er of sustinble production, the biodegrdbility of thermoset polymers hs lso
been improved by the incorportion of biodegrdble mterils, such s cellulose nd protein
bers, s reinforcing components of the mtrix. In ddition to their biodegrdbility, they com-
bine good mechnicl properties with low density (Mtos Ruiz et l., 2000). New reserch
development of thermoset nnocomposites in the re of me retrdncy is lso offering sig-
nicnt dvntges over conventionl me-retrdnt formultions nd pure thermoset polymer
composites. This cn give rise to intrinsiclly new properties tht re not displyed by the pure
components. Such new properties typiclly originte from the chnge of the polymer nture
in the surrounding of the ller. The polymer cn be bsorbed by the ller surfce or trpped
between llers.

6.3 THERMOSET/MXene-BASED NANOCOMPOSITES

Despite the mssive pplictions of thermosets, properties such s poor mechnicl nd electricl
properties (poor exibility, insultion to het nd electricity, poor wer properties, etc.) hve hin-
dered the growth of thermosets in certin pplictions prticulrly in res where friction resistnce
is required, in energy storge, electromgnetic shielding, nd vibrtion-resistnt components in
structures nd gdgetry (Mgbemen et l., 2018; Pul nd Robeson, 2008). One of the min resons
ssocited with the chllenges is the difculty in meliorting the previously mentioned proper-
ties of epoxies by physicl or chemicl mens. The incorportion of other mterils is necessrily
required to improve upon its qulities to expnd its ppliction. Thermoset epoxy resins re the most
frequently used clss of thermoset polymer, hence the recent increse in reserch on the preprtion
nd ppliction of thermoset/MXene nnocomposites.
Nnoprticles endow polymer composites with improved functionlities, such s conductivity,
enhncement in ctlytic ctivity for environmentl remedition, nd pplictions in detecting gses,
nd mny more. Due to the discrete chrcteristics of MXene nd their multiple vritions, explo-
rtion into their usge s nnollers hs become  mjor focus since their discovery (Crey nd
Brsoum, 2021) Aside MXene, mny different mterils hve been incorported with thermoset
to form nnocomposites. Among them re nnomterils like grphene, CNTs, montmorillonite,
nd lyered hydroxides. MXene is primrily formed by selectively extrcting the A elements of
the Ti3AlC2 MAX phse with trnsition metl elements vi etching. Notbly, MXene hs received
 broder ppliction s  result of its unique chrcteristics, fcile fbriction strtegies, nd its
reproducibility t mssive scle. It possesses good stbility in het, excellent electricl conductiv-
ity, nd mechnicl properties similr to grphene. Aside from the lrge surfce re of the unique
grphene-like nnomteril MXene, it presents ccessible surfce hydroxyl, oxygen, nd uorine
termintion points thn crbon, TiO2, nd other 2D nnomterils. Owing to the physicl brrier
effect of its 2D nnosheets, MXene grnts better retrdncy nd suppresses smoke when incorpo-
rted into polymers (Ansori et l., 2017; Hi et l., 2020). MXene hs been incorported in unstu-
rted polyester to mitigte pek het relese rte, enhnce the suppression of smoke, nd inhibit the
relese of crbon monoxide. These results revel tht the essentil function of the chemicl con-
stituents of MXene impcts the ctlytic ttenution effect of the thermosetting polymer nnocom-
posites during combustion. Undoubtedly, the chemicl constituents of MXene hve n inuentil
114 MXene-Filled Polymer Nanocomposites

role in determining the nture of the physicl brrier effect, especilly the me-retrdncy of
MXene-bsed nnocomposites (Hi et l., 2020).
With regrd to synthesis, MXene predominntly possesses rective functionl groups, useful in
ensuring good rection with other constituents during the fbriction of nnocomposites. Primrily,
the mgnitude of exfolition of the MAX phses is chiey dependent on determinnts, nmely, the
vriety of MAX phses, nd the prmeters (such s temperture, the length of time, nd concentr-
tion) employed in the etching process. A hydrouoric cid etchnt is reported to be very efcient
for the fbriction of MXene from MAX phses. Nevertheless, its high corrosiveness necessitted
the usge of lterntive etchnts. The vrieties of MAX phses usully employed for the fbric-
tion of MXene by etching include Ti3AlC2 nd Ti2AlC. MXene prepred vi wet chemicl cidic
etching is employed in two bsic forms, tht is,  single to  few kes or in the form of multilyer
MXene stcks (Crey nd Brsoum, 2021; Verger et l., 2019). The synthesized MXene is incor-
ported in thermoset polymers vi mny different strtegies of nnocomposite fbriction such s
in situ polymeriztion, solvent mixing, hot press/injection molding, nd others, which re further
detiled in the next subtopic. Even though there exist more thn 20 fbricted MXenes, such s Ti3–
xC2Ty,V2CTx, (Ti, V)3C2, nd (Cr, V)3C2), Ti3CN, Ti4N3, nd Nb3C2Tx nd mny more (Zho et l.,
2019), s detiled by Bbk Ansori et l.(Ansori et l., 2017), the most widely used MXene is the
Ti3C2Tx. TheTi3C2Tx ws the rst MXene discovered in 2011 (Go et l., 2020; Sun et l., 2017).
MXene hs found ppliction in energy storge (Ahmed et l., 2020; Ansori et l., 2017), ctly-
sis (Ahmed et l., 2020; Zho et l., 2019), sensors (Ansori et l., 2017; Li et l., 2021; Lee et l.,
2019), me retrdnce (Yu et l., 2021; Si et l., 2019), electronic mgnetic interference shielding
(Go et l., 2020; Ansori et l., 2017; Hu et l., 2020), rechrgeble btteries (Ming et l., 2021),
fuel cells (Liu et l., 2018), nnogenertors, nd mny others (Go et l., 2020). As illustrted
in Figure 6.2, the MXene suspension is dded to the polymer solution nd subsequently cured to

FIGURE 6.2 Formtion of thermoset polymer/MXene nnocomposite.

Thermoset/MXene Nanocomposites 115

TABLE 6.1
MXene, Application, and Properties
MXene Field of Application Properties
Ti3C2Tx MXene-welded Aerospce nd militry pplictions Electromgnetic interference shielding (Chen et l.,
AgNW lm 2020b)
Ti3C2Tx modied Protection from microbes High ntimicrobil ctivity ginst E. coli nd B.
membrne subtilis (Rsool et l., 2017)
Ti3C2Tx Energy storge pplictions High electrochemicl performnce of electrode (Fu
(supercpcitor) et l., 2018; Li et l., 2017; Luktsky et l., 2013)
Ti3C2Tx nnosheets Trnsient electronic skin, intelligent High exible nd sensitive piezo-resistive sensor,
robots, nd humn–mchine sensors. nd excellent durbility (Yn et l., 2020b)
Ti3C2TxMXene@Pd Novel hydrogen sensor Lightweight, exible, nd high sensitivity to
colloidl nnoclusters hydrogen t room temperture t either t or bent
pper lm sttes (Zhu et l., 2020)

form  thermoset/MXene nnocomposite. The orienttion of the MXene in the nnocomposite is

inuenced by the percentge of MXene llers to polymer, solvent, nd the fbriction method used.
Some MXenes nd their pplictions re outlined in Tble 6.1.

6.4 THERMOSET/MXene NANOCOMPOSITES FABRICATION

Fbriction strtegies form n inuentil fctor in the outcome of products. They could ffect the
orienttion, interction, nd shpe of the nnocomposite. It is noteworthy tht thermoset polymer
resins re liquids with low viscosity, which grnts esy processbility during fbriction; hence,
they do not require high pressure in the formtion of the composite. The fbriction of thermoset/
MXene nnocomposites cn be done by mny different routes, including in situ polymeriztion,
solution mixing/blending, freeze-drying, hot press/injection molding, vcuum-ssisted ltrtion,
resin trnsfer molding, intercltion, templte-ssisted, nd soniction-ssisted fbriction, mong
others.

6.4.1 IN SITU POLYMERIZATION BLENDING

In situ polymeriztion is n effective wet processing method of composite fbriction tht enhnces
good dispersion of MXene in the thermosetting resin, solvent-bsed curing solution, nd inititors.
During synthesis, MXene llers re initilly dispersed in the monomer by subjecting them to physi-
cl stirring. Subsequently, the mixture is exposed to het soniction nd polymerized using the
pproch pproprite for  specic thermosetting resin. Aside from the preceding steps, MXene
could lso be dispersed in  solvent nd dded to the monomer solution before polymeriztion. To
ensure  stble suspension, the solvent comptible with the resin is used for the dispersion of MXene
before the initition of polymeriztion. In some occurrences, interfcil gents could be dded to
enhnce stbility in the suspension. Most reports use solvents, nmely, cetone or dimethylfor-
mmide during this process to ccelerte dispersion. Also, studies on the in situ polymeriztions
of polypyrrole, polyniline, polycrylmide (PAM), nd others in queous solutions using solvents,
such s cetonitrile, hve been disclosed. Figure 6.3 shows the process of fbricting nnocomposite
by in situ polymeriztion. A good dispersion of MXene llers with high interfcil strength in the
interfce of the MXene–polymer mtrix is chievble with this method. However, this strtegy is
not well received for the fbriction of some prticulr nnocomposite mterils, due to its demnd
for low elstomer viscosity before polymeriztion. In other words, low viscosity necessittes good
interction between constituents t their bsic level. The strong interction between thermoset nd
116 MXene-Filled Polymer Nanocomposites

MXene Monomer
solution

Insitu polymerization

Cross-linked Monomer/MXene
polymer/MXene dispersion

FIGURE 6.3 In situ polymeriztion process of thermoset/MXene nnocomposites fbriction.

MXene is benecil in chieving the required functionl properties. Prticulrly, this fbriction
strtegy is gretly efcient for the preprtion of polymers, such s epoxides nd polypropylene,
mong others, contining heterocyclic compounds or liner molecules (Ndyishimiye et l., 2020).
These polymers hve been integrted with MXene to prepre more functionl nnocomposites to
widen their ppliction in mny different elds.
Generlly, direct mixing of the vrious constituents nd intercltive polymeriztion of interc-
ltion hve been the most used synthesis methods in fbricting epoxy nnocomposites, owing to
the uidity of epoxy monomers. For in situ polymeriztion by intercltion, the epoxy moleculr
chins interclte in between the lyers of MXene, which consequentilly leds to the increment in
the distnce between MXene lyers nd the stripping of lyers fter curing. Furthermore, the exfoli-
ted nnosheets in the polymer mtrix could contribute to the enhncement in surfce re existing
t the interfce of the dditive nd the mtrix. In other words, MXene nnosheets ply  crucil role
in ttining good interction with the polymer in exfolition vi in situ intercltion.
A typicl polymeriztion mechnism of DGEBA/MXene ws prepred with the hrdener ct-
ing s  ctlyst initilly resulting in ring opening nd the breking of C–O bonds in the monomer
(Zhng et l., 2016). At the sme time, n intermedite is formed, where the N–H links brek nd
trnsfer H to O. Subsequently, the tertiry mine initites the ring opening of the monomer to com-
mence the rection process. Upon the incorportion of MXene, its functionl groups were ttched
to the epoxide groups (comprble to etheriction rection), longside the proceeding ring open-
ing. In other words, the MXene functioned s  meditor tht promotes curing nd the genertion of
 crosslinking between the numerous chins in the epoxy mtrix.

6.4.2 SOLUTION MIXING/BLENDING

A well-known nd fcile strtegy for the fbriction of MXene/polymer nnocomposites is solu-
tion mixing/blending. Solution blending is mostly recommended for polr polymers. It constitutes
the predominnt technique used for composite fbriction due to the hydrophilic chrcteristic of
MXene resulting from its lrge functionl groups. In this fbriction process, MXene nd polymer
resin re seprtely dispersed, similr to the procedure used in in situ polymeriztion. The resin
Thermoset/MXene Nanocomposites 117

solution nd MXene suspension re stirred together to ensure  good mixture of the two com-
ponents. Alterntively, the MXene/polymer resin could be dispersed in  polr solvent tht hs
good solubility for the polymer being processed. Upon stirring,  uniform viscous mixture is
obtined. The nl step in this method is the solvent evportion process to remove the solvent.
Thermoset polymer, such s polyurethne, hve been successfully combined with MXene to pro-
duce nnocomposite using this method. The mjor demerits of this technique re s follows: wek
mechnicl properties, production of  lrge volume of environmentl wstes resulting from the
composites production process, nd the chllenge in drwing out solvents using evportion. These
chllenges re considered impediments to the ppliction of this technique in the fbriction of
nnocomposites.
Aside from the production of MXene/polymer nnocomposites using hydrophilic polymers,
nmely, poly(dillyldimethylmonium chloride), poly(crylmide), nd polyethylene oxide,
employing wter s  solvent hs been reveled. In ddition to wter, MXene/polymer nnocom-
posites re processble in other polr solvents. This is nother re of study tht remins unex-
plored, nd n investigtion of dispersion in  model polymer by this processing technique could
mke  signicnt contribution to the eld of MXene/polymer nnocomposite reserch (Crey
nd Brsoum, 2021).
Another solvent-relted method of preprtion is ultrsonic mixing. In this technique, polymer
nd MXene re physiclly mixed, similr to the initil step of in situ polymeriztion. However, the
ultrsoniction process is pplied for  while to chieve suitble dispersion of the MXene in the
mtrix, fter which the composite is subjected to curing t the pproprite temperture. This method
is especilly suitble for epoxy/MXene-bsed composites. Another derivtive of the solvent pproch
is the solution csting method, which involves seprte dispersion of MXene nd polymer mterils
in different solvents. The vrious dispersion is brought together by blending, followed by grdul
removl of the solvent either by evportion or freeze-drying pproch (s shown in Figure 6.4), fter
which curing tkes plce t n pproprite temperture.

FIGURE 6.4 Freeze-drying of MXene/epoxy composite.

Source: Aghmohmmdi et l. (2021).
118 MXene-Filled Polymer Nanocomposites

6.4.3 HOT PRESS/INJECTION MOLDING

Hot press/injection molding is  fcile technique used for fbricting MXene/polymers. This strtegy
is lso referred to s melt blending. Unlike solution mixing, hot press/injection molding is minly
suitble for nonpolr polymers, which hinders its wider ppliction. It is done by rst melting the
polymer, nd subsequently dding the MXene to the polymer solution. Under  controlled condition,
the dispersion of MXene nd  melted polymer mtrix re stirred to ttin the desired viscosity. The
composition is injected into  heted die within  period. It is then cooled down to obtin the solid
nnocomposite. The extruder hs been the min device used for mixing nnocomposite mterils in
this technique. Mostly, the mixing of MXene nd polymer mterils is done t high tempertures,
speciclly bove the melting point of the polymer. This method hs shown gret potency in the pro-
duction of nnocomposites in lrge quntities. Notbly, the hot press/injection molding technique for
nnocomposite fbriction nds severl pplictions for hydrophobic polymers becuse hydrophobic
polymers re not solution-or solvent-friendly (Jy Prksh nd Kndsubrmnin, 2021).
Furthermore, due to the high bulk density of MXene (~4.26 g/cm3), which is essentil in esing the
feeding process in this technique, MXene hs signicnt dvntges over grphene. Melt processing
hs been used to produce MXene/polymer nnocomposites with polymers, such s polyurethne nd
phthlonitrile (Derrdji et l., 2019; Crey nd Brsoum, 2021; Jy Prksh nd Kndsubrmnin,
2021). With the quest to improve upon the comptibility of hydrophilic MXene nd the nonpolr poly-
mers, the surfce of the MXene is subjected to modiction. Compred to polymeric mterils, MXene
displys good stbility t high degrdtion tempertures. Also, benets such s the exibility in redy-
ing the constituents, the noninvolvement of solvent, low-cost, nd, bove ll, environmentl-friendly.

6.4.4 VACUUM-ASSISTED FILTRATION

This technique is primrily used to dry nnocomposites by drwing out solvent from  disper-
sion. In this method, the driving force for ltrtion results from the ppliction of suction t the
re contining the ltrte s seen in Figure 6.5. It hs been extensively used in the fbriction
of nnocomposite lms. Prior to suction, the desired quntity of MXene is dded to  polymer

MXene dispersion

(b)

(c)

Vaccum
suction
MXene/polymer MXene/polymer film
dispersion
(a)

FIGURE 6.5 Vcuum-ssisted ltrtion of MXene/polymer nnocomposite.

Source: Hung nd Wu (2020).
Thermoset/MXene Nanocomposites 119

queous solution, which might be contining  curing gent. The mixture could sometimes be
diluted by deionized wter, mixed for some minutes or hours, nd/or sonicted to form uniform
suspension before ltrtion with  membrne ssisted by  vcuum pump to prepre MXene/
polymer nnocomposite lm. The nl weight of the polymer used in the preprtion of nno-
composite by this technique is most t times modertely lower thn its nominl weight. The loss
in weight is ttributble to the loss of the polymer or some constituent in the polymer during
the ltrtion. Subsequently, the lm is heted in  vcuum oven to get rid of ir pockets nd
then t n pproprite temperture nd time (Mirkhni et l., 2019; Co et l., 2018; Hu et l.,
2020; Ji et l., 2020).
MXene/polymer lm produced through regulr vcuum-ssisted ltrtion hs the dvn-
tges of high conductivity, excellent mechnicl performnce, good surfce wettbility, nd
others. However, the production method is time nd energy consuming. This limits the ppli-
ction of lms prepred by vcuum-ssisted ltrtion t  lrge scle (Wng et l., 2021; Wn
et l., 2021; Chen et l., 2020). A vcuum ws used to dry  lter-coted Ti 3C2Tx dispersion by
which  homogeneously dispersed nd bubble-free polydimethylsiloxne solution ws dropped
on  polymeric lter. The decorted lter ws sndwiched between two polyethylene tere-
phthlte (PET) pltes in its wet stte nd then cured t 100°C for 120 min (Hu et l., 2020).

6.4.5 RESIN TRANSFER MOLDING

Resin trnsfer molding (RTM) is  exible nd economicl substitute for utoclve processing used
in the mnufcture of intricte polymer composites tht nd ppliction in structurl constructions.
It is  good method for producing dimensionlly controlled prts, which re chllenging to duplicte
in series of productions. One of the min differences between this method nd hot press/injection
is the rw mterils used. As the nme implies, the low-viscous resin is used in RTM, while in hot
press/injection molding, the polymer is melted to ttin low viscosity. RTM is economiclly prefer-
ble to hot press/injection molding.
Two ctegories of RTM, nmely, vcuum-ssisted nd pressure-ssisted RTM methods, hve
been employed in the production of composites. In generl,  resin is injected into the mold with
the id of  vcuum nd/or pressure. The drwing of resin into the mold using vcuum rther thn
injection pressure is clled vcuum-ssisted RTM. The overriding merit of vcuum-ssisted RTM
is its prospect for lower cost in its setup nd propensity to produce lrge-size composite prts.
This process does not need  complex chmber or device for curing. Prior to curing  ltrtion of
resin,  wet-stte composite is done with  single-sided tool together with vcuum bg mteril.
Before injection of resin/MXene suspension, it is of gret importnce to ensure tht low viscosity is
ttined fter stirring to fcilitte the genertion of the compct nd less defective nnocomposite.
To keep processing times to  minimum, the RTM is heted to ccelerte the curing process nd
solidiction of resin/MXene slurry. After curing, the mold cvity is opened, nd the prt removed.
The MXene/polymer nnocomposites tke the form of the mold nd/or mndrel used during the
fbriction. Although the dvncement of RTM is still underwy, it hs been employed for decdes
in fbricting composites pplied in the construction of commercil bots nd high-performnce
composites. An illustrtion of RTM hs been presented in Figure 6.6.

6.4.6 TEMPLATE-ASSISTED FABRICATION

Templte-ssisted fbriction method could lso be produced thermoset/MXene nnocomposites.
The templte-ssisted method enbles the formtion of porous rchitecture nnocomposite. This
technique hs been used for ssembling 2D MXene into 3D porous mcrostructures, so is  poly-
mer. It is propounded to be more preferble in the formtion becuse MXene hs  high tendency to
gglomerte nd restck, which leds to the reduction in their specic surfce re. This negtively
ffects the desirble properties of MXene. In light of tht, the MXene kes ssemblge into 3D
120 MXene-Filled Polymer Nanocomposites

Slurry
Inlet
(a)

Vaccum
suction

(c)
Hinges
Empty mold
Nanocomposite

(b)

Demolding

Mold filling and curing

FIGURE 6.6 Grphicl representtion of the stges in RTM.

rchitecture is  good mens of hindering stcking (Zho et l., 2018). Primrily, the templte-
ssisted method involves the employment of  scricil templte to regulte the porosity nd con-
gurtion of MXene/polymer in solvent. Some mterils used s templtes include slt, Al2O3, nd
others. These templtes re leched out by dissolving in wter or mostly by exposing the nno-
composite to het tretment fter the fbriction of the composites. Also, nnostructured mterils
in different shpes such s pillrs, bers, or spheres could be used s templtes to crete pores or
rchitecture surfces on the nnocomposite. Following the templte-ssisted fbriction technique,
MXene kes hve been fbricted on the surfce of the sphericl scricil templte to obtin 
sphericl hollow composite (Bu et l., 2020). The size nd rtio of the scricil templtes employed
in templting the nnocomposites enct  criticl role in tuning the dimensions of the nnocompos-
ite’s rchitecture.
The procedure for templte-ssisted fbriction is reveled in the following using some proce-
dures used in some studies for the fbriction of nnocomposites. An MXene or  polymer could
be templted before the incorportion of the two components. This implies tht the thermoset poly-
mer, in the form of solution could be incorported fter the preprtion of the MXene rchitecture
structure. Chen et l. used slt s  templte in prepring epoxy/HBN–polyvinylidene diuoride
nnocomposites, which yielded  reltively high conductivity to het. Templting ws done by rst
mixing the HBN–polyvinylidene diuoride with  slt followed by the dissolution of the polyvinyli-
dene uoride in cetone. The polyvinylidene uoride in cetone served s n dhesive tht rises the
thinness in viscosity nd hindered the precipittion of HBN–polyvinylidene diuoride. Upon the
incorportion of  slt, insoluble in cetone, the HBN–polyvinylidene diuoride orients betwixt
the slt prticles, which leds to the formtion of  continuous HBN–polyvinylidene diuoride
complex fter leching out cetone nd slt. The thermoset polymer solution ws incorported by
vcuum-ssisted impregntion to form the nnocomposite, during which the pores in the frmework
of HBN–poly vinylidene diuoride were occupied by epoxy without ffecting its structure. This
resulted in considerbly good therml conductivity of thermoset nnocomposites.
Thermoset/MXene Nanocomposites 121

Another templte-ssisted fbriction technique used to obtin  3D porous structure is freeze-cst-

ing. In this method, the rchitecturl design structure of the end product is gorged from the shpe of the
mold employed during freeze-drying. This is to sy, the shpe of the mold determines the shpe of the
nnocomposites, becuse the nnocomposites tke the form of the mold, hence the nme freeze-csting.
When employed effectively, not only the outer design but lso the inner morphology, including the size
nd shpe of the internl pores, cn be tuned (Tontini et l., 2020). An ice-templte method ws used in
prepring MXene nd MXene/Ag erogel before the fbriction of MXene-epoxy nnocomposite lms.
MXene nd MXene/Ag were dispersed in poly(vinyl lcohol) queous solution, which ws then poured
into  cubic Teon-coted mold glued on the surfce of  copper pillr immersed in liquid nitrogen.
After freezing the suspension, MXene/Ag erogels were then prepred t the required conditions by
freeze-drying t −55°C nd 50 P for 2 dys. They were subsequently nneled t 250°C for 2 h under
Ar/H2tmosphere. The templte-ssisted method hs found few pplictions in fbricting thermoset
nnocomposites; nevertheless, it is deemed pproprite for the fbriction of lyer-to-lyer lm nno-
composites whereby the templte mterils re used to perforte  lyer before the dispersion of MXene.
A ctionic surfctnt cn be used to tune the hydrophilic chrcter of MXene by the exchnge of
H+ with the –OH groups to synthesize high internl-phse emulsions. The stediness of the emul-
sions is highly dependent on the pH of the solutions. Furthermore, polymeriztion initition of the
binder remoted by temperture leds to the fbriction of  porous monolith with  cellulr structure
(Bin et l., 2018). Also, n electrospun polymer in the form of bers or  3D frmework could
be used s  templte nd immersed in n MXene dispersion, followed by drying in ir or posttret-
ment to enhnce the interction of MXene on the polymer (Yun et l., 2018; Estrny et l., 2016).
More so,  honeycomb Al2O3 structurl-reduced grphene-ssisted templte ws synthesized
by high-temperture nneling nd then freeze-dried using honeycombAl2O3 pnels for MXene/
epoxy composites. This method is suggested to provide regulr structures, which could pve wy
for the regultion of design in terms of cell size, shpe, nd uniform dispersion of MXene in the
mtrix. The mtrix ws prepred ccording to the illustrtion in Figure 6.7, where the honeycomb

FIGURE 6.7 Honeycomb-ssisted fbriction of rGMH/epoxy nnocomposites.

Source: Song et l. (2020).
122 MXene-Filled Polymer Nanocomposites

structurl reduced grphene oxide (rGO) ws initilly prepred with n Al2O3 honeycomb plte
s  templte. The MXene dispersion is mixed with quternry mmonium surfctnt to trns-
form the ctionic chrge on the surfce of MXene into negtive chrges. Subsequently,  honey-
comb structurl rGO-MXene with impeccble electricl conductivity, hving good lodbering is
ttined by MXene self-ssembly on honeycomb structurl rGO through electrosttic ttrction
nd dsorption. After obtining the honeycomb structurl rGO-MXene, the mixtures of epoxy
resin nd curing gent re dded nd then cured using n pproprite time/durtion to produce
thermoset/epoxy nnocomposites (Song et l., 2020).

6.4.7 IONIC INTERCALATION AND SONICATION-ASSISTED METHOD

Prior to the discussion on thermoset/MXene intercltion, MXene hs been mostly fbricted by
ionic intercltion. Metl ions hve been interclted into MXene due to its high rectivity, chelting
role, nd bility to enhnce the functionl properties. Ionic intercltion of MXene hs proved to be
dvntgeous by reducing the pressure on less bundnt lithium used in energy storge (Lei et l.,
2020; Kjiym et l., 2016). In ddition, surfce modiction of MXene, such s Ti3C2Tx, with
other nnoprticles (viz. sulfur nd titnium dioxide) hs meliorted stediness incpcity. Even
though multivlent ionic species interclted in MXene do hve numerous interesting fetures, like
higher chrge-to-rdii rtio, they re redily vilble thn lithium nd sfer. However, drwbcks,
such s low-chrge efciency, still exist. The chllenges spn from low suitbility of electrolyte
to unstisfctory plting/stripping of the node or excessive bondge between the MXene nd the
interclted ions.
Even though MXene mterils hve displyed good properties for mny pplictions in vrious
elds, they re fced with serious chllenges in chieving desirble exible devices becuse of the
high stiffness nd reltively smll lterl sizes. In light of tht, exibility could be introduced with
polymers (M et l., 2016). Hence, thermoset/MXene nnocomposite, tking dvntge of the ex-
ible structure of polymer chins, moleculr-level coupling between MXene nd polymer molecules
cn be chieved by interclting polymers into MXene kes. In this wy, the resultnt MXene/
polymer membrnes could exhibit some level of exibility with enhnced properties becuse of
the synergistic effect between polymers nd MXene kes, thus fcilitting their ppliction for
ltrtion, electromgnetic interference (EMI) shielding, energy storge, sensor, nd ctutors (Go
et l., 2020).
Depending on the degree of dispersion of MXene in  polymeric mtrix, two min types
of thermoset/MXene nnocomposites cn be obtined: interclted or exfolited nnocompos-
ites. The intercltion of thermoset/MXene nnocomposite in which the polymer chins diffuse
between pltelets nd increse the interlyer spces of MXene without cusing seprtion of
pltelets hs been reveled. Furthermore, exfolition occurs when the stcked MXene structure
is destroyed nd the pltelets re no longer bonded together. In exfolition, the specic re of
MXene could be extensively incresed leding to more interctions between MXene nd poly-
mer solution. The exfolited MXene structure is the optimized form of the 2D mteril which
mkes it esy to disperse within the polymer mtrix becuse it is only  few lyer thicker, hence,
the reduced possibility of gglomertion. As  result, severl properties such s stiffness, glss
trnsition temperture, nd storge modulus of the composite re gretly enhnced (Guvin nd
Robert, 2015).
One of the simplest wys for the fbriction of MXene/polymer nnocomposites is the sonic-
tion pproch. Soniction could be used to delminte MXene sheets into single lyers (Deshmukh
et l., 2020). In this method, fter initilly stirring the mixture of polymer solution nd MXene, the
suspension is ultrsonicted for  period to chieve good distribution of the MXene. This method is
usully employed in producing thermoset epoxy-bsed composites. Ultrsoniction hs been used
together with other fbriction methods to improve the dispersion of MXene in n queous solution
Thermoset/MXene Nanocomposites 123

or polymer solution nd for the intercltion of the polymer into MXene (Monstyreckis et l.,
2020). It is minly done by inserting the soniction rod in the suspension or plcing  beker con-
tining the suspension in  soniction bth. The soniction-ssisted method could be used to fbri-
cte peroxide-decorted MXene, which needs no conventionl inititor for polymeriztion (Rizi
et l., 2021). MXene/polymer nnocomposite ws fbricted by this method in which delmintion
nd etching were chieved concurrently. It is suggested tht cvittion bubbles, produced by sound
wves generte hydrogen peroxide groups in the etching medium, which then rects with the func-
tionl hydroxyl groups on the surfce of MXene to generte peroxide groups. Through this process,
the initition of free-rdicl polymeriztion is fesible in the bsence of  conventionl inititor (To
et l., 2019).
Aside from the extensively used vcuum-ssisted ltrtion, csting, nd hot press techniques,
nd so on, other fbriction strtegies like lyer-by-lyer ssembly, cold press, electrospinning, nd
electrochemicl deposition hve been used to produce 2D MXene/polymer nnocomposites with
superior functionl properties.

6.5 STRUCTURE AND MORPHOLOGY OF THERMOSET/

MXene NANOCOMPOSITES
The structure nd morphology of the individul components of the nnocomposite hve some
inuence on the performnce of the nl product. As observed in the erlier sections, nno-
mterils or nnocomposites could be structured by modiction with templtes, intercltion,
exfolition, nd others. The morphologicl structure could lso positively enhnce the interction
of the components in  nnocomposite. The frequently used tools for exmining the morphologi-
cl structure of nnocomposites re X-ry diffrction (XRD) nd scnning/trnsmission electron
microscopy instruments. XRD could be used to determine the spces between lyers in structures
using Brgg’s lw. For instnce,  lower XRD diffrction ngle is mostly indictive of  widened
interlyer distnce in the low-ngle region, reveling the formtion of n interclted structure.
On the other hnd, the disppernce of peks owing to the loss of structurl registry of the lyers
indictes exfolited component (MXene) or nnocomposite. Mostly, in situ polymeriztion leds
to the formtion of interclted structures, whiles the exfolition–dsorption process genertes
exfolited nnostructures (Zhng et l., 2016), which could be conrmed by XRD diffrction
peks.
At low MXene frction, the diffrction peks relted to MXene t 2 θ = 7.5° re wek nd some-
times dispper, reveling tht MXene lyers hve been exfolited. Conversely, t  high frction
of MXene, the pek ppers t 2θ = 6.1°, indicting  lrge inter-distnce lyer tht is most suitble
for intercltion of thermoset polymer composites. Howbeit, nnocomposites contining  high
lod of MXene revel  pek t 9.5°. This is evidenced tht the MXene nnollers re prtilly
delminted in the nnocomposites (Zhi et l., 2018). In the SEM surfce structurl microgrph
(Figure 6.8), pure polymer showed  smooth nd fetureless frctured surfce, but tht of the
MXene/polymer nnocomposite surfces re typiclly rough, suggesting the interclting of ther-
moset polymer moleculr chins into the interlyers of MXene, which cn serve s reinforcement
for thermoset/MXene nnocomposites. The roughness of the nnocomposite increses s the rtio
of MXene increses in the composition.
The morphology of MXene nd thermoset epoxy/MXene composite revels tht the MXene
develops  higher interlyer distnce—typicl of interclted MXene prepred by etching (Zhng
et l., 2016). In ddition, the MXene Ti3C2Tx/epoxy nnocomposites disply frctured nd rough
surfces s compred to net thermoset epoxy due to the intercltion of the polymeric moleculr
chins into Ti2CTx lyers s shown in Figure 6.8. Similr results hve been reported in mny stud-
ies relted to thermoset/MXene nnocomposites (Aghmohmmdi et l., 2021; Jy Prksh nd
Kndsubrmnin, 2021; Alhbeb et l., 2017b). The TEM microgrphs give  cler view of the
124 MXene-Filled Polymer Nanocomposites

FIGURE 6.8 SEM nd TEM imges of MAX Ti2AlC phse (, d), MXene Ti2CTx (b, e), MXene/epoxy (c, f)
nnocomposite, respectively.
Source: Aghmohmmdi et l. (2021).

intercltion of thermosetting epoxy polymer into the interlyers of MXene, thereby hindering the
restcking of MXene, which results in good dispersion.

6.6 MECHANICS OF THERMOSET/MXene-BASED NANOCOMPOSITES

The composition of thermoset/MXene nnocomposite works hnd in hnd to present enhnced per-
formnce in mny different res. Understnding the interction between polymer nd MXene nd
their corresponding mechnisms in their ppliction (wer resistnce, electric shielding interfer-
ence, nd mechnicl properties, etc.) is still premture. The mechnicl properties of  nnocom-
posite cn be enhnced by mnipulting the crystllinity of the mtrix. One of the mjor resons
tht cuse the enhncement in the performnce in most fbricted thermoset/MXene nnocom-
posites is the existence of hydrogen bonding between OH groups of MXene nd polymer. Strong
interfcil interction between Ti3C2Tx nd the polymer mtrix positively inuences the surfce
hrdness of the nnocomposite. Also, the mgnitude of crosslinking in polymer could mrginlly
increse t the interfce of MXene, leding to the improvement of interction between the polymer
nd MXene nnosheets. The unique lyered morphology of Ti3C2Tx MXene enhnces the mechni-
cl properties of the polymer. Incresing the lod of the MXene could result in more interction t
the MXene nd polymer interfce. This leds to the occurrence of more lod trnsfer mechnisms
to ensure wer resistnce. It is noteworthy tht excessive frction of MXene could negtively ffect
the interfcil property nd performnce of the nnocomposite.
Furthermore, the meliortion in wer resistnce of nnocomposite cn lso be ttributed to vn
der Wl bonding. The mechnicl nd brsion resistnce of MXene/polymer nnocomposites
could similrly be improved by the existence of vn der Wls bonding, hydrogen bonding, nd
electrosttic forces t the interfce of the polymeric mteril nd the MXene lyers s shown in
Thermoset/MXene Nanocomposites 125

FIGURE 6.9 Interfce bonding in MXene–epoxy composites: () Density function theory of DGEBA nd
MXene interfce, (b) corse-grined moleculr dynmic simultion MXene–DGEBA composite interfce,
(c) TEM imge of MXene–DGEBA interfce, nd (d) schemtic illustrtion of MXene–DGEBA interfce.
Source: Sliozberg et l. (2020) nd Go et l. (2020).

Figure 6.9d. In MXene/nonpolr polymers,  comptibilizer, such s mleic nhydride, is used to

enhnce hydrogen bonding in MXene/nonpolr polymer nnocomposites (Dong et l., 2016).
It hs been estblished tht the tensile strength of polymer nnocomposites cn be enhnced
by incresing the frction of Ti3C2Tx nnosheets in the mtrix due to the physicl hindrnce of the
polymer chins’ mobility in the nnoconnement structure. The stronger dhesion t Ti3C2Tx/poly-
mer interfce reltes to the presence of multiple hydrogen bonds; s  result, the storge modulus
nd the elongtion t brek of nnocomposites get enhnced with  smll percentge of Ti3C2Tx
nnosheets. The good distribution nd exfolition of the Ti3C2Tx in the polymeric resin lso ccount
for the improvements in the mechnicl properties of nnocomposites s the concentrtion of
MXene increses. Also, the development of the conned nnoscle cused by the existence of
numerous hydrogen bonds in the Ti3C2Tx lyers nd polymer reduces the deformtion nd filure of
the polymer chin to improve the strength of the nnocomposite. Generlly, Ti3C2Tx MXene/poly-
mer nnocomposites disply superior mechnicl properties due to the good dispersion of MXene,
the strong interction, nd the effective lod trnsfer between the stiff MXene nd the polymer
mtrix (Liu et l., 2021). Becuse of the verstile nture of MXene surfce chemistry, orgnic
ddends tht cn form  good interconnection between MXene nd polymers re used, resulting in
the formtion of rections. The MXene cts s  bridge tht holds polymer chins together. Besides
the obvious effect of MXene on the mechnicl properties of thermosets, their positive effects on
het conductivity cn be lso be ssigned to strong bonding or comptibility in the nnocomposite
126 MXene-Filled Polymer Nanocomposites

between the MXene nd polymer resulting from hydroxyl groups. Furthermore, the MXene hs 
high intrinsic therml conductivity, which cn elevte the therml conductivity of polymer nno-
composites compred to most pristine polymers. In this function, the effects of MXene on therml
conductivity re more pronounced t reltively higher loding (Aghmohmmdi et l., 2021). It hs
been estblished tht MXene/polymer nnocomposite hve superior dvntges to 2D (grphene
oxide/MoS2/CNT)/polypropylene nnocomposites (Shi et l., 2019)
For therml stbility,  well-dispersed MXene in the nnocomposite could ply  physicl br-
rier role during therml decomposition to improve the stbility of the nnocomposite nd concomi-
tntly improve the mechnicl properties. The trnsfer of het is restrined due to the comptible
interction of the MXene lyers with the polymeric mteril. In EMI shielding, the electromgnetic
wves re reected, scttered, nd bsorbed, leding to the lengthening of the pths of the electro-
mgnetic wves, which results in electricl loss. In Ti3C2Tx MXene/nturl rubber nnocomposite
studies (Luo et l., 2019), lrger bsorption thn reection enhnces the electromgnetic shielding
effect of the MXene polymer nnocomposite. The Ti3C2Tx nnocomposites disply  continuous
interctive ller network in the polymeric mtrix, which enhnces the trnsporttion of electrons
throughout the whole mtrix. The negtively chrged MXene nd polymer ensure n even distri-
bution of MXene t the polymer interfces. Regrding tribologicl performnce, dhesive wer is
considered the principl wer mechnism. The severe plstic deformtion nd more contct re
of the thermoset polymer cotings nd counter-body become more severe in friction. Nevertheless,
the incorportion of the MXene into the nnocomposite increses its hrdness nd strength, thereby
restricting the distortion of plstic nd reducing the wering rte of the nnocomposite. It is pro-
posed tht the homogeneous dispersion nd interconnection of MXene within thermoset polymer
is the bsis for the optiml efciency of mino-functionlized Ti3C2Tx in enhncing the wer nd
deformtion resistnce of nnocomposites, compred with MXene Ti3C2Tx (Yn et l., 2020).
Generlly, Young’s modulus of MXene-thermoset epoxy composites is signicnt compred to the
pristine epoxy becuse of the distribution of stress between the polymeric mteril nd the MXene
nnosheets. In terms of energy storge, the cpcitnce of nnocomposites such s MXene Ti3C2/
polypyrrole membrne is bout 30% higher thn tht of net polyppyrole, with high stbility in
cpcitnce fter thousnds of chrging/dischrging cycles. In the electrochemicl performnce,
the conductive polypyrrole chins were closely ttched to the MXene lyers, owing to the strong
hydrogen bonds, which grnts direct route for the trnsporttion of electrons. Also, using elec-
trochemicl polymeriztion for polymer/MXene mtrix, porous lm structure could be chieved,
due to the even dispersion of MXene kes within the composite, which fcilittes electrolyte
permetion.

6.7 APPLICATION OF THERMOSET/MXene-BASED NANOCOMPOSITES

Due to the verstile nd desirble properties of MXene in thermoset/MXene nnocomposites, it hs
remined the obvious option in multiple pplictions. The ttrctive qulities of thermoset/MXene
nnocomposites such s good mechnicl properties, electricl conductivity, nd uniqueness in the
structure mke it n exceedingly fvorble choice for high-performnce composite pplictions.
In ddition to the previously mentioned properties, its chemicl stbility nd ion inter-cltbility
mke MXene more fvorble for ctlysis (electroctlysis, photoctlysis), the detection of gs
or chnges in n environment (gs sensors, strin sensors, biosensors), biomedicl (phototherml
therpy, bio-imging, bone regenertion, ntimicrobil ctivity), energy storge (btteries, superc-
pcitors; Ji et l., 2020; Wei et l., 2020), photovoltic devices, thermoelectric power genertion),
me retrdnce, nd EMI shielding pplictions (Wng et l., 2019; Liu et l., 2018b). With the
incresing utiliztion of electronic equipment, the hrm cused by electromgnetic rdition to
humn helth nd sfety is ruinous. As  result, the use of MXene/polymer nnocomposites s
EMI shielding mterils hs received gret ttention due to the excellent electromgnetic shielding
performnce of MXene in composites compred to most of the lredy existing mterils (Wng
Thermoset/MXene Nanocomposites 127

et l., 2019). Aside from electromgnetic shielding, they re lso used in other res, such s opto/
spintronic, for the processing of informtion, tribologicl, nd medicl pplictions. MXene lso
nds ppliction in the mnufcture of btteries nd supercpcitors, providing  lrge energy den-
sity pplicble for compct-volume uses in portble electronics nd offering high power density
nd fster chrging nd dischrging, which is idel for mobile pplictions. Also, the existence of
surfce functionl groups in lrge numbers nd their biocomptibility cn be tilored for biomedi-
cl pplictions. In MXene composites, the biocomptibility, high conductivity, nd tunble surfce
properties of thermoset/MXene nnocomposites enhnce their pplicbility in electrochemicl bio-
sensors (Xu et l., 2020). Coupled with stble mechnicl properties nd excellent surfce chrc-
teristics, these mterils re considered superior trnsducing mterils for vrious sensors (such s
bio-electrochemicl, electrochemicl, gs, strin, chemiluminescence, pressure, nd photochemicl
sensors). Studies show tht the low coefcient of friction, the possibility of super-lubricity effect
through the unixil strins, nd the low brrier for sliding mke thermoset/MXene nnocompos-
ites n excellent mteril for tribologicl pplictions.

6.8 CHALLENGES IN THERMOSET/MXene NANOCOMPOSITES:

FABRICATION AND APPLICATIONS
Despite the extensive explortion of thermoset/MXene nnocomposites for vrious pplictions
in recent yers, chllenges with environmentl sfety nd of most polymers nd dvnced tech-
nologies for lrge exfolition of MXene still exist. Hitherto, severl resins employed in fbricting
nnocomposites re obtined from petroleum sources. These resins re mostly not degrdble nd
could exist for  number of yers in n nerobic environment. Undoubtedly, it is not worthwhile
to hve composites degrde during the ppliction; nevertheless, they project  huge disdvntge
to the environment fter usge, owing to their nondegrdbility. Unlike the recyclbility of thermo-
plstics, technology does not exist to reuse thermoset resins.
Although signicnt progress hs been mde with regrds to MXene synthesis, most of the tech-
niques do not ensure homogeneity in termintions cross the surfce of MXene lyers. Theoreticl
studies hve lredy shown tht bre MXene shows better performnce thn surfce-terminted
ones in mny pplictions, so it is recommendble to develop lrge-scle techniques to synthesize
bre MXene (MAX) into rened MXene to enhnce broder pplictions.
The issue of irrevocble restcking of MXene kes during synthesis hs been  mjor set-
bck restricting further industril exploittion nd utiliztion for certin pplictions (Fu et l.,
2018). The vcuum‐ssisted ltrtion tht nds ppliction in fbricting lm nnocomposite
mterils is quite time‐consuming nd, therefore, not commercilly sustinble. In other words,
using this method to drin out solvent is inefcient, hence the need to improve on the fbriction
method to reduce time nd ensure high drying cpcity (Chen et l., 2020).RTM is considered
to be n excellent strtegy, but the issue with the cost of the tooling is  mjor setbck for wide
doption. Also, process-induced defects such s microvoids, incomplete lling,  low degree of
cure, nd dry spots often hinder the broder ppliction of nnocomposites fbricted by RTM
in sophisticted or crucil pplictions in which high effectiveness nd efciency re required.
Understnding the cuse nd the morphology of these defects, together with the mechnism nd
techniques for removing the nnocomposites is  vitl step towrd the development of qulity
RTM of nnocomposites.
The most used MXene (Ti3C2Tx) is prepred with hydrouoric cid, which is  strong cor-
rosive cid, which is hrmful to humn helth nd the environment. Additionlly, the hrsh
etching ptness of hydrouoric cid tends to cuse defects on the surfce of MXene lyers. These
defects come long with generted crbon blls on the surfce of the MXene sheets, which is
unfvorble for the ppliction of MXene. This necessittes the quest to undertke studies to
obtin  more effective nd hrm-free technique to etch MAX-phse TiAlC into MXene Ti3C2Tx
(Song et l., 2021b).
128 MXene-Filled Polymer Nanocomposites

6.9 CONCLUSION
Generlly, the remrkble ttributes MXene hs led to  gret improvement in the functionl proper-
ties of not only thermoset nnocomposites but lso, other polymeric composites, even t low lodings.
The functionl groups of MXene nd the genertion of hydrogen bonding improve the dispersion
of MXene within mtrices nd ensure good interfcil interction which inuences the mechnicl
properties of polymer nnocomposites. Also, the lyered morphology nd the self-lubricting lms
on the surfce of polymers, spering from their interction with MXene enhnces the tribologicl
properties of polymeric composites. Mny different fbriction strtegies such s in situ polymer-
iztion blending, solution mixing, injection molding, vcuum-ssisted ltrtion, templte-ssisted
fbriction, nd RTM re the crdinl techniques for prepring functionlly novel nnocompos-
ites. New emerging methods for the construction of rchitecture nnocomposites re underwy to
improve the properties of thermoset/MXene nnocomposites. Thermoset/MXene nnocomposites
hve found ppliction in mny res even though most of them re still in their erly stge of
development. The proper dispersion of the MXene into the polymers, strong hydrogen bonds, nd
vn der Wls bonding, which forms the mjor nchor in sustining the nnocomposites, improved
their functionlities by het nd electricl conduction, EMI shielding, nd so on. Undoubtedly, the
interfcil interction gretly impcts the required outcome of the composite nd is one of the huge
drwbcks in the fbriction of qulity thermoset/MXene nnocomposites for wider pplictions,
especilly for MXene/nonpolr polymers. Consequently, reserch focusing on enhncing properties
in MXene/nonpolr polymer nnocomposites cn be chieved by surfce modiction with  solid
comprehension of the interction between the nnollers nd the polymeric mtrix.

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 7 Thermal and Crystallization
Behavior of MXene/
Polymer Nanocomposites
Sarkodie Bismark and Benjamin Tawiah

CONTENTS
7.1 Introduction ........................................................................................................................... 133
7.2 Methods of Evluting the Therml Behvior of Polymer Nnocomposites ........................ 134
7.3 Therml Properties of MXene............................................................................................... 136
7.4 Therml Behvior of MXene/Polymer Nnocomposites ...................................................... 138
7.5 Thermodynmics of Crystlliztion nd Melting of Polymers ............................................. 141
7.6 Crystlliztion of Polymer Nnocomposites......................................................................... 142
7.7 The Therml Phenomenon .................................................................................................... 143
7.7.1 Glss Trnsition Temperture.................................................................................... 143
7.8 Non-Isotherml Melt nd Cold Crystlliztion of MXene-Bsed Polymer Composites ....... 146
7.9 Effect of MXene on the Crystlliztion Behvior of Polymer Nnocomposites .................. 148
7.10 Conclusion............................................................................................................................. 149
References...................................................................................................................................... 149

7.1 INTRODUCTION
Most nturl nd synthetic polymers hve semi-crystlline structures, which ffect their mechni-
cl, opticl, nd therml properties. For this reson, it is impertive to comprehend the behvior
of polymer crystlliztion upon exposure to different conditions. Polymer crystlliztion cn be
induced by fctors such s compositions, therml history, chemicl structures, sptil connements,
nd pressure. To understnd the crystlliztion phenomenon of polymeric mterils, theoreticl nd
simultion is usully combined with systemtic experimentl investigtions [1]. Reserch works
relted to the crystlliztion process of polymers re of gret importnce in their processing, due
to the dependency of the resulting physicl properties on the morphology formed nd the extent of
crystlliztion [2].
Therml behvior is  mjor limiting fctor in the processbility nd ppliction of polymer
nnocomposites. This property is gin closely linked crystlliztion behvior of polymers nd
their composites [3, 4]. With the quest to reduce therml degrdtion of nnocomposites, especilly
for the obvious dvntges of me retrdncy, polymer crystlliztion behvior,  thorough under-
stnding of the crystlliztion nd the melting phenomenon of polymers is vitl. The crystlliztion
behvior of most semi-crystlline polymers is ffected when other mterils re introduced into
their mtrix for composites. More often, the specic therml chrcteristics of the polymer com-
posites, such s glss trnsition temperture, crystlliztion phenomenon, nd melting behvior,
re either enhnced or compromised. As  result, it is importnt to understudy the dynmics of the
vrious mterils used in polymers for the formtion of composites nd their mechnistic effects on
the ensuing composites. Usully, nnollers re incorported into polymer systems to meliorte
their therml stbility nd improve mechnicl performnce. Nnollers such s crbon nnotubes,
nnoclys, grphene nnosheets, nd delminted MXene hve become  common strtegy to

DOI: 10.1201/9781003164975-7 133

134 MXene-Filled Polymer Nanocomposites

improve the functionlity of the polymer for severl pplictions; however, their effect on the crys-
tlliztion behvior of polymers vries gretly. Some nnollers re known to increse or decrese
the glss trnsition temperture of polymer composites while others re well known for ffecting
the nucletion of polymer crystls fter rising or reduction in the rte of crystlliztion [5]. Mny
of these improvements re ttributed to the chnges in the properties of the polymer in the environs
of the prticles due to the interfcil interction between the polymer nd the ller [6]. Besides,
the chnges in glss trnsition nd the crystlliztion induced by the presence of nnollers, the
melting temperture (therml stbility) of the polymer composites cn lso be ffected. Most llers
with conductive properties, esily trnsmit het through polymers quickly, nd reduce the melting
temperture of the composites slightly, wheres llers tht bsorbs het increse the melting point
of the composites. Composites prepred with nnollers often exhibit two pek effects when the
heting rte is mintined constntly t  slow rte.
Also, the synergistic effect of nnollers on the crystlliztion behvior of polymer compos-
ites vries. For instnce, the orgno-montmorillonite/nno-Cu hs been identied to improve the
mechnicl performnce of polymer nnocomposites. Most nnollers improve the melting tem-
perture (therml stbility) nd the crystlliztion behvior of composites [3].
Unlike nnocly with Cu, the synergistic effect between MXene nd other mterils not only
improves the therml nd mechnicl properties but lso provides self-lubricting functionlities
with high therml conductivity nd electromgnetic shielding effect, which mkes it  unique two-
dimensionl (2D) mteril for pplictions in vrious mterils [7–11]. MXene experiences mrginl
weight loss due to decomposition of the orgnic ddends even under extremely high tempertures
[12]. In this regrd, MXene/polymer composites hve been prepred for vrious technicl pplic-
tions. The synergistic efciency between MXene nd orgnic polymer solutions is inuenced by
severl fctors, including the clss of polymer, the type of MXene, the method of exfolition, the
interfcil interction, nd its distribution in the composite [4].
MXene–polymer composites undergo multiphse trnsitions when exposed to het. Glss trnsi-
tion, enthlpy of chin relxtion, cold crystlliztion, nd melting re some of the typicl multi-
phse trnsitions during the therml study of polymers. This property is often ffected due to the
presence of MXene in the mtrix [13]. This chpter describes the methods used in elucidting the
therml nd crystlliztion behvior of polymer–MXene nnocomposites, the vrious methods of
evluting these therml trnsitions, nd their effect on the ensuing nnocomposite.

7.2 METHODS OF EVALUATING THE THERMAL BEHAVIOR

OF POLYMER NANOCOMPOSITES
Different methods exist for evluting the therml behvior of polymers nd composites. However,
the choice of  prticulr pproch is determined by the specic therml phenomenon one wnts to
observe. The most populr methods include the use of thermogrvimetric nlysis (TGA), differ-
entil scnning clorimetry (DSC), thermomechnicl nlysis (TMA), nd dynmic mechnicl
nlysis (DMA). The four min techniques re often complementry; however, sometimes, only 
combintion of the four techniques cn provide  full insight into the smple understudies. Other
therml nlysis techniques include micro/nnoscle locl therml nlysis (MNLTA) nd dielec-
tric nlysis (DEA). This section provides n introduction to the two most populr therml nlysis
techniques, thus TGA nd DSC. Detiled informtion bout these therml nlysis techniques,
including instrumenttion, mesurement procedure, instrument clibrtion, nd pplictions, with
the necessry theoreticl explntions for ll the techniques mentioned cn be found in  book titled
Thermal Analysis of Polymers: Fundamentals and Applications, edited by Joseph D. Menczel nd
R. Bruce Prime [14].
TGA mesures therml trnsitions in the physicl nd chemicl trnsformtions of mterils s
its been subjected to temperture with respect to time. Fluctutions in the mss of  mteril cn be
scribed to mny therml trnsformtions such s desorption due to the removl of dsorbed wter,
Thermal and Crystallization Behavior of Nanocomposites 135

vporiztion, bsorption, sublimtion, reduction, oxidtion, nd decomposition. These chnges re
observed s the mss of the mteril experiences chnges under cumultive temperture swoops.
TGA is, therefore,  verstile pproch suitble for the exmintion of voltile/gseous products
tht re lost during the endotherml degrdtion/rections in thermosets, elstomers, thermopls-
tics, nd composites when it is coupled with Fourier trnsform infrred (FTIR) spectroscopy. The
technique provides insight into vicissitudes tht occur in mterils t specic tempertures, nd the
chemicl breking down occurring in rel time in vrious controlled tmospheres (rgon, oxygen,
nitrogen, etc.). TG-FTIR is  useful technique for monitoring the evolution of gses under therml
degrdtion. Some of the mchines re tted with dditionl functionlity tht help give inform-
tion bout the crystlline nture of mterils, lthough this my not be their fundmentl use.
DSC is  useful therml nlysis tool tht provides  worth of informtion bout mterils like
polymers, nnomterils, nd food products. For DSC thermo-nlytic studies, the vrince in het
essentil to increse the temperture of  specimen under study nd the reference specimen re
determined regrding temperture nd time t  progrmmed heting rte. During this process,
therml chnges chrcteristic to most polymeric mterils such s glss trnsition, crystllinity,
polymorphism, nd eutectic chnges re observed. In thermoset polymers, importnt criteri, such
s curing nd degree of cure, nd other properties re lso observed. Generlly, in conducting the
DSC mesurement, the smple nd reference (usully n empty clibrted DSC pn) re kept t the
sme temperture throughout the experiment durtion t  constnt supply of het with the reference
specimen possessing  distinct het cpcity over the rnge of tempertures to be mesured nd
nlyzed. Most often, pertinent phse trnsitions of the specimen such s glss trnsition melting
point, nd the decompositions temperture re obtined nd nlyzed.
Besides the therml nlysis techniques, studies relted to crystlliztion behvior cn be
obtined using X‐ry diffrction. The chnge in crystllinity of the constituents in  pristine poly-
mer or nnocomposites could be detected by the diffrction pek shift nd spcing. The test is
mostly done t  specic scnning rte in  vrible rnge using  diffrctometer [15]. Most often,
DSC is used to ssess the crystlliztion nd therml properties of nnocomposites with different
MXene content or composition. With DSC, the non-isotherml melt nd cold crystlliztion nd
subsequent melting behvior hve been investigted by differentil scnning clorimetry [16].
Polrized light microscopy (PLM) is one of the methods used in polymer crystllogrphy. PLM
in contrst to other techniques provides  contrst-enhncing effect tht improves imge qulity
with birefringent mterils. Compred to drkeld nd brighteld illumintion, phse contrst, dif-
ferentil interference contrst (DIC), Hoffmn modultion contrst (HMC), nd uorescence, PLM
hs  higher degree of sensitivity tht mkes it  verstile tool for both quntittive nd qulit-
tive studies directed t  wide rnge of nisotropic smples including polymer nnocomposites.
The quntittive spect of polrized light microscopy is employed in crystllogrphy thn the quli-
ttive fcets. As  result, PLM is combined with ex situ or in situ fst scnning clorimetry cn
provide profound insight into crystl formtion nd nuclei evolution even for mterils tht undergo
fst-crystllizing like polymer nnocomposites. The downside, however, is tht the size of the crys-
tls or crystl superstructures like spherulites ought to be in the micrometer rnge to be detectble.
PLM is designed to observe nd photogrph smples tht re visible primrily due to their opticl
nisotropic properties s shown in Figure 7.1.
Ltely, fst scnning chip clorimetry (FSC) hs been developed s  precious tool in polymer
reserch with the bility to provide rel-time evidence bout the crystlliztion phenomenon, crystl
restructuring, glss trnsition, nd the melting phenomenon visully. The dvntge of FSC is tht it
hs  short response time in the order of microseconds tht permits  fst trnsition from scnning
to isotherml modes nd conversely. Beyond the performnce of FSC–tomic force microscopy
(AFM) coupled device hs been reported, where the AFM smple holder is substituted by the FSC
chip sensor to enble recurrent nneling t well-dened tempertures nd sometimes with the
AFM imges cpturing the phse trnsitions from the sme spot of the smple concurrently [18].
With this coupled device, vluble dt on nucletion rte nd crystl growth could be obtined,
136 MXene-Filled Polymer Nanocomposites

FIGURE 7.1 Electronic congurtion of PLM

especilly in situtions in which the heterogeneous nucletion overcomes crystlliztion t  low

supercooling rte of the melt, frequently resulting in spherulitic development of lmellr crystls in
most semi-crystlline polymers.

7.3 THERMAL PROPERTIES OF MXene

The therml properties of MXene re inuenced by severl fctors such s the type of surfce
terminting groups, the method of synthesis, nd the method of storge fter synthesis. It is impor-
tnt to highlight the effect of surfce terminting groups on the stbility (therml) of MXene nd
polymer composites. Also, the stbility under storge nd pplictions is very importnt becuse
severl studies hve indicted tht MXene degrdes when exposed to moisture or exceptionlly high
tempertures [19–21]. In  study of Nb2CTx MXene, it ws found tht the Nb dtoms locted t
the surfce bonded to mbient oxygen when exposed nd destbilized the system, resulting in the
grdul degrdtion of the compound structure [21]. In  similr study, it ws noticed tht  Ti3C2Tx
polyethylene terephthlte exposed to ir for 70 hours presented  signicnt reduction (pproxi-
mtely 20%) in its initil conductivity nd therml properties [22]. To curtil the degrdtion sso-
cited with the storge of MXene, it hs been suggested tht MXene nnosheets should be stored
in n environment free from oxygen with low light intensity. Also,  strong polr solvent such s
dimethyl sulfoxide (DMSO) nd n-methyl-2-pyrrolidinone (NMP) [23], or the ppliction of solu-
tion ltrtion processes re used to produce MXene lms, including  freeze-drying pproch [23,
24]. MXene processed in this mnner produces stble dispersions suitble for further processing
into continuous lms with dequte bonding to polymer mtrices. The ltrtion processes ensure
MXene nnosheets remin stcked, yet loosely pcked, due to the effect of vn der Wls force, nd
most of the time, in  wrinkled mnner; hence, the morpholicl rrngement remins intct with
little or no degrdtion internlly nd round the edges.
Thermal and Crystallization Behavior of Nanocomposites 137

Regrding the method of synthesis nd its effect on the therml stbility of the ensuing MXene
nnosheet, it hs been recommended tht optimized etching procedures tht reduce the dtoms
on the surfce of MXene be used to increse the stbility nd vert possible degrdtion [23]. The
surfce chrcter of MXene (e.g., chemicl ddends nd electricl properties) re undoubtedly lev-
erged s  foundtion for optimized fbriction conditions. The type nd elementl constituents
of MXene inuenced the therml behvior. For exmple, the ABABAB rrngement (hexgonlly
closely pcked stcking) of Mo toms in Mo2C in contrst to Mo3C3Tx (ABCABC ordering [fce-
centered cubic stcking] of Mo toms re deemed to grnt high therml stbility of Mo2CTxthn
Mo3C2Tx [25]. MXene Ti3C2Tx hs been conrmed to possess high therml stbility in  nitrogen
tmosphere from 0–950 °C [26]. Three insignicnt degrdtion steps observed were ssigned to
the evportion of free wter held on the surfce nd between the lyers of Ti3C2Tx followed by the
dissiption of bonding wter nd functionl groups on the surfce. The third stge ws ttributed
to the oxidtive decomposition of the titnium component. The brekdown temperture of the pure
MXene Ti3C2Tx itself ws bout 785 °C indicting better stbility to het [27].
In terms of therml conductivity, the ion interclted into the MAX phse might be metllic or
semiconducting, or hlf-metllic. When MXene is functionlized, the electronic properties differ
from metllic to semiconducting, contingent on the nture of the M, X, nd T clusters. The mjority
of surfce-terminted MXene, however, mintin their metllic properties wheres some undergo
chemicl chnges into semiconductors due to  shift of the Fermi level. Some MXene tht revels
metllic behvior includes Ti2CF2, Ti2C(OH)2, Ti2NF2, V2CF2, Cr2NF2, nd Zr2CF2, while others,
such s Cr2CF2, Ti2CO2, Zr2CO2, nd Mo2CF2, re considered s semi-conducting [28, 29].
Typiclly, MXene therml stbility conducted in the rgon tmosphere showed  three-stge
decomposition ttributed to mny fctors. The Ti3C2Tx mss loss of 0.38% from mbient temper-
ture to 200 °C ws ttributed to the removl of dsorbed H2O nd hydrogen uoride molecules
wheres  mss loss of4.48% between 200–800 °C ws ttributed to OH group removl followed
by nd  2.47% mss loss from 800 °C up to 1000 °C, ttributed to the elimintion of the uorine
toms [30]. Similr weight loss ws detected in other studies [31–33], which ws lter vlidted by
thermogrvimetric-coupled mss spectrometry (TG-MS) nlysis [34].
To remove the orgnic ddends nd further improve the therml properties, severl studies hve
suggested nneling s  therml tretment most effective for removing terminl groups (OH/F)
since ech cn be detched in  precise temperture rnge [33]. The downside of the therml tret-
ment, however, is tht the resultnt mteril cnnot be clssied s pristine MXene but rther s
n oxygented one, except the het tretment is done in  controlled environment without oxygen.
In recent times, exposure of Ti3C2Tx t 750 °C under vcuum hs been reported to remove the
mjority of the oxygen to obtin pristine MXene [35]. Prcticlly, the evlution of the therml
properties of MXene in ir is required. In n oxygen tmosphere, the formtion of rutile crystls
occurs round 500 °C, nd the MXene phse ltertion occurs t considerbly higher tempertures.
Typiclly,  Mo-bsed MXene exhibited high therml stbility up to 530 °C in H2/N2 environment
[36]. Also, the therml properties of MXene hve been studied extensively in  nitrogen tmosphere
nd results showed  much-improved therml property. For instnce, Zr3C2Tx ws studied in N2,
nd the results re shown in Figure 7.2. The MXene hd excellent therml stbility with little mss
loss. In this study, the initil loss in weight took plce t 125 °C, which is ttributble to the evpo-
rtion of bsorbed wter in the lyers of the MXene sheets. Nevertheless, it hs been reveled tht
the het tretment processes hve  signicnt impct on the structure nd properties of MXene.
Het tretment t reltively high tempertures is lible to led to the removl of functionl groups
contining –F or –OH/=O [3, 37]. The bsence of these elements is benecil in Li–ion btteries
due to decresed Li storge cpcity cused by the hydroxyl nd the uorine-terminted groups on
the surfce of Ti3C2 [3].
To evlute the complete removl or otherwise of the surfce terminting groups of MXene fter
nneling, n FTIR ws by Wng et l., to verify the removl of surfce ddends, nd the results
showed tht the intensity of pek t 3440 cm−1 reduced nd the pek t 1400 cm−1 disppered,
138 MXene-Filled Polymer Nanocomposites

100

80
0.5

Derivative weight (%°C)

Weight (%)

60 0.0

-0.5
40

-1.0
200 400 600
20
Temperature (°C)

0
100 200 300 400 500 600

Temperature (°C)

FIGURE 7.2 TGA nd dTG curves (insert) of MXene powder.

indicting  decrese in the content of –F nd –OH groups dhering to the surfce of the nneled
Ti3C2Tx nnosheets. However, the exposure of the MXene to therml reduction could increse the
rtio of C/O rtio—indicting tht the therml reduction hd dissipted prtil oxygen-contining
groups of MXene. Also, XRD results reveled the shifting of the (002) pek of the nneled Ti3C2Tx
from 6.58° to 6.40°. Furthermore, the therml reduction could be benecil to the delmintion of
the Ti3C2Tx nd the increse in the corresponding lyer spcing without necessrily exhibiting ny
by-product [38].
Furthermore, low-temperture conduction ex situ of the electronic properties of interclted
nd de-interclted MXene Ti3CNTx hs estblished tht nneling leds to the de-intercltion
of MXene. Also, the interclted MXene displys semiconductor-like behvior through the whole
rnge of the Physicl Property Mesurement System (PPMS; from RT to 263 °C), while the nneled
de-interclted MXene displyed metllic behvior t bout 150 °C nd below. At this stge, the
de-interclted MXene Ti3CNTx presents  trnsition to the negtive temperture dependence of
resistnce, nlogous to the behvior of multilyer Ti3C2Tx smples. They estblished tht nneling
Ti3CNTxbeyond 300 °C results in prtil de-functionliztion [29].

7.4 THERMAL BEHAVIOR OF MXene/POLYMER NANOCOMPOSITES

Due to the good brsion resistnce, processbility, trnsprency, nd mechnicl performnce of
most polymers, they re widely used in mny different res of life, mostly in the form of nnocom-
posites in utomobiles, medicl devices, sporting goods, nd decortions. However, fctors, such
s therml conductivity nd tensile strength, hve been hindering their ppliction in some elds
[15]. Trditionlly, the use of nnomterils s llers enhnces the generl properties of polymers
such s epoxy. They re lso used to increse the opertionl temperture window of polymer
nnocomposite. A polymer such s epoxy hs low therml conductivity due to the indiscrimintely
disheveled chins tht result in the scttering of the phonons [39]. MXene is one of the few best
solutions s  reinforcement with excellent therml stbility nd conductivity; hence, the ddition of
Thermal and Crystallization Behavior of Nanocomposites 139

MXene to polymers which re usully therml insultors cn improve the therml properties. The
ddition of MXene s nnollers for composites fbrictions connes the mobility of the polymer
chin, which directly inuences the glss trnsition temperture nd the subsequent crystlliztion
of polymers [4]. Comprtively, MXene polymer–bsed hybrids exhibit better therml stbility even
with lesser ller content thn grphene-bsed nnocomposites. The excellent therml conductivity
of MXene reduces the therml resistivity of the polymeric mtrix resulting in  uniform nd high
conductivity, especilly when the MXene lod is sufcient to form  good network with the poly-
mer chins [25]. As  result, MXene uniformly disperses within epoxy mtrixes, nd thus fcili-
ttes the intercltion of epoxy moleculr chins into spce between MXene lyers s discussed in
Chpter 6. Experimentl studies hve reveled the cost-effective MXene/polymer nnocomposites
with improved therml properties t low MXene loding, while in most occurrences, higher MXene
loding negtively ffects the therml stbility of the nnocomposites [4]. The therml behvior of
MXene/epoxy nnocomposites hs been studied extensively due to the wide ppliction of epoxy
polymer nnocomposites [39].
It hs been estblished tht the interply of PVA with MXene exhibits enhnced therml stbility
in both nitrogen nd oxygen tmospheres s shown in Figure 7.3[27]. The degrdtion of pure epoxy
cured with presumed sbestos-contining mteril (PACM) occurs bout 370°C. A minor enhnce-
ment ws noticed t 5wt% MXene Ti3CN lling, which extended the onset degrdtion to round
380°C. A further increse in MXene loding (in Ti3CN-epoxy composites) resulted in low therml
stbility nd demonstrted  shrp drop in initil decomposition temperture. This phenomenon is
ttributed to Ti3CN dispersion throughout the mtrix. Noteworthy is tht the increses in MXene
gve considerbly good stbility t higher tempertures compred to the nnocomposites with lower
MXene lod. In other words, the degrdtion temperture of the nnocomposite reduces s the
MXene ller content increses, rrying the positive impct of MXene in meliorting the therml
stbility of the polymer. The underlining explntion for the improved stbility is tht, in the pres-
ence of MXene nnollers, the mobility of the polymeric chins is restricted, nd thus,  higher
temperture is required for the movement of the moleculr chins. This occurrence is primrily
relted to the negtively chrged MXene kes hving the potency to dsorb mine-bsed hrden-
ers, which inuences the structure of the polymer fter the curing process [26].
Figure 7.3b shows  line grph of MXene content ginst temperture. The line indictes tht
little decomposition is experienced t tempertures between 300–380 °C when higher MXene con-
tent is included in  composite. The higher the MXene content, the lower the mss loss experienced
within the temperture zone stted.

FIGURE 7.3 () TGA curves of MXene-epoxy composites with vrible Ti3CN lling, (b) diminution in
onset degrdtion with incresing MXene lling.
140 MXene-Filled Polymer Nanocomposites

Microstructurl nlysis of Ti3C2Tx/epoxy composite with vrying MXene Ti3C2Tx loding indi-
ctes tht few-lyer Ti3C2Tx MXene disperses homogeneously in polymer mtrixes thn poorly
delminted MXenes with more stcked lyers. MXene Ti3C2Tx promotes therml trnsfer between
moleculr chins nd enhnces the ppliction of such nnocomposite for het conduction. Also, the
coefcient of therml expnsion (CTE) vlues decrese with incresing MXene in most epoxies due
to its bility to restrin the mobility of the polymer chins [39]. Also,  high-temperture degrd-
tion of 1.74 vol% Ti3C2TxMXene in epoxy nnocomposites ws ssigned to the proper delmintion
of the MXene nnosheets, resulting in improved brrier resistnce nd subsequent reduction in the
evolution of orgnic voltiles due to the tortuous effect [40]. Similrly, it hs been demonstrted
tht the initil decomposition temperture of polyurethne nnocomposite (with 0.5 wt.% polyeth-
yleneglycol) improved signicntly fter the ddition of MXene. Contrry to the result reported in
most studies, the initil degrdtion temperture of MXene/polymer nnocomposites lowers s the
MXene lod increses but gets improved fter 400 °C thnks to the high therml conductivity, sur-
fce energy, nd the uniform dispersion of MXene nnosheets, which enhnces the therml trnsfer
in the mtrix [15].
An nlysis of the therml conductivity of Ti3C2/poly(vinylidene uoride) membrnes with dif-
ferent MXene Ti3C2 percentges hs estblished tht low MXene Ti3C2 loding (<1.0 wt.%) grnts
signicnt elevtion in the therml conductivity while further increses in the MXene lod leds to
n excellent therml conductivity. This ws ttributed to the vrying phse structures in the nno-
lms, which form se-islnd structures on the incorportion of reltively low MXene Ti3C2. The
incessnt network formed t high MXene Ti3C2 loding leds to  rpid increse in conductivity.
Other mjor resons tht fcilitte the increse in the therml conductivity re mostly s  result
of the lrge surfce re of MXene Ti3C2 nnokes nd the development of hydrogen bonding
between Ti3C2 nd epoxy, which reduces the interfcil het resistnce, especilly t higher MXene
Ti3C2 loding [37].
Temperture-dependent nd polrized lser power-dependent Rmn tests were dopted to
study the therml conductivity of MXene Ti3C2/polyvinyl chloride (PVA) nnolm nd other poly-
mers. It ws relized tht the therml conductivity of the membrne ws reltively lower thn the
pristine MXene Ti3C2 but signicntly higher thn the composite membrne contining iron, sili-
con dioxide, luminum oxide, nd stinless steel, respectively. Generlly, the therml properties
nd conductivity of MXene-lled polymer nnocomposites re leverged by the percentge of ll-
ing, proper dispersl, phse structure, nd the interfcil therml resistnce. In  typicl study of
the therml degrdtion of MXene Ti3C2/epoxy [41], the temperture rises long with the increse
in the concentrtion of MXene. However, similr to other studies lluded to in the preceding pr-
grphs, the therml stbility begn to decline when the MXene Ti3C2 loding reched 5.44 wt.%.
A similr occurrence ws observed in MXene Ti3C2/liner low-density polyethylene (LLDPE) [3].
Usully, the improvement in the therml stbility of MXene Ti3C2 results from the formtion of
solid Ti−O bond between Ti3C2 nd most polymeric mtrixes, which decreses the therml coef-
cient of the Eg 1 mode. It hs been estblished tht the Ti–O linkge is the most stble bond
mid the functionl groups of Ti–O, Ti–F, nd Ti–OH, hving respective bond strengths of 1.97 Å,
2.17 Å, nd 2.19 Å [42].
More so, n experimentl non-isotherml crystlliztion nd theoreticl clcultion of the crys-
tlliztion kinetics ws studied using the Mo model, which dequtely describes the non-isotherml
crystlliztion kinetics of Ti3C2/LLDPE blends [3]. At 2.0 wt % Ti3C2 loding, the composite
showed the highest crystlliztion rte; however, t 4.0 wt % Ti3C2 loding, the rte of crystlliz-
tion becomes even slower crystlliztion thn the net LLDPE lm. It ws relized tht LLDPE
chins entngled on the surfce of Ti3C2 nd restricts movements nd self-ssembly insted of the
ller serving s nucleting sites for esy crystlliztion. In certin polymers, for instnce, MXene/
nylon 6 nnocomposites, higher MXene loding incresed the rte of crystlliztion nd t the sme
time increses the melting temperture of the composite. Such enhncements in therml stbility
hve been linked to the enhnced brrier qulities due to the torturous pth effect [40].
Thermal and Crystallization Behavior of Nanocomposites 141

It is worth noting tht the therml decomposition nd the crystlliztion behvior of MXene
loding on different polymer nnocomposites vry. For poly(lctic cid) (PLA), the incorportion of
0.5% nd 1% MXene intensies the therml stbility of the nnocomposites signicntly, wheres,
t  higher MXene loding, the therml stbility gets reduced portentously. Hence, it is estblished
tht 1% MXene nnosheet lling is idel for enhncing the therml stbility nd improving the
crystlliztion behvior of MXene/PLA composites. Further increses in the MXene content in the
nnocomposites present  complicted result tht is rrely reported becuse of the pretentious initil
increse in therml stbility of PLA while displying converse results s the heting progresses [43].
Therefore, the clss or composition of polymer could be considered n essentil fctor in improving
the interfcil interction between the polymer nd MXene ller towrd high therml properties.

7.5 THERMODYNAMICS OF CRYSTALLIZATION AND

MELTING OF POLYMERS
Thermodynmics ddresses the reson behind or the circumstnce tht leds to the crystlliztion
of polymers, or their melt phenomenon. As lredy indicted, most polymers re semi-crystlline
in nture, which implies tht polymers re composed of morphous nd crystlline regions in 
single polymer unit. Crystlliztion nd the melting phenomenon re chrcteristiclly rst-order
phse evolutions between the morphous nd crystlline phses. An instntneous chnge in the
proportion or density of the composition is referred to s  rst-order phse trnsition. This is
complemented by the relese of het, lso clled the het of trnsformtion—which is mostly linked
to the primry cuse of chnges in composition. The second-order phse trnsition occurs when
the incresing distnce of one end cuses the trnsition of some physicl quntity t the other end
(equl to zero) to grdully increses from zero. In this cse, the density nd concentrtion of the
composition in the nnocomposite vry incessntly, nd the therml effect creted is not relesed
or bsorbed. The two phses re reversible in thermodynmic equilibrium t  certin temperture.
The temperture is termed the equilibrium melting point of polymer crystls. At the polymer nno-
composite equilibrium melting point, there exists  free-energy chnge (zero), especilly in the bulk
system of polymers [1].
Among fctors ffecting the therml behvior of polymers nd nnocomposites, crystlliztion
is one of the crucil fctors from both  scientic nd industril stndpoint, becuse the mechni-
cl/therml properties of polymers nd their nnocomposites gretly depend on their crystllinity.
Cold crystlliztion (which is discussed in the ltter prt of the chpter) occurs when polymers or
polymer nnocomposites re quenched rpidly fter melting. Also, crystlliztion endotherms re
usully detected when polymers or polymer nnocomposites re slowly cooled fter melting. The
kinetics of the overll crystlliztion phenomenon is well ordered by nucletion mechnism nd
crystl growth rte. These two kinetics cn be ffected by mny conditions including temperture,
the type of llers (size, orienttion, interfcil properties, etc.). For instnce, incresing the tem-
perture fcilittes the increment in crystlliztion in the crystl‐growth sites of most polymers nd
nnocomposites, while there is  decrese in the crystlliztion t the nucletion‐controlled sites.
The degree of crystllinity cn be estimted from the pek re of the curve obtined from  DSC
mchine or n XRD device.
In composite formtion, the degree of crystlliztion cn be ffected by the ddition of specic
compounds. For instnce, the ddition of  plsticizer often results in n increse in the degree of
crystlliztion by ccelerting the spherulite growth rte, while  nucletion gent (which could
be nnollers like crbon nnotubes/bers, grphene, or MXene) cn lso ugment the rte of
crystlliztion vi cumultive nuclei density [44]. The MAX phses from which MXene kes
re obtined, re thermodynmiclly stble nd disply some metllic properties, such s high
electricl nd good mechnicl properties, with some level of good therml conductivity. Due to
their verstility, they lso hve good stiffness, low density, nd excellent corrosion resistnce simi-
lr to cermics. These unique chrcteristics of MAX phses ender them vluble for severl
142 MXene-Filled Polymer Nanocomposites

industril pplictions, including high-temperture cermics, protective cotings, nd electricl nd
electronic prts [25]
As indicted, the crystlline/morphous structure of polymer mterils gives specic proper-
ties. The melting point of crystlline polymers often occurs t elevted tempertures, nd with the
incresing temperture, it improves due to the chnges in the crystllinity of the polymer. Also,
ltertion in the physicl structure of the polymer from solid to  molten stte is very rpid t
incresing temperture. In polymers composed of  high percentge of morphous structure, there
is no brupt chnge of physicl structure like s observed in the crystlline polymer. When the
temperture decreses from the molten to solid stte,  grdul chnge in the physicl ppernce
is reveled in morphous polymers. The cooling down leds to the lowering of the therml expn-
sion of morphous polymer, which hppens bruptly due to decresing temperture. In the level of
crystllinity between these two tempertures, tht is, the high temperture nd low temperture,
the therml chrcteristics of polymers re reveled. Furthermore, bove the melting point of most
polymers, viscous chrcteristics re reveled; they show viscoelstic properties in the region of
glss trnsition nd melting temperture.
The formtion of crystls in polymeric mterils cn occur during either the heting or the cool-
ing cycle depending on the rte t which het is supplied in the heting process or the rte t which
the mteril is cooled down fter heting. With the incresing crystlline structure, the melting
temperture lso increses. Regrding the therml chrcteristics of polymers with high melting
points, such s thermosets nd elstomers, they often show morphous chrcteristics by lowering
the temperture from the liquid stte. In ddition, the decresing temperture leds to the occur-
rence of crosslinks. These crosslinking restrins the crystlliztion of polymeric molecules nd hin-
ders the remelting nd reliquection of polymers owing to the structurl cross-linkges. Given tht
the incorportion of nnollers lso inuences the melting point of  polymer, n investigtion into
the structure nd crystlliztion behvior of nnocomposites, such s MXene Ti3C2/polyethylene
oxide lms were done. Interestingly, in most nnocomposites, the rte of crystlliztion increses
rpidly from the beginning nd then decreses on the ddition of vrying MXene lod. Similr
to the therml phenomenon, the fstest crystlliztion rte is usully observed t low concentr-
tions of MXene. This occurrence is mostly ttributed to the equilibrium between nucletion rte,
which results in crystl formtion, nd the connement effect creted by the MXene nnollers.
Chrcteristiclly, low MXene loding hstens the crystlliztion rte by heterogeneous nucletion
wheres higher MXene loding tends to slow down the crystlliztion rte becuse the nucletion
rte gets reduced considerbly due to n unyielding nd limited connement network.

7.6 CRYSTALLIZATION OF POLYMER NANOCOMPOSITES

Crystlliztion is  two-step route, tht is, nucletion nd growth, which chnges stte s  result of
fctors such s time nd temperture. The bsence of enough time or temperture does not llow
the polymer to crystllize completely. Impurities in crystllites re lible to decrese the melting
temperture. The crystlliztion of polymers nd polymer nnocomposites cn be ctegorized into
three groups, nmely,

. crystlliztion during polymeriztion,

b. crystlliztion induced by orienttion, nd
c. crystlliztion under quiescent conditions.

The hllmrk of polymeriztion crystlliztion is the development of mcroscopiclly distinct crys-

tls. In the course of single crystl formtion, the originl “monomer” crystls re conserved while
the monomers developing into crystls link up into chins by solid-stte polymeriztion. The ter-
minl polymer crystl is ttined upon the interfcil chemicl interction t the gs/solid or liquid/
solid, which cnnot be scribed to chnges in the physicl stte of the mteril s in the cse of the
Thermal and Crystallization Behavior of Nanocomposites 143

FIGURE 7.4 Polymeriztion subsequent to crystlliztion (i, ii) nd crystlliztion in the course of polym-
eriztion (iii).

norml crystlliztion processes. The chrcteristics of the crystls formed vi this method cn
be very interesting, becuse some hve displyed good conduction bility for electricity long its
xis even t reltively low tempertures. A brief description of such mechnisms is simultneous
polymeriztion nd crystlliztion or successive polymeriztion nd crystlliztion illustrted in
Figure 7.4. In the concurrent polymeriztion nd crystlliztion, the prime nd ncillry linkges
occur simultneously. One of the dvntges of simultneous polymeriztion nd crystlliztion of
polymer is tht it cn occur on monomers in gs or melt stte, benecil to mcromoleculr crystl-
liztion tht tkes plce on solely the melt or solution stte. There is lso the tendency tht could
cuse the folding of chin crystls below the glss trnsition temperture of the ultimte polymer or
polymer nnocomposite system.
For crystlliztion induced by orienttion, the procedure cn be termed s distending long polymer
chins to yield brous crystls. This mens of crystlliztion is the fundmentl process identied in
the development of bers into smooth, thin, nd lengthened chin morphology, which is chllenging
to chieve in the most semless conditions. When the polymer is stretched, the polymeric chins tend
to reorient from their initil congurtion (mostly morphous), which leds to  reduction in entropy
(Figure 7.4). Nnollers tht exhibit  lrge surfce re hve  noticeble effect on the crystlliztion
behvior of the polymer. The lrge surfce re of the nnollers nd the movement in the polymeric
chins ner the prticle surfce could ffect crystlliztion. During polymer processing (extrusion,
injection molding, lm blowing), non-isotherml crystlliztion conditions re involved; therefore, 
thorough understnding of the fctors tht ffect crystlliztion is essentil for the optimiztion of the
processing conditions nd the ne-tuning of the properties of the end product. The conditions under
which the crystlliztion of the polymer tkes plce ffect numerous properties of nnocomposites
such s the rte nd the degree of crystllinity. Other known effects in the course of crystlliztion re
heterogeneous nucletion, trns-crystllinity, nd epitxy. Also, the ppernce of solid surfces in the
melt leds to the formtion of heterogeneous nucletion. This nucletion is induced by the decresing
crucil enthlpy during nucletion t the melt nd solid interctive sites. This indictes tht the interc-
tion between the polymer nd the nnollers ffects the polymer morphology.

7.7 THE THERMAL PHENOMENON

7.7.1 GLASS TRANSITION TEMPERATURE
In the morphous sections of the polymer, the molecules re considered to be in  frozen stte
t lower tempertures. In this stte, the molecules cn vibrte slightly but cnnot experience sig-
nicnt mobility. The polymer is brittle, hrd, nd rigid compred to  crystlline solid with the
144 MXene-Filled Polymer Nanocomposites

moleculr hysteri s  liquid with resemblnce to glss, therefore the term glassy state. The glssy
stture is nlogous to  supercooled liquid in which the mobility of polymer molecules is in  fro-
zen stte. Upon heting, the polymer chins cn wggle bout ech other nd becomes soft, exible,
nd lithe, just like rubber, hence the term rubbery state. The point (temperture) t which the glssy
stte trnsitions to  rubbery-like mteril is known s the glss trnsition temperture (Tg). This
property ffects the storge modulus of nnocomposites signicntly. Usully, the glss trnsition
hppens somewht in the morphous regions of the polymer only. The crystlline region is lrgely
intct during the glss trnsition period in most semi-crystlline polymers. When the mobility of
the moleculr chins tkes plce esily, the glssy stte cn trnsition into the rubbery stte t 
lower temperture. In cse the movement of the moleculr chins gets obstructed, then the glssy
stte becomes stble nd, in so doing, restricts ny brekge; however, it results in the immobility
of the polymer chins t the lower temperture. The immobile molecules necessitte more energy to
set them free nd mobile, implying  rise in the Tg. The Tg is usully ffected by such dynmics s
moleculr weight, mesurement method, composition, plsticizer employed, nd, more importntly,
the heting nd cooling rte.
The glss trnsition temperture (Tg) is n importnt prmeter, tht species the upper tem-
perture limit for most pplictions. Also, chnges in glss trnsition temperture gures hve n
essentil connection with reinforcement phses nd the interfcil reltions between reinforcement
mterils such s MXene nd polymeric resins [45]. In this regrd, the effect of MXene on the crys-
tlliztion behvior of epoxy nnocomposite synthesized vi in-situ intercltion polymeriztion
in which the epoxy moleculr chins rected with the hydroxyl groups on the surfce of MXene
Ti2CTx nnosheets to form  3D crosslinked network structure during curing ws studied [45]. The
glss trnsition temperture incresed grdully with  chnge in the concentrtion of MXene
Ti2CTx. It ws noticed tht the integrtion of MXene Ti2CTx into epoxies increses the glss trnsi-
tion temperture due to the interfcil interction nd crosslinking effect between MXene Ti2CTx
nnosheets nd the moleculr chins of epoxy. This implies tht when the temperture increses,

FIGURE 7.5 Grphicl representtion of temperture-dependent glss-trnsition process.

Thermal and Crystallization Behavior of Nanocomposites 145

the surfce of the stiff MXene Ti2CTx nnosheets forms n enhnced interfcil interction with the
epoxy molecules, which hinders the vibrtion of moleculr chins nd leds to n upsurge in the
relxtion period [45].
A study on the glss trnsition temperture vlues of rGMH/epoxy nnocomposites lso con-
rms  positive impct of MXene on nnocomposites s the mss lod of MXene increses [47].
Epoxy resin ws interwoven into 3D rGMH network to form the rGMH/epoxy before the incor-
portion of MXene. It ws relized tht when 3.3wt.% of MXene ws loded in the nnocompos-
ite, the Tg of rGMH/epoxy nnocomposites incresed to 150.9°C, which is 13.9°C higher thn the
vlue recorded on the pure epoxy resin (137.0°C). Upon the elevtion in temperture, the surfce
of the stiff MXene intercts strongly with the epoxy moleculr chins, thereby enhncing the dely
time nd obstructing the epoxy moleculr chins vibrtion, thus incresing the Tg vlue, similr to
the erlier reports [45]. The reson for such vrition in Tg is due to the physicl brrier effect of
MXene, which limits the mobility of the epoxy moleculr chins nd reduces the therml diffu-
sion of rGMH/epoxy nnocomposites. This phenomenon lso contributes to the dely of the ther-
ml decomposition of rGMH/epoxy nnocomposites, which contributes to the improvement in the
therml stbility of the ensued nnocomposites [47]. Also, the effect of MXene loding on the
glss trnsition temperture of MXene/polymer nnolm ws studied by DMA, nd the Tg vlues
were obtined from the pek vlue of the loss fctor from the DMA curves. There ws  rise in the
Tg of MXene Ti3C2/poly(vinylidene uoride) membrnes when the concentrtion of MXene Ti3C2
ws incresed. A similr phenomenon ws observed in MXene Ti3C2/epoxy membrne by DSC. A
grdul increse in the glss trnsition temperture of the nnocomposite ws recorded with the
incresing content of MXene Ti3C2 kes in the composites. The elevtion in the glss trnsition
temperture ws ttributed to the restricted moleculr motion nd incresed crosslinking density
[4] [39]. Other studies hve conrmed the effectiveness of MXene in improving the Tg of polymer
nnocomposite due to the restriction in moleculr motion. More importnt, it hs been observed
tht the higher the degree of crosslinking, the greter the ltertion in the dynmics of the polymer
moleculr chins. Also, the presence of functionl groups on the surfce of n MXene nnosheet
improves the interfcil interction between MXene nd the polymer mtrix, resulting in good nd
uniform dispersion of MXene within the mtrix, which is benecil for chieving  big shift in the
Tg [37]. In totlity, the incorportion of MXene into polymer produces better thermo-mechnicl
properties tht perform better in  wide rnge of pplictions, such s seprtors, btteries, sensors
nd ctutors, smrt scffolds, nd ltrtion membrnes. Tble 7.1 outlines some of the estblished
Tgs of polymer nnocomposites.
To give  comprehensive description of the melting temperture of  nnocomposite,  distinction
between glss trnsition nd melting temperture is necessry. The Tg is ssocited with chnges
tht occur in the morphous regions of the polymer, wheres the melting temperture is connected

TABLE 7.1
List of Polymer Nanocomposites and Their Corresponding Glass Transition Temperatures
Polymers Glass Transition Temperature Range Ref.
Pure epoxy 137 °C [47]
rGO-epoxy nnocomposites 139.8 °C [47]
rGO-(MXene)/epoxy nnocomposites 150.9 °C [47]
Poly(vinylidene uoride) −32 °C [37]
MXene/poly(vinylidene uoride) −25.5 °C [37]
Polystyrene 90 °C [48]
Nnogold/polystyrene 105 °C [48]
Polymethyl methcrylte 40–140 °C [49]
146 MXene-Filled Polymer Nanocomposites

to the trnsitions in the crystlline region. Thermodynmiclly, the ltertions re termed the rst-
nd second-order trnsitions. Tg is the second-order trnsition, while the melting temperture is the
rst-order trnsition. Unlike melting temperture, the vlue of Tg is not unique becuse the glssy
stte is not lwys in equilibrium. All semi-crystlline polymers disply both trnsitions corre-
sponding to their crystlline nd morphous regions. Semi-crystlline polymers possess melting
tempertures t which the well-ordered phse chnges to disrryed phses, while the morphous
sites soften in the glss trnsition temperture rnge. It is worth noting tht melting point is bsent
in morphous polymers, but ll semi-crystlline polymers hve Tg. Inuentil fctors, such s the
presence of romtic groups, double bonds, nd bulky or lrge side groups, could ffect the stte of
polymer melting temperture. These outlined fctors hve the propensity to hinder the mobility of
the polymer moleculr chins, thereby limiting crystlliztion nd ffecting the melting temper-
ture of nnocomposites. Furthermore, the brnching of moleculr chins in  polymer could lso
led to  decrese in melting point. This negtive effect cused by the brnching is ssignble to the
defects creted by the brnches. Hence, the melting temperture is highly dependent on the previ-
ously mentioned fctors.
The melting temperture of polypropylene-grfted MXene nnocomposites shows systemtic
chnges in MXene loding for polypropylene-g nnocomposite. At  considerbly lower Ti3C2Tx
loding, the melting temperture reduces while  higher Ti3C2Tx loding bove 0.5 wt.% results in
incresed melting temperture. The reson for the reduced nnocomposites melting temperture
t low Ti3C2Tx loding (below 0.5 wt.%) is due to the wek connement of polypropylene-grfted
chins in the MXene Ti3C2Tx/polymer nnocomposite, while the increse in temperture is due to
higher Ti3C2Tx loding is scribed to the strong hydrogen bonding from the mleic nhydride-g-
polypropylene nd the –OH groups from the Ti3C2Tx, which restrins the motion of polypropylene-
g chins [50]. It is lso found tht the ddition of Ti3C2Tx nnocomposite into polypropylene-g
mtrix results in  slight improvement in the vlues of crystllinity. This phenomenon indictes
tht the slippge over H-bonds induced nnoconnement nd resulted in improved crystllinity.
Furthermore, the crystllinity of polypropylene-g/Ti3C2Tx nnocomposites decreses slowly with
the incresing Ti3C2Tx lling (tht is when the lod ws more thn 1 wt.%). It is worth mentioning
tht the crystllinity vlues re not consistent with the crystllinity vlues in the XRD nlysis,
due to the therml cpcity of the distorted polymeric molecules improving their intrinsic stte or
equilibrium mode fter the relxtion process [50].

7.8 NON-ISOTHERMAL MELT AND COLD CRYSTALLIZATION

OF MXene-BASED POLYMER COMPOSITES
Crystlliztion tht occurs beyond the glss trnsition temperture when the polymer is heted
in the glssy or morphous stte is referred to s “cold crystlliztion”. This occurrence is often
detected in supercooled phses of polymeric mterils fter the evolution in the thermodynmiclly
stble crystlline phse [51]. Cold crystlliztion, lso clled post-crystlliztion, occurs bove the
Tg when the polymer chins gin dequte motion to rrnge themselves into n ordered crystl-
line structure by chin folding. The cold crystlliztion phenomenon occurs between the Tg nd
the melting temperture. Cold crystlliztion is determined from the DSC exothermic pek. The
importnce of crystlliztion (cold crystlliztion) to industril mnufcturing of composites cn-
not be overemphsized, becuse the mechnicl nd opticl performnce nd the long-term stbility
of nl polymeric products in pplictions depends lrgely on this property. More so, the right pro-
cessing temperture for most semi-crystlline polymer composites is determined by cold crystl-
liztion, which is necessry for product development nd engineering.
The bsence of crystlliztion during the cooling cycle revels tht the polymer hs ttined
stble nuclei. In ddition to the phenomenon of glss trnsition, cold crystlliztion lso occurs
when  polymer is composed of morphous nd crystllizble components. Thus, the exothermic
cold crystlliztion ttined during heting shows the reorgniztion of polymeric chins becuse
Thermal and Crystallization Behavior of Nanocomposites 147

the initilly morphous structure begins to crystllize. Cold crystlliztion of semi-crystlline pls-
tics occurs t elevted tempertures nd increses moleculr mobility bove the glss trnsition,
even though some studies hve reveled tht it cn tke plce t room temperture for rubber or
thermoplstic polyurethne. Cold crystlliztion is  chnge in the physicl structure tht leds to
n increse in the degree of crystlliztion nd the lmell thickness, s well s to the perfection
of the crystl structure. During cold crystlliztion, t the trnsition zone between the existing
crystlline structures nd the morphous regions, new ordered structures (crystllites) grow. These
newly formed crystls cn be differentited from the preexisting ones using their lower melting
temperture.
Cold crystlliztion is mostly reported for mcromolecules with pronounced structurl mobil-
ity; however, cold crystlliztion of smll molecules is possible but quite rre, hence the knowledge
bout the design guidelines for these molecules [51]. Cold crystlliztion gives  typicl crystl
morphologies with remrkble physicl properties. In ddition to the rre observtion of cold crys-
tlliztion in smll molecules, some chllenges remin with the clriction of the reltionship
between stble morphous (glssy), other condensed sttes, nd the development of the comprehen-
sive moleculr model concerning “cold crystlliztion” [51].
Melt crystlliztion is lso known s crystlliztion from the melt (the melt is most correctly
referred to s pure molten solid). Melt crystlliztion is the preferred seprtion technique for renew-
ble mterils. The fundmentl development of the melt crystlliztion processes for renewble
mterils like crylics provides good theoreticl yields for the production of high-purity crylic cid
[52]. Despite the dvntges of this process, melt crystlliztion hs not been utilized most in poly-
mer engineering. The indequte understnding of the het nd mss trnsfer in melt crystlliztion
nd the difculties in hndling the solid trnsport nd solid–liquid seprtion re under investig-
tion to grnt more understnding bout melt crystlliztion. With the ctive reserch in this eld
of endevor, there is  bright future in the fbriction nd ppliction of polymer nnocomposites.
The non-isotherml melt crystlliztion performnce of PLA/MXene nnocomposites ws
investigted, nd the cooling curves of the melt nd the ensuing heting trces were thoroughly
studied. It ws observed tht t  higher cooling rte, no exothermic pek is detected for pristine
PLA due to its poor crystlliztion bility. On the contrry, the introduction of MXene (0.5 wt%
loding) enhnces the crystlliztion of PLA signicntly. Upon further increses in MXene lod-
ing, the crystlliztion temperture (pek) remined virtully constnt. However, s the cooling rte
increses further, the single crystlliztion pek trnsitioned into  double pek. Further increses
in the heting rte often result in chnges from  double pek to  single pek. Isotctic poly-
propylene hs been reported to behve in  similr wy [53]. With such polymers, heterogeneous
nucletion is dominntly reported  slower cooling rte due to the lower super-cooling rte, while
t  higher cooling rte, heterogeneous nucletion is less likely; rther, homogeneous nucletion
previls. However, moderte cooling rtes instigte the coexistence of heterogeneous nd homoge-
neous nucletion nd thus present double crystlliztion isotherms [53]. It is importnt to note tht
double-pek phenomenon in polymer composites is often ssocited with the presence of more thn
one crystl form occurring in the composite. It is worth stting tht, the ddition of MXene does not
usully results in signicnt shift in crystlliztion temperture especilly during cooling; however,
the crystlliztion pek rther gets nrrower [43]. This revels the low crystllinity of the smples
before cold crystlliztion. In certin polymers, cold crystlliztion pek is usully undetected,
implying tht the smples hve  high degree of crystllinity fter crystllizing from the melt due
to melt recrystlliztion [43]
For instnce, the crystlliztion thermogrph for pure liner low-density polyethylene (LDPE)
nd MXene/LDPE nnocomposites t four diverse cooling rtes ws investigted. It ws observed
tht the crystlliztion temperture moved to lower tempertures with  decrese in the crystlliz-
tion enthlpy for 2 wt% MXene composite. The crystlliztion enthlpy decresed further with the
increse in MXene loding in the composites s the cooling rte increses. For the nnocomposites
crystllizing t  higher cooling rte, the production of the nuclei nd the rrngement of chin
148 MXene-Filled Polymer Nanocomposites

segments were negtively ffected due to insufcient time. In contrst, during  lower cooling rte,
the nuclei ctivtion occurred t  higher temperture nd the rry of chin segments remined in
order. In other words, the higher cooling rte hinders the rte of crystlliztion, including nucletion
nd crystl growth. Moreover, when cooling rtes reduce, the onset temperture of crystlliztion
nd the temperture of exothermic of the pek of MXene/LDPE nnocomposites increses signi-
cntly compred to tht of pristine LDPE, which indictes tht MXene is effective in enhncing
the nucletion rte of polymers. However, the composites presented lower crystlliztion enthlpy
t wider temperture rnges—indicting the presence of more lttice defects, poor movement of
moleculr chins, nd low crystllinity [3].

7.9 EFFECT OF MXene ON THE CRYSTALLIZATION

BEHAVIOR OF POLYMER NANOCOMPOSITES
Theoreticlly, crystlliztion is  two-step procedure involving () nucletion nd (b) growth (crys-
tl formtion). The proportion of the nucletion rte to tht of the growth rte is the most importnt
determinnt of the sequence of crystlliztion. The nucletion comprises both homogeneous nd
heterogeneous crystl formtion. Due to the highly ctive surfce of most nnollers, the moleculr
chins of polymers grvitte to the surfce of the nnollers, serving s  heterogeneous nucletion
site in improving the crystllinity of polymer molecules. From this perspective, it could be pro-
pounded tht MXene (such s Ti3C2) cts s  nucleting gent in the nnocomposite in the slurry
before fbriction or during solidiction (drying/cooling) to provide  lrge surfce to serve s
nucletion centers to increse the rte of crystlliztion nd the percentge of crystls in the mol-
ecules of the polymer. In other words, with  similr growth rte, there exist more nucletion sites
which leds to lrge polymer crystllinity. With the increse in MXene lod, the overll crystlliz-
tion rte of polymer tends to increse [54]. The subtopics discussed erlier, buttressed with results
in the literture, revel more bout the effect of MXene on the crystllinity of polymer [39, 50]. In
 typicl study of PVDF composites with 0–5 wt% MXene loding, n improvement in the PVDF
therml conductivity nd the thermodynmic mechnicl properties were obtined. Further study
into the mechnism of crystlliztion reveled the existence of MXene fst-trcked PVDF crystl-
liztion t  low MXene lling, with the fstest crystlliztion occurring in the composite with 0.5
wt% MXene content [9].
In most cses, the existence of MXene Ti3C2Tx hstens polymer crystlliztion t reltively low
MXene lodings; however, the polymeriztion processes get impeded s MXene lling increses.
The fstest crystlliztion rte hs been reported mostly for nnocomposite hving considerbly low
MXene loding due to its enhncement effect in nucletion rte, which results in fster crystl for-
mtion [5]. Nucletion is the process by which polymer molecules cluster together to mke  lrger
structure of  denite criticl size termed crystls. Thus, the MXene llers ct s nucleting gents,
which id the cluster formtion of the polymer molecules. Nevertheless, s the content of MXene in
the polymer mtrix increses beyond  certin threshold,  phenomenon clled nno connement
occurs, where the movement of polymer nuclei get limited (impeded) by the excess MXene ll-
ers, hence reducing the rte of crystl formtion. Generlly, MXene increses the tensile strength
nd the elongtion t the brek of nnocomposites when the loding is minimlly optimized. It is
importnt to stte tht, the delminted MXene provides more dvntges in composites formtion
thn its bulk chrcter. Unlike the bulk MXene, delminted MXene improves the mechnicl
nd tribologicl properties of polymers becuse of the high level of dispersion nd homogeneity
besides the lrger surfce re. The most efcient wys to obtin  uniform dispersion of MXene
nnollers into  polymer mtrix is through covlent functionliztion, surfce modiction with
functionl molecules (surfctnts), or with novel etchnts. The reinforcement effect of MXene poly-
meric mterils is usully ttributed to the increse in interfcil interction between the nnosheets
nd the neighboring polymer mtrices. This interfcil interction effect is not possible with bulk
MXene, hence less usge for engineered polymer composites. The pie chrt in Figure 7.6 shows the
Thermal and Crystallization Behavior of Nanocomposites 149

Low thermal properties

High thermal properties

FIGURE 7.6 Grphicl representtion of the proportion of positive to negtive impct of MXene on polymer
nnocomposites’ therml properties.

proportion of literture tht hve reported signicnt improvement the therml properties of poly-
mer nnocomposite to tht of studies tht hve reported dverse effect of MXene incorportion in
polymer nnocomposites.

7.10 CONCLUSION
The therml behvior nd crystlliztion of polymer discussed in the chpter hve reveled mny
different inuentil fctors tht combine to ensure good therml properties of polymer nnocom-
posites. The ddition of nnoller such s MXene hs  crucil impct on the therml behvior
nd crystllinity of the polymer nnocomposites. Chrcteriztion techniques, such s TGA, DSC,
nd XRD, re primrily used for the evlution of therml properties. Three mjor processes of
polymer crystlliztion nd their behvior on the polymer crystls upon  chnge in conditions hve
been unveiled. It hs been generlly estblished tht low MXene loding fcilittes enhncement
in crystlliztion, which is economiclly benecil in the production nd ppliction of nnocom-
posite. The positive impct of MXene in polymer nnocomposite in enhncing the therml nd
crystllinity of the polymer hve been ssigned to the strong interction between the MXene nd
the monomeric component, dispersion, nd bonds creted between the nnoller nd polymer dur-
ing the fbriction stge, which reduces the mobility of polymer chins. Fctors such s Tg nd
the melting temperture of polymers hve lso been explicitly discussed. Conclusively, lthough
the incorportion of MXene enhnces the properties of polymer nnocomposites, excessive lod is
lible to reduce the required therml properties of the nnocomposites.

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 8 Tribological Performance
of MXene/Polymer
Nanocomposites
Rodrigo Mantovani Ronchi, Hugo Gajardoni
de Lemos, and Sydney Ferreira Santos

CONTENTS
8.1 Introduction ........................................................................................................................... 153
8.2 Atomistic Friction in MXenes............................................................................................... 154
8.3 MXenes s Lubricnt Additives ............................................................................................ 158
8.4 MXenes/Polymer Nnocomposites ....................................................................................... 164
8.5 Concluding Remrks ............................................................................................................. 165
References...................................................................................................................................... 166

8.1 INTRODUCTION
The term tribology ws dened by (Jost 1966) s “The science nd technology of intercting
surfces in reltive motion nd of ssocited subjects nd prctices”. In his pioneer report, Jost
highlighted tht the reduction of wer, friction, nd brekdowns ssocited with tribologicl fil-
ures could result in signicnt economic svings. He estimted tht it could rech bout 1% of
the United Kingdom’s gross ntionl product (GNP), nd over time, some estimtion of economic
svings hs been published with vlues of 1.6% (Mte 2007) or even 4% of the GNP (Bhushn
2017). The nme “tribology” is reltively new, but the tribology issues re prt of everydy life
throughout the history of humnkind s cn be exemplied by the production of re by rubbing
sticks, wheels for grinding cerels, writing with pencils, etc. At the time of Jost’s report, the min
interest of tribology ws relted to the reduction of wer nd filure of moving mechnicl prts
of mchines, which remin  relevnt subject until now, but other ones cme up over time, such
s mgnetic storge devices (e.g., wer t the hed–disk interfces in hrd disk drives), nd lter
the emerging eld micro/nnoelectromechnicl systems (MEMSs/NEMSs). Relevnt tribology
issues cn be even inside us. Wer in joint prostheses is  very complex nd importnt subject, nd
the enhncements in mterils nd design cn extend the durbility of these devices, with obvious
improvements in the qulity of life of ptients. From the scientic point of view, tribology cn be
considered  multidisciplinry eld tht involves mterils science nd engineering, mechnicl
engineering, chemistry, physics, nd so on. Thus, it demnds  body of knowledge in  wide rnge
of subjects such s the development of mterils, mterils processing nd chrcteriztion, sur-
fce science, corrosion, mechnicl design, hydrodynmics, het trnsfer, colloidl suspensions
nd lubricnts, nd much more.
Tody, polymers re used in severl engineering pplictions due to their low unit cost, low
weight, nd esy processing. However, the use of polymers (in bulk) in tribologicl pplictions is
very limited, becuse they usully do not chieve the needed requirements. Therefore, metllic nd/
or cermic reinforcements re usully dded to reduce their wer rtes nd optimize the coefcient
of friction (COF), forming  polymer-mtrix composite (PMC). For exmple, polytetruoroethyl-
ene (PTFE) is  self-lubricting uorocrbon polymer tht presents  very low COF but hs  high

DOI: 10.1201/9781003164975-8 153

154 MXene-Filled Polymer Nanocomposites

wer rte. In order to reduce its wer, it must be used in  composite, with the ddition of cermic
prticles or glss bers, which increses its lod-bering cpcity nd mintins low levels of fric-
tion. Nowdys, PMCs re widely used in gers, berings, rticil humn joint bering surfces,
tires, utomobile brke pds, nd others (Friedrich nd Schlrb 2008).
However, the requirements for higher nd tilored performnces (e.g.,  miniturized lightweight
component with low wer rte t high pressures) mke lmost impossible the use of bre polymers
or even trditionl composites. One promising solution to this problem is the use of nnomterils
s reinforcements, since their lower dimensionlity results in substntil properties enhncements
when compred to trditionl polymer composites. For exmple, different from trditionl com-
posites, nnocomposites cn simultneously enhnce both strength nd toughness (Friedrich nd
Schlrb 2008).
Severl 2D nnomterils such s grphene, boron nitride (BN), molybdenum disulde (MoS2)
nd, more recently, the trnsition metl crbides nd nitrides (MXenes) hve been investigted s
promising lterntives for tribologicl pplictions (Ynbo Guo et l. 2021; Wytt, Rosenkrnz,
nd Ansori 2021). Regrding MXenes, these compounds re obtined from MAX phse (bulk)
precursors through exfolition nd delmintion (Alhbeb et l. 2017). MXenes hve recently
ttrcted much interest due to their unusul combintion of high Young’s modulus, therml, nd
electricl conductivity with hydrophilic behvior, which provides better interction with polymeric
mtrices, differently thn grphene (Jing Chen et l. 2015; Nguib et l. 2016; Ling et l. 2014;
Boot et l. 2017). Moreover, these nnocomposites cn be fbricted through simple nd low-cost
methods (e.g., solution mixing; Ansori et l. 2017; Zhng et l. 2018; Seyedin, Ynz, nd Rzl
2017) nd re suitble to industril techniques, such s electrosprying, emulsion (Zhi et l. 2018),
extrusion printing, nd wet spinning (Akuzum et l. 2018).
Studies of dding MXenes into nnocomposites re still in the beginning but lredy show gret
promises. Addition into ultr-high moleculr weight polyurethne (UHMWPE) (Heng Zhng,
Wng, Chen, et l. 2016) nd epoxy (Heng Zhng, Wng, Zhou, et l. 2016) mtrices showed n
increse in wer resistnce with  lower coefcient of friction compred to their pure mtrices.
For exmple, the ddition of 2.0 wt% Ti2CTx in n epoxy mtrix decresed its COF by nerly 65%
(Heng Zhng, Wng, Zhou, et l. 2016).
In this chpter, the relevnt spects of MXenes nd MXenes/polymer nnocomposites re
reviewed. After this concise Introduction (Section 8.1), atomistic friction in MXenes is discussed
in Section 8.2, where fundmentl spects involved in this phenomenon re depicted such s the
inuence of vcncies nd temperture in friction. Furthermore, experimentl setups used in tomic-
scle friction mesurements re briey introduced. Section 8.3 reviews the use of MXenes as lubri-
cant additives, with emphsis on the production of stble colloidl suspensions, wer mechnisms
in MXenes contining lubricnts, nd tribolm formtion. Section 8.4 is dedicted to MXenes/
polymer nanocomposites, in which the effect of MXenes on the friction coefcient nd the wer
behvior of these nnocomposites is discussed. The mtrices nd MXene compounds lredy used
in these nnocomposites re reviewed, nd the effect of Mxenes on mechnicl properties is briey
discussed. Finlly, in Section 8.5, the concluding remarks re presented, highlighting the trends
nd remining open questions in this subject.

8.2 ATOMISTIC FRICTION IN MXenes

Tribology covers  wide rnge of dimensionl scles with different dominnt mechnisms t ech
scle. For exmple, the mechnicl systems of utomotive prts experience much lower contct
stresses nd pressures thn the geologicl lyers involved in erthqukes. The continuous min-
ituriztion of mechnicl components led to incresing ttention regrding the tribologicl phe-
nomen t the tomic scle. By wy of illustrtion, the so-clled micro/electromechnicl systems
(MEMSs), rst reported in the 1980s, include sensors nd micro-motors in the rnge of 100 nm to
1 µm using silicon-bsed mterils. Since the surfce re/volume rtio increses substntilly with
Tribological Performance of MXene/Polymer Nanocomposites 155

decresing sizes, severl surfce-relted effects rise nd become criticl to these devices, such s
surfce tension nd dhesion. Thus, in order to tilor friction nd wer t the micro/nnoscles, the
tomic-relted phenomen must be understood (Zhou et l. 2021; Gun et l. 2020). In this section,
we focus on MXene nnofriction behvior, evluted through both simultions nd experimentl
studies.
Atomic-scle simultion methods re widely used in nnotribology, becuse they provide infor-
mtion bout the tomic interctions between the lyers. Moreover, since experimentl frictionl
behvior is inuenced by severl fctors (e.g., norml lod, temperture, lyer number, humidity nd
others), the inuence of only one vrible is more clerly ssessed by computtionl methods since
it cn be much more difcult to be isolted in the experiments.
Computtionl ab initio studies (H Zhng et l. 2017; Difn Zhng et l. 2017) hve demon-
strted some of MXenes’ promising fetures to tribologicl pplictions, such s  low COF,  low
brrier for interlyer sliding nd the possibility of superlubricity effect through the unixil strins.
From rst principles clcultions, (H Zhng et l. 2017) different oxygen-functionlized M2CO2
bilyers (M = Ti, Zr, Nb, Mo, Hf, T, nd W) nd the interlyer sliding resistnces were explored.
They found tht lrger lttice prmeters nd smller interlyer distnces induce higher sliding
resistnce. Furthermore, bre MXenes re much more difcult to slide becuse of their strong
metllic bonds between the stcked lyers.
In nother work performed by rst principles nd clssicl moleculr dynmics simultions
(Difn Zhng et l. 2017), Ti3C2O2 presented the lowest energy brrier (0.38 eV/nm2) mong
Ti2CO2, Ti3C2O2, nd Ti4C3O2. The COF ws estimted between 0.24 nd 0.27 t 10 K in these com-
pounds, reching coefcients lower thn 0.04 t 298 K. Titnium nd oxygen vcncies were found
to increse friction (Figure 8.1.) due to the incresed surfce roughness nd ttrction between
the two lyers. Finlly, the uthors evluted different surfce termintions for Ti3C2 compound,
including –OH nd –OCH3, nd found tht both showed lower COFs, reching 0.14 for –OCH3 nd
even 0.10 for hydroxyl termintion, s shown in Figure 8.1.b. This work highlights the inuence of
“n” lyers (n = 2, 3, nd 4), point defects nd surfce termintions into the COF iding experimentl
observtions. For exmple, it indicted tht more controlled synthesis routes (i.e., lower Ti nd O
vcncies) could optimize the lubricnt properties for tribologicl pplictions.
Despite these studies, nnotribologicl simultions of MXenes still need to be explored. For
instnce, studies of uorinted MXenes re still pendent, which is somewht surprising since –F
is the most common termintion fter hydrouoric cid (HF) etching procedure (Hope et l. 2016;

FIGURE 8.1 () Friction coefcient t different Tin+1CnO2 compounds (n = 1, 2, nd 3) nd the effect of oxy-
gen vcncies; (b) effect of termintions on interlyer friction of Ti3C2Tx.
Source: Reproduced with permission (Difn Zhng et l. 2017). Copyright 2017, ACS Publictions.
156 MXene-Filled Polymer Nanocomposites

Nguib et l. 2011). Moreover, studies t lrger systems evluting mixed functionl groups nd/or
number of lyers, re still to be performed, in prticulr using moleculr dynmics.
The predicted promising fetures of MXenes, such s low COF nd low brrier for interlyer
sliding, re very interesting for tribologicl pplictions nd hve ttrcted the ttention of experi-
mentlists. Atomic force microscopy (AFM) is the most common method used to probe friction t
the tomic scle. In this equipment, surfce forces, such s friction nd dhesion, cn be mesured
by the ttrctive or repulsive interctions between the surfce toms of the smple nd those of the
AFM tip (Kim nd Kim 2009). A schemtic digrm cn be seen in Figure 8.2..
Experimentl studies on MXenes identied the inuence of pressure nd temperture on the
friction force (Guo et l. 2019; Gun et l. 2020). The mesurements of friction nd dhesion were
performed by AFM nlyses. The incresed friction force under higher pressures ws  direct result
of the higher contct re between the tip nd the surfce while the decrese of friction with temper-
ture ws ttributed to n increse in the MXene oxidtion degree. Decresing the reltive humidity
ws lso found to reduce MXenes’ friction, becuse the lower number of wter molecules dsorbed
t the MXene surfce decreses the interfcil dhesion nd contct energy (Gun et l. 2020).
Ti3C2Tx friction of  6.5-nm Ti3C2Tx nnosheet ws pproximtely 35% of the one recorded
on the silicon dioxide substrte (Rodriguez et l. 2021). This performnce is inferior to grphene
(5–15% of friction force; Vzirisereshk et l. 2019; Tripthi et l. 2018) but similr to MoS2, which
rnges from 15–40% (Acikgoz nd Bykr 2020; Vzirisereshk et l. 2019). However, this result
contrsts with  previous computtionl study tht predicted n energy brrier for Ti3C2O2 nerly
30% lower thn MoS2 (D. Zhng et l. 2017). Nonetheless, since there re some differences, such
s the number of lyers nd the different functionl groups, more systemtic chrcteriztion nd
modeling must be performed.
The inuence of the functionl groups nd different synthesis routes in nnotribologicl
properties ws evidenced through the comprison of Ti3C2Tx, uorinted-Ti3C2Tx nd TMAOH-
delminted-Ti3C2Tx compounds (Gun et l. 2020). Tetrmethylmmonium hydroxide (TMAOH)
is  common intercltion gent used in MXenes synthesis procedures. It ws shown tht surfce
properties plyed  dominnt role in both dhesion nd friction. These uthors reported tht higher
hydrophilicity increses dhesion nd friction. Thus, the COF incresed in the following order:
Ti3C2Tx< uorinted-Ti3C2Txà TMAOH-delminted-Ti3C2Tx.

FIGURE 8.2 () Schemtic digrm of n AFM experiment of 2D mterils. Friction force mesurements of
Ti3C2Tx nd Nb2CTx with (b) pressure nd (c) temperture.
Source: Adpted nd reproduced with permission (Zhou et l. 2021). Copyright 2021, Elsevier.
Tribological Performance of MXene/Polymer Nanocomposites 157

Besides Ti3C2Tx, AFM ws lso used to evlute the friction behvior of Nb2CTx with more thn
20 lyers (Fig. 8.2). It ws found tht Nb2CTx presented less friction nd dhesion thn Ti3C2Tx t
ll tempertures nd/or pressures (Figures 8.2b nd 8.2c). This behvior ws ttributed to the lower
dipole moment of Nb2CTx, which induces  lower chrge ccumultion t the surfce nd  more
uniform electron cloud distribution (Zhou et l. 2021).
The friction nd dhesion of both mterils increse with pressure (Figure 8.2b) due to the probe
contct re growth, in greement with previous works (Guo et l. 2019; Gun et l. 2020). With
incresing tempertures (Figure 8.2c), the friction of both compounds decresed signicntly. For
exmple, Nb2CTx hd its vlue decresed by nerly 92% t 40°C compred to 25°C. Reserchers
ttributed this reduction to the lower polriztion of the compound resulting from n increse in oxi-
dtion (Guo et l. 2019), fster tomic movements, nd decresed strength of moleculr interctions.
Tble 8.1 summrizes some published dt of tomic-scle friction of MXenes compred to other
2D nnomterils. It cn be observed tht nnotribologicl investigtions of MXenes re brely
reported nd need further investigtions. Only Ti3C2Tx nd Nb2CTx were experimentlly investi-
gted, despite of more thn 30 MXene compounds lredy synthesized, such s the newly discov-
ered ordered in-plne nd out-of-plne MXenes (Persson et l. 2018; Ansori et l. 2015). Moreover,

TABLE 8.1
Published Data of Atomic-Scale Friction of Mxenes Compared to Other 2D Nanomaterials
Number of Layers Friction
2D Material Synthesis (height) Measurements Ref
Ti3C2Tx Not informed <8 (~6.5 nm) FMXene/Fsilic = ~0.35 (Rodriguez et l. 2021)
Ti3C2Tx HF Monolyer (1.42 nm) Friction fctor 0.00657 (Gun et l. 2020)
Fluorinated Ti3C2Tx HCl-LiF Monolyer (1.46 nm) Friction fctor 0.00704 (Gun et l. 2020)
TMAOH- Ti3C2Tx HF + TMAOH Monolyer (1.60 nm) Friction fctor 0.02513 (Gun et l. 2020)
Ti3C2Tx HF >20 lyers (~35 nm) FMXene/Fmic = ~0.58 (Zhou et l. 2021)
Nb2CTx Not informed >20 lyers (~42.5 nm) FMXene/Fmic = ~0.25 (Zhou et l. 2021)
Graphene Commercil chemiclly Monolyer (~0.4 nm) Normlized COF (Tripthi et l. 2018)
vpor deposited (CVD) Bilyer (~1.1 nm) µ1LG/µsilic = 0.102;
grphene µ2LG/µsilic = 0.065
MoS2 mechnicl Monolyer (~1.0 nm) FMXene/Fsilic = ~0.4 (Acikgoz nd Bykr
exfolition 2020)
MoS2 CVD Monolyer (~0.8 nm) Friction force = ~ 3.95 (Vzirisereshk et l.
nN 2019)
µ1LG/µsilic = ~0.07
Graphene CVD Monolyer (~0.4 nm) Friction force = ~ 8.55 (Vzirisereshk et l.
nN 2019)
µ1LG/µsilic = ~0.151
Graphene CVD 7–9 lyers (estimted µGrphene/µsilic: ~0.08 (Bermn et l. 2015)
by Rmn)
Graphene Oxide Commercil GO Multilyer (not µGO/µsilic: ~0.55 (Bermn et l. 2015)
(GO) solution informed)
Graphene mechniclly Bilyer (~0.6 nm) µ2LG/µ1LG = ~0.8 (Lee et l. 2010)
exfolited (Scotch tpe 3-lyer (~0.9 nm) µ3LG/µ1LG = ~0.6
method) 4-lyer (~1.2 nm) µ4LG/µ1LG = ~0,45
Bulk (>20 lyers) µBULK/µ1LG = ~0,45
MoS2 mechniclly Bilyer µ2LG/µ1LG = ~0.9 (Lee et l. 2010)
exfolited (Scotch tpe 3-lyer µ3LG/µ1LG = ~0.7
method) 4-lyer µ4LG/µ1LG = ~0.6
Bulk (>20 lyers) µBULK/µ1LG = ~0,3

(Continued)
158 MXene-Filled Polymer Nanocomposites

TABLE 8.1
(Continued)
Number of Layers Friction
2D Material Synthesis (height) Measurements Ref
h-BN Mechniclly Bilyer µ2LG/µ1LG = ~0.85 (Lee et l. 2010)
exfolited (Scotch tpe 3-lyer µ3LG/µ1LG = ~0.65
method) 4-lyer µ4LG/µ1LG = ~0.6
Bulk (>20 lyers) µBULK/µ1LG = ~0.3
Graphene CVD ~4-lyer (1.97 nm) F ≈ 8 nN (cycle =200) (Peng, Wng, nd Zou
2015)
Graphene Mechniclly ~4-lyer (1.90 nm) F ≈ 2.5 nN(cycle =200) (Peng, Wng, nd Zou
exfolited (Scotch tpe 2015)
method)
Graphene Oxide Modied Hummer’s Bilyer (2.10 nm) F ≈ 40 nN (cycle =200) (Peng, Wng, nd Zou
method 2015)
Reduced Graphene chemicl reduction of Bilyer (2.10 nm) F≈ 35 nN (cycle =200) (Peng, Wng, nd Zou
Oxide the GO 2015)

s the topologicl structure nd the interlyer forces re directly relted to nno-friction phenomen,
severl prmeters need to be systemticlly studied in order to understnd their effects. Among oth-
ers, it cn be cited the number of lyers nd the inuence of different synthesis procedures (the most
common, HF [Nguib et l. 2011], HCl-LiF [Ghidiu et l. 2014], nd MILD (Liptov et l. 2016;
Sng et l. 2016] etching), surfce defects, nd lterl sizes.

8.3 MXenes AS LUBRICANT ADDITIVES

Friction nd wer criticlly ffect  wide rnge of pplictions, resulting in mssive wste of energy
nd loss of mterils. The use of lubricnts consists of one the most efcient methods to decrese
these negtive phenomen. The high-performnce lubricnts currently vilble usully consist of
 bse uid nd dditives. The former comprises the min component of the lubricnt by determin-
ing its primry chrcteristic. The dditives, on the other hnd, my tune the lubricnt properties
by providing  vriety of fetures such s better ntiwer cpbilities, friction reduction, viscosity
modiction, ntioxidnt properties, or corrosion inhibitors.
Two-dimensionl mterils hve been extensively studied s lterntive dditives for lubricnts (Xio
nd Liu 2017). These mterils show lyered structures with reltively low sher strength, which permits
sliding mong djcent lyers under sher force. They lso exhibit high specic surfce re tht llows
them to be dsorbed onto rubbing surfces to form  protective tribolm. The tribolm cn be dened
s “ thin solid lm creted s result of sliding contct, which is dhered on its prent worn surfce but
hs different chemicl composition, structure nd tribologicl behvior” (Luo 2013). It prevents direct
contct between the rubbing surfces, lowering the friction nd wer. In ddition, 2D mterils cn ct by
lling concve res nd gps usully present in surfces due to mnufcturing limittions. The resultnt
smoother surfce leds to  reduction of loclized contct pressure nd plstic deformtion. Moreover, the
2D dditives cn ffect the uid viscosity nd drg, which comprises  dominnt fctor in the lod-bering
cpcity nd friction force of the lubricnt. Figure 8.3 summrizes the min proposed mechnisms in the
literture, which explins the role of 2D structures s dditives in lubricnts (Xio nd Liu 2017).
Grphene nd its derivtives hve shown promising results s dditives for lubricnts due to
their enhnced mechnicl properties nd chemicl stbility (Bermn, Erdemir, nd Sumnt 2014;
Mungse, Kumr, nd Khtri 2015). In ddition, other 2D structures, such s trnsition metl dichl-
cogenides (Xu et l. 2015; Tng et l. 2014) nd zirconium phosphtes (Xio et l. 2015), lso
hve shown excellent lubricnt properties. However, most of these 2D dditives present disdvn-
tges regrding their dispersibility into the lubricnt, s they show  tendency to gglomerte nd
Tribological Performance of MXene/Polymer Nanocomposites 159

FIGURE 8.3 Proposed mechnisms of 2D nnosheets to enhnce tribologicl properties: () sliding sur-
fces, (b) tribolm formtion, (c) lling the intrinsic gps of surfces, nd (d) ffecting the uid viscosity.
Source: Reproduced with permission (Xio nd Liu 2017). Copyright 2017, Elsevier.

precipitte within  short period. This phenomenon results in negtive effects on the shelf life nd
lubriction performnce, which limit their widespred use s dditives. Therefore, endevors re
serching for new mterils tht cn ttend to the desired tribologicl properties, chemicl stbility,
nd fvored dispersibility in uids.
Experimentl nd theoreticl studies hve evidenced the excellent mechnicl nd tribologi-
cl properties of MXenes (Mlki nd Vrm 2020). Additionlly, MXenes show good dispersion
chrcteristics in  wide rnge of solvents due to the presence of vried functionl groups, which
could overcome the stbility issues involving lubricnt dditives. Recent studies demonstrted the
fesibility to obtin stble MXene solutions in nonpolr solvents. Crey et l. (2020) showed tht
MXenes become orgnophilic nd form stble colloidl suspensions in nonpolr solvents, through
the exchnge of lithium ctions between MXene multilyers fter etching with di(hydrogented tl-
low)benzyl methyl mmoniumchloride (DHT). Moreover, Lim et l. (2019) obtined stble nonpolr
colloidl dispersions of MXenes chemiclly grfted with lipophilic octyltriethoxysilnes. Thereby,
the progress in obtining stble solutions of MXenes with different solvents hs encourged their
use s dditives in lubricnts or reinforcing gents in composite mterils.
Recent works hve shown tht even low content of these 2D mterils my signicntly enhnce
the ntiwer nd ntifriction properties of uids. (Yng et l. 2014) prepred Ti3AlC2 MAX phse by
pressureless sintering followed by exfolition using HF to obtin lyered Ti3C2Tx. The uthors showed
tht the ddition of 1.0 wt% of the 2D mteril in prfn bse oil resulted in  decrese of the COF
from 0.125 (pure oil) to 0.063 (1.0 wt% of MXene). The improvement on the ntifriction property
could be explined by the formtion of  uniform lubricnt lm preventing direct contct between the
mting surfces. On the other hnd, under higher concentrtions of MXenes, n increse of the COF
nd  deprecition of ntiwer property could be noticed due to the ggregtion of the 2D mteril.
Similr results were obtined by Zhng et l. (2015), who studied the ntifriction nd ntiwer
properties of Ti3C2(OH)2 nnosheets (10–20 nm of thickness) s dditives for bse oil lubricnts.
The uthors found tht under MXene concentrtions below 1.0 wt%,  decrese of the COF could
be obtined when compred to the oil without n dditive. Through scnning electron microscopy
(SEM) nd energy dispersive X-ry spectroscopy (EDS), they proposed tht the sliding friction of
the Ti3C2(OH)2 nnosheets nd the presence of  stble nd uniform tribolm prevented  direct
contct nd decresed the shering stress between the mting surfces.
160 MXene-Filled Polymer Nanocomposites

The concentrtion nd dispersion of MXenes into the lubricnt ply  key fctor for the enhnce-
ment of the tribologicl properties. It ws proposed tht under optiml conditions, the lrge surfce
re of the exfolited Ti3C2Tx contributes to chnge the uid viscosity resulting in stble tribolm
formtion (Liu et l. 2017). In ddition, the high surfce energy of Ti3C2Tx nnosheets leds to their
bsorption into the surfce vlleys contributing to surfce roughness depletion. On the other hnd,
under high dditive concentrtions, the colloidl system of Ti3C2Tx nnosheets nd bse oil my
become unstble, promoting dditive gglomertion nd consequent tribolm dmges.
In order to further enhnce the tribologicl properties of Ti3C2Tx, strtegies to incorporte other
nnomterils with MXene nnosheets hve been explored. Xue et l. (2017) promoted the growth of
TiO2 nnoprticles onto Ti3C2Tx by hydrotherml process. The TiO2/Ti3C2Tx hybrid nnocomposites
showed n effective decrese in wer nd friction when incorported s dditive in PAO 8 bse oil.
COF vlues decresed from 0.103 (pure oil) to 0.073 (1.0 wt% TiO2/Ti3C2Tx) t 20N lod condition.
According to the uthors, during sliding, desqumted TiO2 nnoprticles cn mend the scrtched
surfces resulting in decrese of surfce roughness. Moreover, the exfolited Ti3C2Tx nnosheets
tend to be dsorbed onto the rubbing surfces, preventing their direct contct through tribolm
formtion. Similrly, Zhng et l. (2019) synthesized potssium titnte nnowires uniformly dis-
tributed onto Ti3C2Tx surfce. An evlution of tribologicl performnces of titnte-Ti3C2Tx-lled
poly-α-olen (PAO)8 oil, commonly pplied in utomotive nd industril ger oils, bering lubri-
cnts, nd so on, showed  decrese of COF nd wer width by 4.9% nd 22%, respectively, when
compred to unmodied-Ti3C2Tx-lled oil. The superior performnce of the titnte–Ti3C2Tx-lled
oil could be ttributed to the enlrged interlyer spcing of the nnocomposite nnosheets fter
intercltion tretment besides the enhnced stbility nd lod cpcity of the formed tribolm.
Recently, environment-friendly wter-bsed lubricnts hve ttrcted ttention due to their
high sfety, me retrdnt, nd excellent cooling property. However, their low viscosity nd
reltively high surfce tension when compred to oil-bsed lubricnts limit their widespred use.
The MXene functionl groups (–O, –OH, nd –F) provide high hydrophilic properties, mking
them  promising lterntive s n dditive for wter-bsed lubricnts. Chen nd Zho (2021)
used n lternte pressure technique to obtin 2-nm Ti3C2Tx nnosheets. Its thin lmellr struc-
ture resulted in high-stble MXene wter dispersions, which contributed to the formtion of 
more continuous nd effective lubricting lm between the contct surfces s shown by EDS
nlysis (Figures 8.4 nd 8.4b). The MXene ddition with n optiml concentrtion of 0.8 mg/
ml decresed the COF nd the wer rte by 34.74% nd 45.58%, respectively, when compred to
pure wter-bsed lubricnt (Figures 8.4c nd 8.4d).
In order to further enhnce the stbility of Ti3C2Tx nnosheets solution in wter, (Yi et l.
2021) pplied glycerol to  Ti3C2Tx lled wter-bsed lubricnt. The Ti3C2Tx/glycerol/wter sys-
tem showed excellent dispersibility nd stbility rendering solutions without gglomertion for t
lest 60 dys. Ti3C2Tx on glycerol/wter uid lubricting performnce ws tested in  pin-on-disk
tribometer with n Si3N4 bll nd spphire disk (Figure 8.5). The Ti3C2Tx/glycerol/wter system
resulted in n impressive minimum COF vlue of 0.002. According to the uthors, this triggered
superlubricity ws minly ttributed to  resultnt mixed lubriction regime, which comprises the
boundry nd elstohydrodynmic lubriction (Figure 8.5b). For the former, tribochemicl rec-
tions between Ti3C2Tx nd Si3N4 led to tribolm formtion primrily composed by colloidl silicon
oxide nd titnium oxide on the Si3N4 surfce, wheres, t the spphire surfce, MXene nnosheets
were physiclly dsorbed onto the surfce wer trcks (Figures 8.5c–8.5e). These tribolms, uni-
formly formed on both mting surfces, contributed to prevent direct sperity contct between
Si3N4 nd spphire. Besides, t the elstohydrodynmic lubriction, the strong fnity mong the
hydrophilic Ti3C2Tx nd wter/glycerol molecules produced  hydrtion lyer onto the nnosheets,
which reduced the sher strength of the liquid lm (Figure 8.5f).
Even though the MXenes fmily consists of  wide vriety of compounds, to dte, most of the
work iming t their use s lubricnt dditives were limited to the study of Ti3C2Tx. Recently,
Cheng nd Zho (2022) showed tht exfolited Nb2CTx nnosheets could lso be effectively used
 Tribological Performance of MXene/Polymer Nanocomposites

FIGURE 8.4 SEM nd EDS nlyses of wer scrs on steel mtching surfces lubricted with pure wter () nd 0.8 mg/ml of Ti3C2Tx (b), COF curves (c), nd men
COF/men wer rte (d) of Ti3C2Tx lled wter under different MXene concentrtions.
Source: Reproduced with permission (Chen nd Zho 2021). Copyright 2020, Elsevier.
161
 162

FIGURE 8.5 () Schemtic representtion of the pin-on-disk tribometer with Si3N4 bll nd spphire disk. (b) Schemtic representtion of the contct zone between
Si3N4 nd spphire surfces with the lubriction of the MXene-glycerol solution. (c–e) Boundry lubriction showing formed tribolms on the Si3N4 nd spphire sur-
fce. (f) Schemtic illustrtion of elstohydrodynmic lubriction showing the hydrted MXene–glycerol networks.
Source: Reproduced with permission (Yi et l. 2021). Copyright 2021, Elsevier.
MXene-Filled Polymer Nanocomposites
Tribological Performance of MXene/Polymer Nanocomposites 163

s n dditive for wter-bsed lubricnt. Tribologicl tests exhibited  COF reduction of bout
81.2% for wter-lled MXenes (0.5 mg/mL) when compred to pure wter. The uthors lso stud-
ied the effect of Nb2CTx oxidtion on the tribologicl performnce. By oxidizing Nb2CTx sheets
in solution, Nb2O5 nnoprticles nd morphous crbon could be formed onto MXenes sheets
contributing to  further COF reduction of bout 90.3% nd  decrese of wer rte by 73.1%
when compred with pure wter. It is believed tht the synergistic effect between Nb2CTx /Nb2O5
components strongly contributed to n enhnced ntifriction nd ntiwer properties. The uthors
suggested tht the Nb2CTx lyers nd crbon could be esily dsorbed on the rubbing surfces,
leding to  tribolm formtion, wheres Nb2O5 nnoprticles ct by incoming nd lling the worn
trcks, reducing wer rte.
Tble 8.2 summrizes the up-to-dte published works involving MXenes s lubricnt ddi-
tives. A detiled inspection on these studies revels tht  fvored dispersion nd stbility of

TABLE 8.2
Tribological Performance of MXene-Filled Lubricants
Rubbing Surfaces Tribological Performance
MXenes Base Fluid (test conditions) COF Wear Ref.
Ti3C2Tx Prfn oil 440-C stinless steel bll 0.125 (bse oil) – (Yng et l.
(∅4 mm) on 45# steel disc. 0.063 (1.0 wt%) 2014)
100 rpm, 15N
Ti3C2(OH)2 100SN oil 440-C stinless steel bll 0.092 (bse oil) Width: (Zhng
(10–20 (∅10 mm) on 45# steel disc. 0.075 (1.0 wt%) 220 µm (bse oil) et l.
nm) 200 rpm, 15N 200 µm (1.0 wt%) 2015)
Ti3C2Tx PAO8 oil 32100 steel bll (∅9 mm) on 0.126 (bse oil) Volume: (Liu et l.
steel disc. 0.114 (0.8 wt%) 7.7% wer reduction (0.8 2017)
240 rpm, 10N wt%)
TiO2/ PAO8 oil 440-C stinless steel bll 0.103 (bse oil) Width: (Xue et l.
Ti3C2Tx (∅4 mm) on 45# steel disc. 0.073 (1.0 wt%) 280 µm (1.0 wt%) 2017)
150 rpm, 20N
Titanate- PAO8 oil 440-C stinless steel bll 0.111 (bse oil) Width: (Zhng
Ti3C2Tx (∅4 mm) on steel disc. 0.077 (1.0 wt%) 173 µm (bse oil) et l.
200 rpm, 5N 138 µm (1.0 wt%) 2019)
Ti3C2Tx PAO8 oil 440-C stinless steel bll 0.111 (bse oil) Width: (Zhng
(∅4 mm) on steel disc. 0.081 (1.0 wt%) 173µm (bse oil) et l.
200 rpm, 5N 167µm (1.0 wt%) 2019)
Ti3C2Tx DI Wter SiC bll (∅6 mm) on 316 steel 0.275 (pure wter) Rate: (Chen nd
disc. 0.180 (0.8 wt%) 8.8 .10−7 mm3.N−1.m−1 (bse oil) Zho
2 Hz, 5N 4.8 .10−7 mm3.N−1.m−1 (0.8 wt%) 2021)
Ti3C2Tx DI Si3N4 bll (∅4 mm) on sphire 0.011 (bse uid) Width: (Yi et l.
Wter- disc. 0.002 (1.0 wt%) 278 µm (bse uid) 2021)
Glycerol 0–900 rpm, 3N 219 µm (1.0 wt%)
Nb2C DI Wter Al2O3 bll (∅6 mm) on 316 0.44 (pure wter) Rate: (Cheng nd
steel disc. 0.08 (0.05 wt%) 45 .10−7 mm3.N−1.m−1 (bre) Zho
5 Hz, 5N 18 .10−7 mm3.N−1.m−1 (0.8 wt%) 2022)
Nb2C/ DI Wter Al2O3 bll (∅6 mm) on 316 0.44 (pure wter) Rate: (Cheng nd
Nb2O5 steel disc. 0.04 (0.025 wt%) 45 .10−7 mm3.N−1.m−1 (bre) Zho
5 Hz, 5N 12 .10−7 mm3.N−1.m−1 (0.8 2022)
wt%)
Ti3C2Tx DI Wter 440-C stinless steel bll 0.30 (pure wter) Width: (Nguyen
(∅3 mm) on 304 steel disc. 0.24 (5.0 wt%) 452µm (bse oil) nd Chung
120 rpm, 3N 236µm (5.0 wt%) 2020)
164 MXene-Filled Polymer Nanocomposites

MXenes in the lubricnts ply  key role in the enhncement of the tribologicl performnce.
Most of the published studies gree tht  low concentrtion (usully 1.0 wt%) contributes to
 better dispersion nd prevents nnosheets gglomertion into the lubricnts. In generl, high
degree of exfolition usully results in  lower COF nd wer rte (Mlki nd Vrm 2020).
However, the effect of the nnosheet size should be further investigted. In ddition, most of the
works re limited to the study of Ti3C2Tx. MXenes comprise  wide fmily of 2D compounds for
which mny predicted structures hve not yet been synthesized. Therefore, we cn expect in the
future to come cross mny studies focusing on other MXene compounds nd their nnocompos-
ites s dditives for lubricnts.

8.4 MXenes/POLYMER NANOCOMPOSITES

The use of MXenes to reduce friction nd wer is not limited to dditives in lubricnts, s lredy
discussed in Section 8.3. Some studies hve evluted MXene cotings nd MXene-reinforced com-
posites s wer-resistnt nd/or ntifriction mterils (Lin et l. 2018; Mi et l. 2019; Mrin
et l. 2020; Hu et l. 2020). However, despite these promising fetures, their use s reinforcements
in composites remins signicntly underexplored. For exmple, only UHMWPE (Zhng, Wng,
Chen et l. 2016) nd epoxy (Zhng, Wng, Zhou et l. 2016) polymeric mtrices were screened.
Therefore, there re severl open questions nd opportunities for scientic nd technologicl inves-
tigtions into this subject.
The rst studies on the ddition of Ti3C2Tx into UHMWPE (Zhng, Wng, Chen, et l. 2016)
nd epoxy resins (Zhng, Wng, Zhou, et l. 2016) hve shown similr behviors: MXene ddition
enhnced wer resistnce nd decresed the COF compred with pure mtrices. The COF ws
grdully decresed with MXene loding, reching  reduction of 65% for 2.0 wt% of reinforce-
ment. This decrese of the COF ws ssocited with (1) the exfolition nd slipping of MXenes
multilyer previously held only by wek vn der Wls bonds, (2) tribolm formtion t the surfce,
nd/or (3) n increse of mechnicl properties nd crystllinity degree. In the ltter, MXenes
nnosheets cn ct s nucleting substrtes, incresing the crystlliztion rte.
The enhncement of wer resistnce ws lso ttributed to improvements of the nnocomposite
mechnicl properties, resulting in better plowing nd scrtching resistnce nd tribolm form-
tion, which promotes  lower contct re for plstic deformtion between the composite nd the
counterbody (Zhng, Wng, Chen, et l. 2016; Zhng, Wng, Zhou, et l. 2016). However, the wer
ws evluted minly through opticl nd scnning electron microscopy, but no quntiction ws
performed (e.g., wer rte). In ddition, since tribo-physicl nd chemicl rections during the tri-
bolm formtion re very complex (Lihe Guo et l. 2021), more experimentl investigtions re
necessry to llow  deeper understnding of the wer mechnisms involved.
Lihe Guo et l. (2021) performed more extended reserch on MXene/epoxy (EP) nnocomposites
under ultr-low sulfur diesel (ULSD) oil lubriction. They found tht the ddition of 3 wt% Ti3C2Tx
decresed the wer rte by 79.6%, reching 97% reduction when combined with Al2O3 nnopr-
ticles. It is worth highlighting tht 3.0 wt.% ws not evluted in the previous studies, which hd
mximum MXene lodings of 2.0 wt% (Zhng, Wng, Chen et l. 2016; Zhng, Wng, Zhou et l.
2016), nd thus, their performnce my be further enhnced if higher MXene concentrtion is used.
In ddition, for the rst time, they reported  superlubricity effect of MXenes in the mcroscle
(COF lower thn 0.01 fter  4.5-h sliding process), which ws only previously predicted comput-
tionlly (Zhng et l. 2017). From the results of Rmn spectroscopy, Trnsmission electron micros-
copy (TEM), nd EDS techniques, the uthors proposed tht, during the tribologicl tests, the epoxy
molecules re frgmented nd grphitized by het nd sher stress. These frgmented molecules,
crbon mteril, nd nnomterils (MXene nd Al2O3) re trnsferred to the counterprt steel sur-
fce nd oriented prllel to the sliding direction due to sher stresses. Thus, the formed tribolm
(~100 nm) enbles  high lod-bering cpbility nd esys hering, effectively seprting the fric-
tion pirs nd mitigting the oxidtion of steel surfce (Guo et l. 2021).
Tribological Performance of MXene/Polymer Nanocomposites 165

FIGURE 8.6 Comprison of friction coefcients with MXene ddition in polymer-bsed composites.

Enhncements on the tribologicl response could lso be seen in  freeze-dried nnocomposite

of epoxy with  3D Ti3C2Tx structure with  modied crbon nnober (Meng et l. 2021). The
wer rte decresed 67% thn tht of epoxy resin when 3 g of MXenes were used, while the COF
decresed by 76% using only 1 g. A grphicl summry showing the decrese of friction coefcient
of ll nnocomposites with MXenes discussed in this section is presented in Figure 8.6.
Although their outstnding potentil s lubricnts nd reinforcements, s we presented, the
reserch on this topic is quite scrce nd needs to be further explored. First, prt from Ti3C2Tx,
other MXenes should be evluted since nerly 30 compounds were lredy synthesized. Severl
mtrices of interest still need to be studied, such s poly ether ether ketone nd PTFE (Friedrich nd
Schlrb 2008). Moreover, the inuence of MXene synthesis nd functionl groups on their surfces
remins n open question, since their different termintion my inuence the mtrix comptibility.
Finlly, the inuence of different MXene-relted fetures on tribologicl properties, such s lterl
sizes nd number of lyers, still needs to be investigted.

8.5 CONCLUDING REMARKS

Among others, MXenes re 2D nnomterils with promising pplictions in tribology, mostly
s dditives in lubricnts nd reinforcements in self-lubricting nnocomposites. Despite their
bright prospect, the quntity of results from both experimentl nd simultions is still quite
scrce. This scrcity is limited not only to pplied reserch but lso to fundmentl ones. More
informtion on the friction coefcient, Young modulus, therml conductivity, nd so on is
still missing. This lck of informtion is especilly true when we remember tht the mjority
of these dt were collected from the compound Ti3C2Tx nd severl compositions re unex-
plored for tribologicl purposes. Likewise, when we consider the MXene nnocomposites, this
lck of informtion is even more expressive. Different possible combintions of MXenes nd
166 MXene-Filled Polymer Nanocomposites

mtrices, different methods of exfolition nd delmintion, lrge number of processing routes,
surfce functionliztion, nd mny other signicnt vribles mke this subject lmost inex-
hustible. This scenrio evidences the necessity of rtionliztion in the serch for new MXene-
bsed mterils for tribologicl purposes. This rtionliztion my be performed using different
pproches. One of them is to design nd perform investigtions bringing together computer
simultion techniques (density functionl theory (DFT), moleculr dynmics, mchine lerning,
etc.) nd experiments (synthesis nd chrcteriztion) in order to precisely determine nd vli-
dte certin trends. These pproches will then provide the possibility to screen  lrge number
of mterils, their potentil for tribologicl pplictions, coefcient of friction, supported ber-
ing lods, wer mechnisms, nd much more. In our perspective, some criticl spects hinder
the development of MXene-bsed mterils s potentil wer-resistnt mterils nd lubricnts,
which need to be ddressed in the future. Some promising topics of reserch re the produc-
tion of stble MXene colloidl solutions, llowing esier incorportion of MXenes in lubricnt
oils nd polymeric mtrices, development of new (self-lubricting) MXene nnocomposites nd
development of theoreticl modeling to predict mterils of interest.

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 9 Self-Healing Activity
of MXene/Polymer
Nanocomposites
Shikha Agarwal, Ayushi Sethiya,
Divyani Gandhi, and Jay Soni

CONTENTS
9.1 Introduction ........................................................................................................................... 171
9.1.1 History of MXenes.................................................................................................... 171
9.1.2 History of Self-Heling Polymer Composites........................................................... 172
9.2 Designing of MXene-Bsed Compositions........................................................................... 173
9.2.1 Self-Heling Chrcteristics of MXene-Bsed Hydrogels ....................................... 173
9.2.2 Self-Heling Chrcteristics of MXene-Bsed Nnocomposites/Nnosheets.......... 178
9.2.3 Self-Heling Chrcteristics of MXene-Bsed Suprmolecules............................... 180
9.2.4 MXene-Bsed Supercpcitors nd Their Self-Heling Chrcteristics................... 181
9.2.5 MXene-Bsed Films, Electrodes, Other Compositions nd Their
Self-Heling Behvior............................................................................................... 183
9.3 Applictions of Self-Helble MXene-Bsed Mterils....................................................... 185
9.4 Conclusion............................................................................................................................. 186
Abbrevitions ................................................................................................................................. 186
Acknowledgment ........................................................................................................................... 186
References...................................................................................................................................... 186

9.1 INTRODUCTION
Presently, two-dimensionl (2D) mterils re one of the intense res of reserch in the sci-
entist community due to their lrge specic surfce re, wide-bnd-gp modultion cpcity,
high ctlytic ctivity, nd so on, nd these mterils re used in disruptive pplictions such s
medicl pplinces, ctlysis, energy, optoelectronics, biologicl, nd industril pplictions.1–2
These signicnt properties increse curiosity nd thus led to  novel eld of reserch on 2D
mterils. Discovered in 2011, MXenes belong to n exclusive fmily of hydrophilic, conductive
2D nnomterils.
The min objective of this chpter is to summrize the self-heling behvior of MXene-bsed
nnocomposites. Herein, different nnocomposites of MXenes nd their processing pthwys, inte-
grtion with polymer hosts, mechnism of ction, nd pplictions in different elds of science re
deliberted. This chpter gives n outline of the diverse chemistries engged in the synthesis of
self-helble nnocomposites, with their pros nd cons.

9.1.1 HISTORY OF MXENES

The discovery of MXenes (Ti3C2Tx) took plce in 2011 t Drexel University,3 without ny previous
knowledge of the stbility of this type of 2D mteril. Since tht time, more thn 30 composi-
tions of MXenes hve become vilble, nd dozens more hve been investigted by computtionl

DOI: 10.1201/9781003164975-9 171

172 MXene-Filled Polymer Nanocomposites

FIGURE 9.1 Development on MXenes in the pst yers.

Source: Modied from Reference no. 4.

techniques.4 MXenes becme fmous due to fscinting chrcteristics tht led to their utility in
severl rel-life pplictions.
MXenes re 2D sheets of trnsition metl crbonitrides, nitrides, nd crbides tht were pre-
pred by Mn+1AXn, or MAX phses, where ‘M’ is  trnsition metl, ‘A’ belongs to IV–V group
elements, nd ‘X’ denotes C or N. They re synthesized from MAX by prticulrly etching the ‘A’
lyer.3, 5–7 After etching, the MXene is best depicted like Mn+1XnTz, where Tz represents the func-
tionl groups tht exchnge during the etching procedure. T is supposed to mintin the chrge
neutrlity in MXene. In generl, T represents F, O, nd OH.8–11 They hve n exclusive combintion
of chrcteristics due to the functionlized surfces of MXenes tht mke them hydrophilic nd pre-
pred to bind with diverse clsses. MXenes hve  high vlue of (−) zet-potentil, high mechnicl
properties, nd electricl conductivity. MXenes nd their composites possess enormous pplictions
in vrious elds, nmely, cting s electrochemicl cpcitors, Li–ion, N–ion cpcitors, nd bt-
teries; on-chip energy storge; hybrid energy storge; electromgnetic interference (EMI) shielding;
MXene inks for supercpcitors; binders for Si nd crbon; electroctlysis; textile industries; elec-
trochromic devices; biomedicl pplinces; sensors, nd mny more.4, 12–18 Recently, severl review
rticles hve been published on MXenes nd their polymer nnocomposites,19–20 membrnes,21 nd
their pplictions in werble pressure sensors.22 In 2021, Crey nd colleuges23 deliberted the
vrious methods of synthesis of polymer nnocomposites nd their properties. The development of
MXenes in pst yers hs been depicted in Figure 9.1.

9.1.2 HISTORY OF SELF-HEALING POLYMER COMPOSITES

Nture itself is n inspirtion for scientic reserch. For exmple, skin cts s n efcient protective
brrier for the humn body nd possesses self-heling cpbility. The conversion of these physi-
ologicl chrcteristics into synthetic mterils could unlock new prospects in numerous strtegic
elds from biomedicl to robotics. Self-heling in compounds nd mteril science is the cpbility
of  mteril to refurbish its dmges individully nd keep its structurl integrity. The demon-
strtion of, quest for, nd pplictions of self-heling polymers rose in the 21st century, motivted
by the perceptive interfcil properties t the nnoscle nd the progression of exible devices. A
Self-Healing Activity of MXene/Polymer Nanocomposites 173

MXene-Based Materials

MXene-based
Mxene-based MXene-based other
MXene-based Mxene-based
nano- super- composites,
hydrogel supramolecules
composites capacitor films, coating
material

FIGURE 9.2 Clssiction of MXene-bsed composites.

swift investigtion t the Web of Science demonstrted tht pproximtely 360 ppers were pub-
lished from 1965 to 2000, nd more thn 5,000 ppers were vilble since 2000 with the theme of
“self-heling.”24–27
Momentous development hs been ccomplished in the progress of mterils tht cn sense nd/
or self-repir.28–29 Suprmolecules ct s efcient composites for self-heling.30–33 Polyborosiloxne
(PBS) is  suprmoleculr polymer tht demonstrtes  fundmentl self-heling property due to its
dtive bonds nd is embedded with others to improve its chrcteristics.34 The ssimiltion of self-
heling nd other functionlities in  strong nd weightless mteril is still  subject of chllenge. In
the pst yers, diverse types of self-heling mterils hve been synthesized by employing different
methodologies. The integrtion of pproprite functionlities with these mterils stimultes  self-
heling chrcter.35 MXene mterils fullled these criteri s vritions in stoichiometric compo-
sitions nd surfce functionl groups llow the tiloring their physicl nd chemicl properties. The
key property of MXene is its self-heling nture. In this chpter,  detiled mechnistic pproch
to self-heling cpcity of MXene nd its composites hs been deliberted. The chpter is divided
in vrious subsections like MXene-bsed hydrogels, MXene-bsed nnocomposites, MXene-bsed
suprmolecules, MXene-bsed supercpcitors, nd other compositions, with  detiled study bout
the synthesis nd their self-heling behvior (Figure 9.2).

9.2 DESIGNING OF MXene-BASED COMPOSITIONS

In this chpter, efforts hve been mde to bridge the current dvnces in the self-heling behvior
of MXene-bsed compositions. It hs been instigted by reviewing diverse production pthwys nd
their effects on the surfce chemistry nd structure of MXene-bsed composites. The rrngement,
chrcteristics, constncy, nd different types of lyered MXenes re demonstrted over  period
of time. Moreover, different types of MXene-bsed supercpcitors re bridged to emphsize the
importnce of MXene-bsed composites in mking sensors, energy storge pplinces, biomedi-
cl pplictions, nd so on. Ultimtely, chllenges, limittions, nd severl spects in this emerg-
ing re need to be explored for better development nd progress in the self-heling behvior of
MXenes.

9.2.1 SELF-HEALING CHARACTERISTICS OF MXENE-BASED HYDROGELS

Currently, the self-heling chrcteristics of hydrogels bsed composites hve provoked interest
of reserchers owing to their promising pplictions nd potentil to extend service life. Severl
strtegies hve been designed for the synthesis of hydrogels to blnce self-heling efciency nd
enhnce high mechnicl properties.36–38 The hydrogels hve been embedded with other 2D mteri-
ls like grphene, MXene, crbon nnotubes, nd others to boost their properties. The reserchers
174 MXene-Filled Polymer Nanocomposites

re focusing on the designing of MXene-incorported hydrogels to improve their self-heling chr-
cteristics s well s ugment their industril nd medicl pplictions.39–41
Zhng nd collegues42 designed self-helble MXene-bsed polyvinyl lcohol (PVA) hydro-
gels with outstnding sensing bilities vi  simple method through mixing of MXene nnosheets
with commercilly vilble hydrogel nmed “crystl cly” tht include nti-dehydrting gents,
wter, PVA, nd others. The obtined MXene-hydrogel exhibited notble stretchbility (3400%).
The ddition of MXene nnosheets with negtively chrged surfces cused formtion of secondry
crosslinking s well s dditionl hydrogen bonding into the hydrogel system nd, thus, fcilitted
the self-heling property. Furthermore, MXene hydrogels were lso used in sensing mterils to
identify severl bodily motions (fcil expression, hndwriting), monitoring vitl signls with high
ccurcy nd sensitivity.
Lter on, in 2019, Zhng nd coworkers43 designed  highly efcient cpcitive strin sensor
by developing MXene/PVA-bsed hydrogel. The integrtion of PVA with MXene ugmented the
self-helbility nd conductivity of the hydrogel composite. The electrode displyed  high vlue
of stretchbility next to the brek point (≈1200%) with spontneous self-heling in just 0.15 s. The
MXene/PVA hydrogel ws synthesized s per the following method. Initilly, 8 wt% PVA solutions
ws prepred using PVA powder hving Mw ≈ 145000, by dissolving in 3 mL DI wter nd kept
t 90°C for pproximtely 8 h. After this, the prepred solution ws poured into 5 mg/mL MXene
solution with stirring t room temperture for pproximtely 1.5 h. Then,  trnsprent sodium
tetrborte solution ws mixed in this solution to furnish the hydrogel. The ddition of borx to this
system cused crosslinking between the functionlities of PVA chins tht formed the diol–diol
bonds. Moreover, the functionlities of MXene hving oxygen could mke covlent bonds with
borte ions, s well s with the PVA chins tht trit to self-helbility. The cpcitive sensor bsed
on MXene/PVA hydrogel demonstrted elevted linerity up to 200%, sensitivity up to 0.4, less
hysteresis, ne mechnicl strength, nd durbility.
In the sme yer, Zhng nd coworkers44 synthesized MXene hydrogels. Initilly MXene ws
prepred using the “Yury mild method” nd then crylmide (15 wt%), luryl methcrylte with
concentrtion 1.5 mol% of the concentrtion of crylmide nd OP-10 (3 mol%), nd n queous
dispersion of MXene (1.3 mg/mL) were mixed. Nitrogen gs ws pssed to it, nd the resultnt mix-
ture ws stirred constntly for 50 min followed by the ddition of potssium persulfte (KPS) hv-
ing  concentrtion of 0.1 mol% crylmide with 10 μL of N,N,N′,N′-tetrmethylethylenedimine
(TEMED). Furthermore, the solution ws kept t room temperture for 3 dys, nd thus, hydro-
gels were prepred. Now N-isopropylcrylmide (NIPAM) (10 wt%), deionized H2O, nd N,N′-
methylene dicrylmide (1 wt% of NIPAM) were dded in  sk nd stirred on ice bth for 1 h
with  pssing of nitrogen; subsequent to this, KPS hving  concentrtion of 0.1 mol% NIPAM with
10 μL of TEMED were dded. Thus, the nnocomposite double-network (NCDN)-bsed hydro-
gel, homogeneous nd blck in color, ws chieved. Using this procedure, other hydrogels like
double network (DN) hydrogel without MXene, hydrophobic polycrylmide (HAPAM) hydrogel,
grphene-bsed composite hydrogel, nd pure poly(N-isopropyl crylmide) hydrogels were synthe-
sized. NCDN hydrogel hving MXene demonstrted n elevted storge modulus, possibly due to
the presence of crosslinking in hydrogels, therefore enhncing the mechnicl strength of the hydro-
gel. The DN nd NCDN hydrogels possessed self-heling chrcteristics due to H-bonding nd
hydrophobic interctions. A self-heled tensile test ws used to determine the heling chrcteris-
tics. The strip of NCDN hydrogel ws cut in two prts; then, these two prts were plced together
t room temperture. Three dys lter, the heled hydrogel ws extended, nd it did not brek s
depicted in Figures 9.3 nd 9.3b. MXene embedded with hydrogels ugmented the self-heling to
59.5% due to the hydrogen bond nd crosslinking (Figure 9.3c nd 9.3d).
A self-heling, conductive, ntifreezing, nd excellent mechnicl strength, long-lsting mois-
ture bsed on MXene nnocomposite orgnohydrogel (MNOH) ws developed by Lio et l.45 The
MNOH ws prepred by incorporting MXene nnosheets with  hydrogel polymer network pre-
pred from polycrylmide nd PVA. Furthermore, there ws  crosslinking interction between
Self-Healing Activity of MXene/Polymer Nanocomposites 175

FIGURE 9.3 () Self-heling bility of NCDN hydrogel. (b) Stretching imge of NCDN hydrogel. (c) Tensile
curves. (d) Self-heling efciency of the HAPAM, DN, NCDN-heled hydrogels (error brs, SD; n = 3).
Source: Reprinted with the consent from Reference no. [44] with Copyright {2019} Americn Chemicl Society

the OH group nd the tetrhydroxyl borte ions nd  suprmoleculr interction between the PVA,
ethylene glycol, nd MXene, resulting in n outstnding self-hel bility in the developed MNOH.
A high number of hydrogen bonds formed between H2O, nd ethylene glycol molecules hindered
the evportion of wter s well s prevented ice formtion. The fbricted MNOH showed  strong
ntifreezing bility t very low tempertures (−40°C), moisture retention for pproximtely 8 dys,
heling bility, nd higher mechnicl strength. Furthermore, the fbricted hydrogels my hve
pplictions s werble strin sensors to distinguish humn ctivities with high-sensing sensitivity
t extremely low tempertures (−40°C).
Wng et l.46 synthesized MXene nnosheet self-ssembled with polycrylic cid (PAA) hydro-
gel hving nti-ggregtion nd ultr-stretchble (nerly 1400%) properties. For the synthesis, TiO2
nnoprticles were grown on the MXene surfce. Furthermore, the reduced TiO2@ MXene initi-
ted rpid polymeriztion of monomer cryl mide (AA) without heting nd induced crosslinked
polymer chins to mke hydrogel in very short time (in min). Moreover, the structurl, mechnicl,
conductive nd dhesive properties of synthesized hydrogel were modied by vrying the content of
TiO2@MXene. The developed pthwy minimized the ggregte of MXene nnosheets nd thereby
incresed its stretching power. The synthesis of TiO2@MXene-PAA hydrogel involved peeling off
thick multilyer of (M-MXene) to form delminted MXene (d-MXene) by ultrsoniction followed
by in situ development of TiO2 NPs on d-MXene surfce by solvo-therml method (Figure 9.4).
Further, n ultrsonic tretment ws done to increse the interction mong AA nd mmonium
persulfte (APS) nd mintin dispersion. Afterwrd,  redox rection took plce between the
reduced TiO2@MXene nnosheets with oxidnt APS. There is decrese in decomposition ctiv-
tion energy (Ed) of APS nd generted  lrge mount of SO4 –. Then, OH. rdicls were generted
by hydrolysis of SO4 – tht initited ultrfst polymeriztion of AA to PAA chin hving  vine-
like structure. The developed stble hydrogel showed outstnding mechnicl properties, nmely,
stretchbility up to 15 times the originl length nd recoverbility. Furthermore, it did not rupture
even fter being subjected to 95% compression.
176 MXene-Filled Polymer Nanocomposites

FIGURE 9.4 () The excittion of crylmide monomers conned on the surfce of TiO2@MXene in pres-
ence of soniction.(b) The TiO2@MXene ctlyzed preprtion of PAA.(c) Self-crosslinked nd self-ssembled
chrcteristics of PAA with TiO2@MXene.(d) Scnning electron microscopy imges of synthesized hydrogel.
Source: Reprinted with the permission from Ref. [46] Copyright {2020} Elsevier.

MXene contining PVA/polyvinyl pyrrolidine (PVP) double-network hydrogels (MDN hydro-

gels) were synthesized by Lu et l.47 for exible strin sensors. The mechnicl properties of MDN
hydrogels were highly improved by the strong interction between MXene nd PVP nd PVA
mtrix. The MDN hydrogels with 3 wt% PVP content nd moleculr weight 55,000 exhibited the
best performnce. The synthesized MDN hydrogels showed outstnding mechnicl properties
of puncture resistnce, high stretchbility (2400%), excellent stress tolernce, nd cyclic stbility.
Moreover, the strin sensor bsed on the MDN hydrogel showed high sensitivity (10.75k/P), excel-
lent durbility, quick response (33.5 Ms), nd low detection limit (0.87 P). The sensors could be
used to detect humn motions nd embedded with certin devices to detect pressure nd provide
severl pplictions in helth dignosis.
A superfst self-helble PVA/Bn/PEI/Ti3C2Tx (PBPM-2)-bsed dul-network exible hydro-
gels were prepred by PVA, nd polyethylenimine (PEI) with Bn nd further dding MXene to
Self-Healing Activity of MXene/Polymer Nanocomposites 177

furnish the desired polymer network. Fbricted hydrogels PVA/Bn/PEI/MXene (PBPM-2) exhib-
ited direction wre nd fst self-heling bility with nerly 0.06 s self-heling time nd rpid
response performnce (nerly 0.12 s). The outstnding self-heling bility ws chieved by the for-
mtion of verstile chemicl bonds, nd suprmoleculr interction between PEI, PVA, nd MXene
in the polymer network. Bn cted s  crosslinker between the functionl groups OH of PVA nd
functionl group NH2 of PEI tht formed severl imine nd borte bonds nd induced self-heling
property. The fbricted hydrogel exhibited  high direction recognizing bility tht cn be used for
electronic skin.48
In generl, MXene-bsed hydrogel did not fulll the self-heling nd mechnicl necessities
needed to be pplied for soft electronics but due to the luminosity of intricte moleculr interctions
mde by MXenes composites, stretchbility, quick geltion chrcteristics, nd self-heling prop-
erties in different polymer-bsed hydrogels re perhps chievble. MXene-bsed hydrogels hve
become good cndidtes for stretchble electronics. In 2021, Gng ge et l.49 synthesized MXene-
bsed hydrogels, mixed Ti3C2Tx nnosheets with  monomer, like crylic cid with (NH4)2S2O8 nd
glycerol, to produce poly(crylic cid)MXene hydrogels.
Ti3C2Tx MXene cts s  crosslinker for ctivting fst geltion of  brod rnge of hydro-
gels (monomers to polymer-bsed precursors). The monomer precursors include AA (crylic
cid), DMA (N,N-dimethylcrylmide), AM (crylmide), HEMA (hydroxyethyl methcry-
lte), NIPAM, ANI (niline), nd PEGDA (poly(ethylene glycol) dicrylte nd the polymer
bsed precursors include gr, geltine, PVA, chitosn, nd lginte. The mechnism of fst
geltion involved esy genertion of free rdicls using Ti3C2Tx MXene nd moleculr interc-
tion between MXene nd polymers. MXene,  verstile crosslinker, dded high stretchbility,
dhesion, nd self-heling properties to hydrogels in perspective of stretchble nd werble
electronics. The dt nlysis showed tht the induced geltion process of mixing MXene
with polymer chins ws slower compred to mixing with only monomers. The properties
like threshold concentrtion nd geltion of polymer-bsed MXene hydrogels minly depends
on chrcteristics of polymers. It is interesting to note tht PAAMXene1.43 hydrogels could
uphold 530.81% heling strin with 147.86 kP recovered. After heling for 6 h, the restored
strins for PAA MXene2.86 ws 992.86% nd PAAMXene 4.29 ws chieved to be 1503.35%,
respectively. The PAAMXene 4.29 ws used s  reference to evlute the self-heling prop-
erty (Figure 9.5–g). Both PAAMXene2.83 nd PAAMXene 4.29 hydrogels displyed good self-
heling cpbility even fter 15 dys’ storge. (Note: The subscript in MXene represents the
concentrtion of MXene in hydrogel.)
Yu nd coworkers50 designed  two-step procedure to synthesize hydrogel-bsed exible elec-
trode by crosslinked PAA/chitosn/Ti3C2Tx (PCT). The exclusive 2D-lyered-type structure of
MXene Ti3C2Tx fcilitted the hydrogel electrode to endure substntil ltertion in pressure with-
out breking it nd hs tremendous tensile property. The electrode demonstrted n outstnding
tensile power up to 0.083 MP. This give reserch nd expnsion pproch for nontoxic, binder-free,
nd esily portble storge devices.
A multifunctionl conductive epiderml sensor bsed on stretchble, biocomptible, helble
hydrogel ws developed by Li nd couthors.51 The developed hydrogel ws coted with MXene
network with (PAA) nd morphous CCO3. The developed epiderml sensors cn be pplied for
the identiction of humn movements with  quick response time (20 ms). Moreover, the fbricted
sensors could be degrded in the solution of phosphte buffer sline tht cused no pollution to the
environment.
Ai et al.52 fbricted self-heling MXene nnocomposite hydrogels (MNH) using MXene nd
PVA s bsic frmework crosslinked by diol–borte ester bonding. The fbricted MNH exhibited
high self-heling performnce nd outstnding tensile nd ftigue resistnce. They lso showed
92% self-heling bility, enhnce slintion cpcity (51 mg/g), good mechnicl property, elec-
trochemicl heling property (95.8%) nd excellent cyclic stbility. The developed mterils could
self-hel dmged interfces with pplictions in cpcitive deioniztion.
178 MXene-Filled Polymer Nanocomposites

FIGURE 9.5 () The pictoril representtion of the self-heling property of hydrogels t different MXene
concentrtions. (b) Stress−strin rc for PAAM-Xene 4.29 hydrogels in different time intervls. (c) N,N’-
methylene-biscrylmide (MBAA) concentrtion effect on self-heling chrcteristics of hydrogels. (d) The
imges by the opticl microscope of the cut re fter heling for subsequent 0 (I), 10 (II), 20 (III), nd 30 (IV)
min. (e) Interprettion of heling power of PAA (red) nd PAAMXene1.43 (green) hydrogels. (f) Ner-infrred
lser–induced self-heling power. (g) Mechnism of self-heling.
Source: Reprinted with the consent from Ref. [49] with copyright {2020} Americn Chemicl Society

9.2.2 SELF-HEALING CHARACTERISTICS OF MXENE-BASED NANOCOMPOSITES/NANOSHEETS

The designing of werble nd trnslucent mterils with self-heling chrcteristics, which my
recuperte their functionlity even fter mechnicl demolishment is essentil. In lieu of this, Fn
nd coworkers53 synthesized hybrid sheets of Ag-Np@MXene with polyurethne (PU). The incor-
portion of MXene with Ag nnoprticles gve rise to high photo-therml conversion efciency
becuse of the grouping in plsmonic chrcteristics of Ag-NPs in combintion with the therml
conductivity of the MXene. The synthesis of Ag-NP@MXene hybrid is done s per the previously
reported literture.54–56
Wu et al.57 synthesized n dhesive, conductive, moist, nd helble MXene-bsed nnocompos-
ite hydrogel using MXene nnosheets, phenylboronic cid grfted with sodium lginte (Alg-PBA),
dopmine-grfted sodium lginte (Alg-DA), nd polycrylmide in the  presence of mixture of
Self-Healing Activity of MXene/Polymer Nanocomposites 179

SCHEME 9.1 Grphicl presenttion of fbriction of MXene nnocomposite orgno-hydrogel.

Source: Reprinted with the consent from Reference no. [57] Copyright {2020} Royl Society of Chemistry

wter nd glycerol. First, MXenes were synthesized using LiF/HCl method. In prllel to this,
crylmide ws mixed to mixture of glycerol nd wter. Now, Alg-PBA nd Alg-DA were mixed to
this solution nd stirred continuously. Lter on, upon complete dissolution, the MXene nnosheets
solution nd Tris-HCl were dded, with subsequent ddition of N,N’-methylene-biscrylmide nd
2,2’-zobis[2-(2-imidzolin-2-yl)propne] dihydrochloride. The resultnt mixture ws stirred t
60°C for 2 h to obtin the orgno-hydrogels. The schemtic presenttion of synthesis procedure is
depicted in (Scheme 9.1). Polycryl mide ws integrted with the orgno-hydrogels to improve the
mechnicl chrcteristics of orgno-hydrogels. The mss rtio of wter nd glycerol ffected the
mechnicl nd other properties of composites. With increse in glycerol rtio, the conductivity of
orgno-hydrogels diminished wheres the other properties, like self-dhesiveness nd the tensile
strin, were ugmented. These MXene nnocomposite orgno-hydrogels exhibited  self-heling
cpbility ttributble to PBA ctechol bonds s shown in Figure 9.6. When their helbility ws
tested by cutting the sheet into two prts nd then were put bck together, they heled t room
temperture fter 12 h. The heled orgno-hydrogels cn be stretched up to 71.0% with the heling
efciency (88.75%). The self-dhesive property is ttributed to OH groups of glycerol nd ctechol
group of PDA, nd due to these miscellneous ctivities, these composites hve been used in wer-
ble epiderml sensors.
Zheng nd coworkers58 synthesized  multifunctionl hydrogel scffold to cure infection-
impired skin. Herein, multifunctionl hydrogel scffold CeO2@MXene nnocomposites were
synthesized via merging the 2D ntibcteril MXenes (Ti3C2Tx) nd ntioxidnt CeO2. These mul-
tifunctionl hydrogels hve  plethor of properties like nti-inmmtory, self-helble, ntibcte-
ril, conductive bioctivities, ntioxidtive, hemosttic cpcity, nd tissue dhesiveness. Here, the
180 MXene-Filled Polymer Nanocomposites

FIGURE 9.6 Imges of self-heling process for MXene nnocomposite orgno-hydrogels.

Source: Reprinted with the consent from Reference no. [57] Copyright {2020} Royl Society of Chemistry

uthors estblished the impertive role of multi-functionl CeO2@MXene in vrious pplictions

like multidrug-resistnt infection therpy, collgen deposition, promoting broblsts prolifertion,
nd grnultion tissue formtion, helpful in wound heling.
MXene-bsed composites hve gined much scientic interest in electronic sensors, btteries,
ctlysis, puriction, biomedicl pplictions, nd EMI shielding. On the other hnd, their nti-
corrosion property is hrdly investigted due to oxidizing nture of MXene nnosheets. Zho nd
coworkers59 synthesized ntioxidnt Ti3C2 MXene nnosheets via noncovlent functionliztion of
MXene with n ionic liquid (IL) nd used them s nticorrosion coting. The resultnt IL@MXene
nnosheets were employed s brrier provoked by wterborne epoxy (WBE) to improve the nticor-
rosion ctivity. The interprettion of nticorrosion ctivity of steels coted with IL@MXene–WBE
displyed greter corrosion inhibitory ctivity thn WBE. Furthermore, the heling chrcteristics
of the IL@MXene–WBE coting were estblished by the SVET. This study gives n pproch to
devise the synthesis of MXene-bsed composites for nticorrosion cotings.

9.2.3 SELF-HEALING CHARACTERISTICS OF MXENE-BASED SUPRAMOLECULES

Zhng nd coworkers60 deliberted nd synthesized conductive silicone-bsed polymer composite.
MXenes nd mino polydimethylsiloxne (PDMS) were customized through n esteriction rec-
tion nd Schiff bse rections of tiny bio-orgnic molecules. MXene ws tilored by the rection
between the functionl groups COOH nd OH of D-sprgine, which ws extrcted from Liliaceae
plnts. In the mentime, 3,4-dihydroxybenzldehyde ws embedded in PDMS mcromolecules.
The A-MXenes@D-PDMS hs self-heling bility t room temperture due to the presence of cru-
cil interctions, nmely, H-bonding nd imine interction. These crucil interctions lso improve
the tensile chrcteristics nd heling efciency. The customized MXenes re evenly dispersed,
bestowing the newly fbricted composites with good electricl conductivity.
The self-heling chrcteristic ws demonstrted using  stereomicroscope.
It ws estimted by using  formul:

Healing Efciency = helble/org × 100%.

Self-Healing Activity of MXene/Polymer Nanocomposites 181

SCHEME 9.2 Synthesis of MXene-bsed elstomer via the ltex ssembly method.
Source: Reprinted with the consent from Reference no. [61] Copyright {2020} Americn Chemicl Society.

Sorg nd Shelble were relted to the tensile cpbility of the originl smple nd the helble one,
respectively.
The designed composites hving 10 wt% of A-MXenes exhibited stretching cpcity up to 81%
nd mechnicl power (1.81MP). Tensile chrcteristics nd electricl conductivity cn be regined
to 98.4% nd 97.6%, respectively, fter regenertion. The helble composites cn lso precisely
perceive petite humn motion.
Suprmoleculr-bsed hydrogen bond interctions in  polymer composite re n efcient
pproch for bestowing designed composites with self-heling chrcteristics. In 2020, Guo nd
coworkers61 devised n efcient, helble nnostructured Ti3C2MXenes@rubber (NMSE) for
intelligent sensing. For this, nnokes of MXenes were customized via mino cid serine by the
condenstion rection of OH group of MXene nd COOH group of serine. The H-bonding mid
the surfce of customized MXenes nd elstomer helped recuperte its mechnicl nd electricl
performnce t room temperture nd provided outstnding self-heling properties (Scheme 9.2).
The s-synthesized suprmoleculr elstomers offered concurrently improved mechnicl power
nd higher heling bility without externl stimulus (Figure 9.7). The designed NMSE gve desir-
ble toughness (12.34 MJ/m3) nd tremendous heling chrcteristics of nerly 100% just t room
temperture. The sensors tht re bsed on NMSE hve high guge fctor (107.43), fst responding
time (50 ms), nd low strin detection limit (0.1%) cn ccurtely determine subtle humn ctivity
like speech, hertbet, fcil expression, nd pulse, s well s moisture vrition, even fter cut/
heling procedure.

9.2.4 MXENE-BASED SUPERCAPACITORS AND THEIR SELF-HEALING CHARACTERISTICS

Micro-supercpcitors (MSCs) re one of the relible energy storge devices for powering nno/
micro devices. Flexible MXene-bsed MSCs re currently in demnd due to their low-cost
182 MXene-Filled Polymer Nanocomposites

FIGURE 9.7 Self-heling chrcteristics of exible NMSE: () Dynmic rupture nd reformtion of supr-
moleculr H-bond in NMSE. (b) Stress–strin curves. (c) Rmn spectrum. (d) Representtion of blueshift of
the G bnd t different strins in MXenes/ENR. (e) Blueshift for SMXenes/S-ENR smples.(f) Tensile curves
for S-MXenes (6 wt%) t dissimilr times. (g) Tensile curve for S-MXenes t different times. (h) Evlution
of heled mechnicl chrcteristics mid diverse helble elstomers. (i) Microscopic imge of rough nd
heled smples. (j) Different imges of  heled smple showing loding weight, twisting, stretching, nd
bending.
Source: Reprinted with the consent from Reference no.[61] with Copyright {2020} from Americn Chemicl Society.

fbriction process nd cycling stbility. Severl studies hve been done in the eld of exible
MXene-bsed MSCs, but some limittions need to be overcome:

• These MSCs re certinly smshed by internl nd externl deformtion.

• MXene’s conductivity corresponds to its nnosheet size.
Self-Healing Activity of MXene/Polymer Nanocomposites 183

In order to combt these limittions,  new kind of self-helble MSCs, dependent on the size of
the MXene, ws reported using spry-coting nd lser-engrving methods.62 Lrge nd smll
MXene-bsed nnosheets (L-MXene, S-MXene) were synthesized by chnging conditions of
mechnicl exfolition. This pproch involved fbriction of lms bsed on MXene by spry-
ing the solution of L-MXene nd S-MXene onto cellulose pper with the help of n irbrush
nd further dried under vcuum for 3 h t 50°C. Then, the interdigitl ptterns of MXene were
engrved by lser-engrving method. Furthermore, n H 2SO 4 -PVA gel electrolyte ws dropped
on the interdigitl ptterns for ssembling MXene-bsed MSCs. Finlly, they were wrpped
by crboxylted PU to convert them into self-helble MXene-bsed MSCs. PU is lible for
the self-heling. The prepred micro-supercpcitors bsed on MXene showed good exibility,
excellent stbility (>87.5%), nd high rel cpcitnce (upto 73.6 mF/cm 2). The synthesized
MSCs lso showed self-helble performnce, nd the cpcitnce ws retined (>80%) even
fter  fth heling.
Yue et al.63 designed  self-helble 3D micro-supercpcitors (MSCs) using (Ti3C2Tx)-@
grphene-(reduced GO) composites s n electrode mteril nd enclosed with gel electrolyte
composed of PVA-H 2SO 4 nd crboxylted PU s self-heling mterils. Simple freeze-dry-
ing nd lser-cutting methods were used to synthesize MXene–rGO composite erogel-bsed
electrode. The crboxylted PU bers  high interfcil H-bond tht helped in the outstnd-
ing self-heling properties, with 81.7% fter  fth heling. The fbricted MSCs showed 
high exterior-re cpcitnce (34.6 mF/cm 2), with  scn rte (1mV/s) nd excellent cycling
performnce.

9.2.5 MXENE-BASED FILMS, ELECTRODES, OTHER COMPOSITIONS

AND THEIR SELF-HEALING BEHAVIOR

A librry of helble, wterborne polyurethne (ADWPU) lms ws developed by combining PU

with Ti3C2Tx MXene mechniclly.64 The ADWPU@ MXene emulsions were synthesized from
cstor oil, tht is, n eco-friendly biomss polyol. 2-minophenyl sulde, the chin extender gve 
reversible verstile network tht led to outstnding self-heling power. The developed MXene-bsed
lms showed excellent EMI shielding (51.37 dB) nd displyed negotible ltertion in shielding ef-
ciency even fter bending nd stretching 200 times. Furthermore, Zho nd coworkers65 designed
n eco-friendly, sfe zinc–ion micro-bttery (ZIMB) hving n node mde up of MXene-TiS2
(de)intercltion nd  cthode bsed on crbon nnotubes-vndium dioxide (MWCNTs-VO2),
with ZnSO4-PAM hydrogel s the electrolytic solution nd PU cting like  defensive shield incor-
ported. The ZIMB displyed n dequte electrochemicl cpcity of 40.8 μAh cm−2,  mximum
energy density up to 1.2 mW cm−2, nd  mximum power density up to 32.5 μWh cm−2. Moreover,
ZIMB possessed thermo-stbility, outstnding exibility, nd high self-helbility. This reserch
gives  vible pproch to develop superior, highly consistent, nd stedy micro energy-storge
devices for integrted electronics nd werble devices.
Wu nd coworkers66 designed  complex structure, by incorporting MXenes with mgnesium–
luminum-lyered double hydroxides (MXenes@Mg-Al-LDHs) with Y(OH)3. The synthesis of
these composites involved smrt coting on Mg lloy AZ31 through the following steps:

• The multilyer MXene ws converted to smll-lyer MXenes.

• Y(NO3)3 ws dded to  solution of smll-lyer MXenes via  single-step hydrotherml
tretment.
• Due to the electronegtive nture of MXenes, it could prociently tke up ctions from the
rection mixture nd endorse growth of Mg–A–LDHs nd Y(OH)3 on its surfce.
• As per the corrosion nlysis, the results specied tht coting of yttrium hve  splendid
nticorrosion property nd self-heling bility. Their self-heling behvior ssists nticor-
rosion ctivity.
184 MXene-Filled Polymer Nanocomposites

Ci nd couthors67 designed  composite heterostructure by in situ ssembly of Ti3C2Tx @MgAl–
LDH via electrosttic interction. The interfce mid the MXene Ti3C2Tx nd MgAl–LDH is exm-
ined by DFT theory. This Ti3C2Tx@MgAl–LDH ccomplished tremendous comptibility s well
s dispersibility in presence of epoxy resin. The synthesized Ti3C2Tx@MgAl–LDH/epoxy coting
(C-MXene@LDH) demonstrted cceptble sher nd wer defense with  denite self-heling
property, becuse of the excellent dispersibility, the corrosion inhibitor dischrge, nd the brrier
effect of Ti3C2Tx@MgAl–LDH. This study is  huge impliction for MXene-bsed heterostructure
nlogs to cquire n enormous pthwy pproch for the nticorrosion nd ntiwer pplictions.
Zou et al.68 synthesized kes tht re light-induced helble hving n epoxy coting on
MXene. This helble coting hs reversible crosslinking network between the mleimide groups
nd the furn groups from oligomers by Diels–Alder rection. As the temperture becme high,
the bonding between the multi-furn nd the multi-mleimide broke, which produced  movble
phse tht stremed nd lled up crcks. Heling is done t low tempertures. MXene ws prepred
by dissolving 10 g of Ti3AlC2 in 100 mL HF solution (49%) t optimum temperture of 30°C for 
period of 7dys. The solution ws centrifuged nd wshing with solvents like wter nd ethnol.
The ppt. ws treted with 50 mL of tetrpropylmmonium hydroxide, with stirring for 3 dys t
room temperture. Then this solution ws centrifuged severl times nd wshed with wter nd
ethnol to remove excess of tetrpropylmmonium hydroxide. In subsequent to this, oligomers were
synthesized using DGEBA nd FA ws liqueed with DMF. This mixture ws stirred for 6 h t
100℃. BMI ws mixed with this solution. A denite quntity of delminted MXene ws dispersed
with DMF (1 mL) under soniction for 1 h nd stirred briskly. Leveling gents cn lso be mixed s
needed. In this wy, MXenes coted with epoxy were synthesized. With ddition of the MXene, gel
content (G) slightly incresed nd swelling rtio (Q) reduced. The ddition of MXene improves not
only the therml stbility but lso the mechnicl nd nticorrosion properties. Temperture ffects
the self-heling behvior. The hole with  width of 10 µm in MX-0 strted shutting fter exposure
of temperture 150°Cfor 5 s nd then stedily vnished in 30 s.
For the esier understnding of the reders,  comprison tble for self-heling efciency, self-
heling time of some MXene-bsed compounds hs been ppended in Tble 9.1.

TABLE 9.1
Self-Healing Efciency and Self-Healing Time of Some MXene-Based Compounds
Self-Healing
S.No. MXene-Based Compounds Efciency Self-Healing Time Reference
1. MXene hydrophobiclly ssocited/polycrylmide/ 59.5% 72 h [44]
poly(N-isopropylcryl mide)
2. MXene nnocomposite orgnohydrogel synthesized >85% 12 h [45]
from ethylene glycol
3. AgNP@MXene-PU composites 97% 5 min of photo- [53]
therml heling
4. PAA-MXene hydrogels 52.21% with 2h [49]
818.81% strin
1. 74.68% with 4h
1171.70% strin
1. 88.29% with 6h
1385.03% strin
5. MXene-Bsed Nnocomposite 88.75% 12 h [57]
Synthesized by dopmine grfted sodium lginte,
phenylboronic cid
Grfted sodium lginte nd polycrylmide
Self-Healing Activity of MXene/Polymer Nanocomposites 185

9.3 APPLICATIONS OF SELF-HEALABLE MXene-BASED MATERIALS

MXenes hve n exclusive permuttion of properties, together with the mechnicl properties nd
high electricl conductivity of crbides/nitrides of the trnsition metl. The surfce functionliz-
tion, which mkes MXene-bsed mterils hydrophilic, provokes their binding with other com-
posites to enhnce their properties nd pplictions. The miscellneous pplictions of MXenes in
different elds of science re depicted in Figure 9.8.
Trnsprent nd skin-mountble devices re extremely preferred for future pplictions of elec-
tronic devices. Designing of werble, lightweight, esily portble, nd trnsprent mterils tht
hve helble properties nd mintin their originl functionlity even fter mechnicl dmge, is
inevitble. MXenes cover severl res of the bsic sciences, including orgnic chemistry, synthe-
sis, biomedicl, structure designing, werble sensors, energy storge, membrnes, ctlysis, nd
optics. This diversity of elds depict  foremost discovery nd reserch in MXene uses in compri-
son to other 2D mterils. MXene-bsed composites re used for electronic nd photonic devices,69
supercpcitors,70in vitro perspirtion nlysis,71 exible strin nd pressure sensors,47 drug deliv-
ery, dignostic imging, nd biosensors,72–74 mong others.
Although MXenes possess  plethor of pplictions, their use is restricted. In order to increse
their pplictions, self-heling property hs been introduced in MXenes by embedding the self-
heling polymer composites to it. This integrtion not only enhnces the properties of MXenes
but lso provokes their pplictions. Due to the introduction of self-heling chrcteristics, MXene
nd its composites, hydrogels, lms, nd so on hve been designed to cover enormous pplictions
like corrosion coting, re protection, e-skin, werble sensors, nd mny more. MXenes embed-
ded with hydrogels nd suprmolecules hve been used to design sensors tht cn identify body
motions42, 45, 61 nd be used to synthesize werble sensors60nd micro-supercpcitors.50, 62–63 The
designed AgNP@MXene hybrids re efcient moleculr heters, energy trnsformers, nd pho-
ton cptors. They re used to design werble devices.55 MXene nnocomposites hve been used
s epiderml sensors,57e-skin nd infection-impired skin multimodl therpy,58 EMI shielding,64
nti-corrosion coting,59, 67, 75 electrodes,65 MXene/chitosn-coted cotton fbric for intelligent re
protection,76nd so on.

FIGURE 9.8 Miscellneous pplictions of MXene-bsed compounds.

186 MXene-Filled Polymer Nanocomposites

9.4 CONCLUSION
In this chpter, the current dvncements nd success in self-helble MXene-bsed mterils hve
been discussed. The self-heling property ws enhnced by integrting the MXene with other poly-
mers/suprmolecules/hydrogels. There hs been n enormous rise in MXene-bsed self-helble
mterils over the pst decdes. These mterils work s potentil cndidtes in extensive pplic-
tions, nmely, electromgnetic interference shielding, electroctlysis, the puriction of wter, nd
werble devices, ctlysis, biomedicl pplictions, nd others. MXene polymer–bsed composi-
tions re noticebly promising for n extensive rnge of pplictions, still this eld of reserch is in
its infncy, Furthermore, the chpter investigtes the emerging potentil of the self-heling property
of MXene-bsed composites up to dte. We suppose tht this work will stimulte more reserch
interest in MXene-bsed compounds in other elds of chemistry nd  quick focus on sclble pro-
duction of these mterils is indeed required.

ABBREVIATIONS
Acrylic cid : AA
Acrylmide : AM
Aniline : ANI
2, 2’-zobis[2-(2-imidzolin-2-yl)propne] dihydrochioride : AIBI
Amino polydimethylsiloxne : PDMS
Bis(4-mleimidopheny)methne : BMI
Diglycidylether of bisphenol A : DGEBA
Dopmine grfted sodium lginte : Alg-DA
Furfurylmine : FA
4-Formyl benzoboric cid : Bn
Hydroxyethyl methcrylte : HEMA
Luryl methcrylte (96%) : LMA
Methyl methcrylte : MMA
N,N-dimethylcrylmide : DMA
N,N′-methylenedicrylmide : MBAA
N-isopropylcrylmide : NIPAM
N,N,N′,N′-tetrmethylethylenedimine : TEMED
Polyethylenimine : PEI
Polyurethnne : PU
Poly(ethylene glycol) dicrylte : PEGDA
Polyborosiloxne : PBS
Phenylboronic cid grfted with sodium lginte : Alg-PBA
Scnning vibrting electrode technique : SVET

ACKNOWLEDGMENT
The uthors re thnkful to Deprtment of Chemistry, M. L. Sukhdi University, for providing
necessry librry fcilities. A. Sethiy is lso thnkful to UGC-MANF (201819-MANF-2018-19-
RAJ-91971) for providing senior reserch fellowship.

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61. Guo, Q., Zhng, X., Zho, F., Song, Q., Su, G., Tn, Y., To, Q., Zhou, T., Yu, Y., Zhou, Z., nd Lu, C.
2020. Protein-inspired self-helble Ti3C2 MXenes/rubber-bsed suprmoleculr elstomer for intel-
ligent sensing. ACS Nano 14(3): 2788–2797.
62. Li, X., M, Y., Shen, P., Zhng, C., Yn, J., Xi, Y., Luo, S., nd Go, Y. 2020. Highly-helble micro-
supercpcitors with size-dependent 2D MXene. Chem. Electro. Chem. 7(3): 821–829.
63. Yue, Y., Liu, N., M, Y., Wng, S., Liu, W., Luo, C., Zhng, H., Cheng, F., Ro, J., Hu, X., Su, J., nd
Go, Y. 2018. Highly self-helble 3D microsupercpcitor with MXene−grphene composite erogel.
ACS Nano 12: 4224−4232.
64. Lu, J., Zhng, Y., To, Y., Wng, B., Cheng, W., Jie, G., Song, L., nd Hu, Y. 2021. Self-helble cstor
oil-bsed wterborne polyurethne/MXene lm with outstnding electromgnetic interference shield-
ing effectiveness nd excellent shpe memory performnce. J. Colloid Interface Sci. 588: 164–174.
65. Zho, B., Wng, S., Yu, Q., Wng, Q., Wng, M., Ni, T., Run, L., nd Zeng, W. 2021. A exible, het-
resistnt nd self-helble “rocking-chir” zinc ion microbttery bsed on MXene-TiS2 (de)intercltion
node. J. Power Sources 504: 230076.
66. Wu, Y., Wu, L., Yo, W., Jing, B., Wu, J., Chen, Y., Chen, X., Zhn, Q., Zhng, G., nd Pn, F. 2021.
Improved corrosion resistnce of AZ31 Mg lloy coted with MXenes/MgAl-LDHs composite lyer
modied with yttrium. Electrochimica Acta 374: 137913
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67. Ci, M., Fn, X., Yn, H., Li, Y., Song, S., Li, W., Li, H., Lu, Z., nd Zhu, M.H. 2021. In situ ssemble
Ti3C2Tx MXene@MgAl-LDH heterostructure towrds nticorrosion nd nti-wer ppliction. Chem.
Eng. J. 419: 130050.
68. Zou, Y., Fng, L., Chen, T., Sun, M., Lu, C., nd Xu, Z. 2018. Ner-infrred light nd solr light cti-
vted self-heling epoxy coting hving enhnced properties using MXene kes s multifunctionl
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69. Kim, H., nd Alshreef, H.N. 2020. MXetronics: MXene-enbled electronic nd photonic devices. ACS
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70. Lee, H., Le, T.A., Trn, N.Q., nd Hong, Y. 2019. Intertwined titnium crbide MXene within 3D tn-
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1037–1043.
71. Lei, Y., Zho, W., Zhng, Y., Jing, Q., He, J.-H., Beumner, A.J., Wolfbeis, O. S., Wng, Z. L., Slm,
K.N., nd Alshreef, H.N. 2019. A MXene-bsed werble biosensor system for high-performnce in
vitro perspirtion nlysis. Small 15: 1901190.
72. George, S.M., nd Kndsubrmnin, B. 2020. Advncements in MXene-polymer composites for vri-
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73. Yng, X., Feng, M., Xi, J., Zhng, F., nd Wng, Z. 2020. An electrochemicl biosensor bsed on
AuNPs/Ti3C2 MXene three-dimensionl nnocomposite for microRNA-155 detection by exonuclese
III-ided cscde trget recycling. J. Electroanal. Chem. 878: 114669.
74. Chen, K., Chen, Y., Deng, Q., Jeong, S.-H., Jng, T.-S., Du, S., Kim, H.-E., Hung, Q., nd Hn, C.-M.
2018. Strong nd biocomptible poly(lctic cid) membrne enhnced by Ti3C2Tz (MXene) nnosheets
for guided bone regenertion. Mater. Lett. 229: 114–117.
75. Yn, H., Li, W., Li, H., Fn, X., Zhu M. 2019. Ti3C2 MXene nnosheets towrd high-performnce cor-
rosion inhibitor for epoxy coting. Prog. Org. Coat. 135: 156–167.
76. Wng, B., Li, X., Li, H., Jing, C., Go, J., nd Zeng, X. 2021. Multifunctionl MXene/chitosn-coted
cotton fbric for intelligent re protection. ACS Appl. Mater. Interfaces 13(19): 23020–23029.
 10 Microwave Absorption and
EMI Shielding Performance
of MXene-Filled Polymer
Nanocomposites
Bhavya Bhadran, Avinash R. Pai, and Sabu Thomas

CONTENTS
10.1 Introduction ........................................................................................................................... 191
10.2 EMI Shielding ....................................................................................................................... 194
10.2.1 Mechnism of EMI Shielding ................................................................................... 194
10.2.1.1 Shielding Efciency................................................................................... 195
10.2.1.2 Absorption Loss ......................................................................................... 195
10.2.1.3 Reection Loss........................................................................................... 195
10.2.1.4 Multiple Reections................................................................................... 196
10.2.2 Mesurement Techniques.......................................................................................... 196
10.3 Designing  Shielding Mteril............................................................................................. 196
10.4 MXene-Bsed Polymer Composites for EMI Shielding nd Microwve Absorption .......... 198
10.4.1 MXene-Bsed Aerogels, Foms, nd Hierrchicl Architectures
for EMI Shielding Applictions ................................................................................ 199
10.4.2 Thermoplstic MXene Nnocomposites ................................................................... 201
10.4.3 Thermosetting Plstic MXene Nnocomposites ....................................................... 203
10.4.4 Elstomer MXene Nnocomposites.......................................................................... 204
10.4.5 Intrinsiclly Conducting Polymer–MXene Nnocomposites.................................... 204
10.5 Conclusion............................................................................................................................. 205
Notes .............................................................................................................................................. 205

10.1 INTRODUCTION
Polymers re revolutionry mterils tht cn be synthesized, processed, nd designed to meet 
brod rnge of pplictions. The science nd technology of these fscinting mterils re running
their course in new directions. Very recently,  self-heling polymer bsed on minopropylmeth-
crylmide tht cn mture, restore, nd strengthen using crbon xtion ws designed by  group
of reserchers.1 In other words, polymers re synthetic mterils tht re cpble of mimicking the
properties of nture through proper modictions. With their lightweight nture, self-heling cp-
bilities, nd high therml stbility, polymers cn stisfy the fst-growing technologicl demnds
nd stringent requirements of spce missions nd stelth technologies, mong others, to  greter
extent. But the min drwbck is tht they possess very low tensile strength nd re inferior to some
properties like therml nd chemicl stbility, conductivity, nd so on, which limit their ppliction.
So the serch for high-performnce polymers ended up in nnoprticles becuse of their outstnd-
ing mechnicl, therml, electricl, mgnetic, opticl, rheologicl, me retrdnt, nd biomedicl
properties.2,3,4,5,6,7 Also, the size, shpe, nd geometry of nnoprticles ply  crucil prt in decid-
ing the overll properties of  composite.
DOI: 10.1201/9781003164975-10 191
192 MXene-Filled Polymer Nanocomposites

Among the 1D (one-dimensionl), 2D, nd 3D nnoprticles, the intriguing physicochemicl

properties of lyered 2D nnoprticles, such s grphene, boron nitride, nnoclys, nd others,
hve received signicnt interest becuse of their high spect rtio, surfce re, conductivity, nd
so on. The ltest ddition to this 2D fmily is the MXene– trnsition metl crbides nd crboni-
trides. They re fbricted by selective etching of “A” lyers from MAX phses (Mn+1 AXn), where
M describes erly trnsition metls, A constitutes group III or IV elements, nd X corresponds to
crbon, nitrogen, or both nd n = 1, 2, or 3 (Figure 10.2). The generl formul used to represent
MXenes is Mn+1XnTx, where Tx symbolizes the surfce functionlities like hydroxyl group (OH), O,
hlogens like uorine or chlorine, nd so on. The rst type of MXene (Ti3C2Tx) ws discovered in
2011 by Yuri Gogotsi, nd it ws nmed fter grphene.
The high metllic conductivities (~6000–8000 S/cm) nd hydrophilic nture mke them superior
to other 2D mterils like grphene. The lrge negtive–zet potentil vlue of MXenes enbles
them to form stble colloidl dispersions in wter. MXenes re of two types—the rst type belongs
to out-of-plne ordered double trnsition-metl MXenes (M2′M″ X2A) nd the second is in-plne
double trnsition-metl (M′2/3M″1/3)2X type.8 More thn 30 compositions of MXenes re known to
dte.9,10 Its inherent electricl conductivity, ctive functionlized surfces, dielectric nd mgnetic
properties, nd the like mke them tunble to  myrid of pplictions, comprising energy storge
nd conversion, hydrogen storge, ctlysis, wter puriction, fbriction of biosensors, opticl
nd trnsprent conductive electrodes, piezoelectric mterils, nd others. The importnce of this
2D mteril in electronic pplictions cn be clerly understood from the br chrt indicting pub-
liction sttistics (dt collected from Web of Science) given in Figure 10.1. According to the dt
collected, there hs been  huge increse in the number of reserch outputs relted to pplictions
in the sphere of electronics since 2013. It should be noted tht lthough  lot of reserch is going on
regrding MXenes, the work bsed on rdition shielding nd microwve bsorption properties of
MXenes is still in its infncy stge.
One of the mjor concerns now fced by humnkind is exposure to high-energy electromg-
netic rditions rising from electronic devices s  result of dvnced technologies. The forth-
coming 5G telecommuniction system, the growing populrity of portble nd werble devices,

FIGURE 10.1 Number of publictions in MXenes in the eld of electronics versus yer.
Source: Dt collected from Web of Science.
Microwave Absorption and EMI Shielding Performance 193

FIGURE 10.2 () MAX phse to MXene by selective etching of A lyer. (b) Mechnism of EMI shielding.

nd the like generte hrmful electromgnetic pollution, which dversely ffects humn helth
s well s the opertion of other communiction nd electronic devices. Thus, electromgnetic
interference (EMI) is  perilous problem tht rises from electrosttic dischrge (ESD), electronic
gdgets, lightning, solr res, nd so on. The only wy to reduce the effect of these rditions is
to fbricte lightweight, EMI shielding, nd microwve-bsorbing mterils tht cn operte t 
broder bndwidth. Mterils with strong conductivity, better mgnetic permebility, nd dielectric
constnt re used for EMI shielding purposes. A gret del of effort hs been put to diminish EMI
using metls, dielectric/mgnetic mterils, nd so on. But the lightweight, exible, nd corrosion-
resistnt nture of polymers mke them more ttrctive for mnufcturing shielding components.
Polymer nnocomposites with conducting llers provide effective shielding by both bsorption nd
reection methods by enhncing the δ vlue or skin-depth vlue (the distnce tht electromgnetic
rdition cn penetrte t  certin high frequency). Thus, conducting nnomterils like grphene,
silver nnowires, crbon nnoribbons, crbon nnobers, crbon nnotubes (CNTs), nd the like re
incorported into polymer mtrices to develop high-performnce shielding polymer nnocompos-
ites. EMI shielding devices nd ppliction in vrious domins like telecommuniction, militry (in
rdrs), erospce, biomedicl science, etc.11
Tody, soft, exible, nd stretchble electronic devices re gining signicnt ttention s they
constitute the next genertion of smrt devices. The bility to bend, compress, nd twist mkes them
suitble for  myrid of pplictions (werble electronics, soft robotics, etc.) tht cnnot be ccom-
plished using conventionl rigid, plnr devices. Polydimethylsiloxnes (PDMS), polyurethnes
(PU), liquid crystlline elstomers (LCE), styrene butdiene rubber (SBR), nd the like re some
of the stretchble elstomers used s soft substrtes for mnufcturing electronic devices.12 The
exible nture of PDMS, long with excellent mechnicl properties, therml stbility, oxidtion
resistnce, nd low glss trnsition temperture (Tg), mkes it  potentil cndidte for fbricting
mterils tht cn meet high-end requirements.13 Literture reports suggest tht block copolymers
bsed on polyimide nd polydimethylsiloxnes cn lso be used for low-erth-orbit pplictions.14
194 MXene-Filled Polymer Nanocomposites

LCEs re considered to be excellent soft substrtes for innumerble pplictions in the res like
soft robotics, electronics, deployble devices, nd so on.15

10.2 EMI SHIELDING

As discussed erlier, EMI is n unwnted electromgnetic signl tht disturbs electronic nd com-
muniction devices nd their performnce. They sometimes cuse sudden power uctutions, which
ultimtely results in totl dmge to the devices. The process of blocking these electromgnetic
rditions is clled EMI shielding.16 Thus, the shielding mterils function s  brrier ginst
these hrmful rditions by either bsorbing, reecting, or subduing them. The mechnism of EMI
shielding17 is given in Figure 10.2b. It is stted tht while the mechnism of bsorption shielding
is completely grounded on the presence of electric nd mgnetic dipoles, reection is governed by
electricl conductivity, nd the subduing or multiple internl reections of the rditions cn be due
to irregulrities, porous, multilyered structures, nd so on in the shield. If the shielding mteril is
electriclly conductive, it contins mobile chrge crriers in the form of electrons or holes. When
n electromgnetic wve strikes the surfce of the shield, these chrge crriers come in contct with
the wve nd cuse n opposing electromgnetic eld due to the redistribution of electrons or holes
in the shield. This opposing electromgnetic eld formed within the shield cncels the externl
electromgnetic eld nd thus protects the device from hrmful rdition. If the shielding mteril
displys better dielectric constnt nd mgnetic permebility, they contin electric nd mgnetic
dipoles tht block the pssge of externl mgnetic eld through the shield nd thus ct s  protec-
tive brrier. Sometimes, induced eddy currents in the shield lso increse the shielding cpcity of
the mteril. Shielding due to multiple internl reections is predominntly due to the scttering of
electromgnetic wves from the cvities or porous structures or multilyers nd the like present in
the shield. The shielding efciency is clculted s  decrese in the mount of incident power on
moving through the shield. Most commonly shielding mterils were mde of dielectric, conduct-
ing, or mgnetic mterils. Due to their high conductivity, metls re often preferred for mking
EMI shielding mterils, but their density, low exibility, nd corrosive nture limit their ppli-
ction in fbricting lightweight structures. These limittions cn be solved using polymer-bsed
nnocomposites becuse of their high exibility, mechnicl strength, tilor-mde properties, nd
lightweight nture. An idel EMI shielding device is supposed to show minimum reection with
mximum bsorption of EM wves, which is still considered the most chllenging tsk.

10.2.1 MECHANISM OF EMI SHIELDING

In the cse of polymer-bsed nnocomposites, the shielding mechnism relies on the mount s well
s proper dispersion of nnoprticles in the polymer mtrices. Reection or bsorption of electro-
mgnetic rditions depends on whether the nnoprticle loding is bove or below the percoltion
threshold vlue. To be more precise, it is the vlue t which the electricl conductivity of  mteril
or polymer displys  steep increse t  prticulr volume frction of the conductive nnoprticle.
It is well known tht polymer nnocomposites with high electricl conductivity disply superior
shielding efciency. But most commonly,  higher mount of conductive llers must be loded into
polymer mtrices to chieve high electricl conductivity nd thus better shielding efciency. Tht is,
the percoltion threshold vlue will be very high. As  result, the weight of the composite increses,
which compromises its exibility s well s processbility nd ppliction. So polymer nnocom-
posites with  low percoltion threshold vlue re considered to be more signicnt to fbricte
suitble lightweight, exible, nd stretchble EMI shielding devices.
MXenes, the gship of 2D nnomterils, in this context, show extremely low percoltion
threshold vlues when compred to grphene, crbon nnotubes, nd others. Due to its inherent
electricl conductivity, MXene is considered s the future mteril for pplictions like 5G, rti-
cil intelligence, soft robotics, nd more.
Microwave Absorption and EMI Shielding Performance 195

10.2.1.1 Shielding Efciency

Shielding efciency is expressed in decibels (dB), nd it nlyses how effectively  smple mte-
ril blocks the electromgnetic energy of  denite frequency when sweeping through it. Different
interctions rising when electromgnetic rdition psses through  mteril re depicted in
Figure 10.2b. When these rditions strike on the surfce of  smple mteril, some mount of the
incident power (PI) gets reected (PR), wheres  certin mount of it gets bsorbed nd relesed
in form of energy, while some portion of the power gets trnsmitted (PT) cross the surfce of the
mteril. Thus bsorbnce, reection, nd multiple internl reections re the mjor three criteri
tht determine the shielding efciency of  mteril. Shielding efciency (SE) is the function of the
logrithmic rtio of the incident nd trnsmitted power (P). SE cn be clculted in terms of inci-
dent nd trnsmitted electric (E) elds nd mgnetic (H) elds lso.

PI E H
SET = 10 log = 20 log I = 20 log I
PT ET HT

The overll EMI shielding effectiveness (SET) of  mteril cn be clculted by employing the
eqution

SET = SER + SEA + SEM,

where SER, SEA, SEM represents shielding effectiveness due to reection, bsorption, nd multiple
internl reections, respectively. When SE > 10 dB, shielding efciency due to multiple internl
reections is not counted. R nd T re the coefcients of reection nd trnsmission, respectively.

10.2.1.2 Absorption Loss

When n electromgnetic wve psses through  medium, its mplitude decreses exponentilly.
This is due to the fct tht the currents generted in the medium give rise to ohmic losses nd result
in the heting of the smple. In this cse, E1 nd H1 cn be clculted by employing the eqution

E1 = Eoe−t/δ nd H1 = Hoe−t/δ.18

Thus, skin depth cn be dened s the distnce needed by the wve to be ttenuted to or the depth
t which the eld strength flls to 1/e or 37% of the incident vlue. So SE A cn be clculted s

t t
SE A ˜ dB ° ˛ 20 loge ˛ 8.68 ,
˝ ˝
Where t gives the thickness of the shielding mteril in millimeters; f represents the frequency in
meghertz, μ expresses the reltive permebility, nd σ gives the conductivity reltive to the metl
Cu. The δ vlue, which is otherwise clled skin depth in the preceding eqution, cn be clculted s

˜˙ 2 .
°˛˝ ˆ
10.2.1.3 Reection Loss
The reection loss is ssocited with the reltive discrepncy between the incident wve nd the
surfce impednce of the shield. The mgnitude of the reection loss cn be nlyzed by using the
following equtions:
° ˘ ˙
RE ˜ K1 10 log ˝ 3 2 ˇ
˛ f r ˆ
196 MXene-Filled Polymer Nanocomposites

° fr 2˘ ˙
RH ˜ K 2 10 log ˝ ˇ
˛  ˆ
° f ˘ ˙,
RP ˜ K 3 10 log ˝ ˇ
˛  ˆ
where R E (dB) represents the reection losses for the electric eld; R H, for the mgnetic eld; nd
R P, for the plne-wve eld. The reltive conductivity with respect to the metl Cu is denoted by
the term σ. The terms f, μ, nd r in the preceding equtions symbolize frequency in Hertz, reltive
permebility with respect to free spce, nd the distnce from the source to the shielding mteril
(m), respectively.

10.2.1.4 Multiple Reections

The SE due to multiple internl reections cn be positive or negtive (usully it is found to be
negtive), nd it cn be neglected when SE A is greter thn 10 decibels. It is tken into ccount only
when the frequency is very low (< ≈ 20 kHz) nd the metls used were thin. SEM cn be mesured
by employing the eqution

SE M ˜ °20 log (1 ° e °2t /˛ ).

The reltive permittivity nd permebility of the mterils nd their conductivity, s well s the
polriztion loss of llers, size, shpe, nd morphology of the nnoprticles, the thickness of the
smple, nd others, re some of the crucil fctors tht ffect the EMI SE of  mteril.

10.2.2 MEASUREMENT TECHNIQUES

EMI SE cn be mesured using network nlyzer instruments. They re of two types, nmely, sclr
network nlyzers (SNAs) nd vector network nlyzers (VNAs). The SNAs mesure only signl
mplitudes wheres the VNAs mesure signl mgnitude long with different phses. So VNAs re
used to nlyze shielding efciency under fr-eld conditions. VNA consists of two ports, nmely,
S1 nd S2. S1 nd S2 indicte the incident nd trnsmitted wves s complex scttering S prm-
eters, tht is, S11 or S22 nd S21 or S12, respectively. S11 represents the forwrd reection coefcient,
S22 gives n ccount of the reverse reection coefcient, S12 gives the forwrd trnsmission coef-
cient, nd S21 represents the bckwrd trnsmission coefcient. Numerous methods like short circuit
line (SCL), the Ntionl Institute of Stndrds nd Technology (NIST) itertive, new non-itertive,
delt function, trnsmission line theory, nd others re used to clculte complex permittivity nd
permebility vlues by employing these scttering prmeters. Among them, the Weir nd Nicolson
method19,20 is widely ccepted for clculting the permebility nd permittivity in the frequency
rnge 50 MHz to 18 GHz.
Reection nd trnsmission coefcients (S prmeters) re determined by introducing the mte-
ril to be tested in  specimen holder ssocited with the wveguide nges of the VNA (Figure 10.3).
In the rectngulr wveguide mesurements, the smple size vries with the frequency rnge. For
exmple, 22.8 ×10 mm2 is employed for X bnd (8.2–12.4 GHz) nd 15.8 ×7.9 mm2 is used for P
bnd (12.4–18 GHz).

10.3 DESIGNING A SHIELDING MATERIAL

An idel rdition shielding mteril must be designed in such  wy tht it should possess n ppro-
prite structurl geometry, nd must exhibit better mgnetic permebility (μ), electricl conductiv-
ity (σ), nd dielectric permittivity (ε). The mjor concern is tht shield must be conducting in nture
Microwave Absorption and EMI Shielding Performance 197

FIGURE 10.3 Internl block digrm of  spectrum nlyzer.

since the rst step in the EMI shielding mechnism is the reection of incident wves when it strikes
the surfce of the shield. So the mteril to be used for shielding must contin mobile chrge crri-
ers like electrons or holes tht cn interct with the incident rditions to crete ohmic losses in the
mteril. The second importnt fctor to be tken into ccount is tht it must be mgnetic in nture;
tht is, it must contin electric or mgnetic dipoles to bsorb (bsorption mechnism) the incom-
ing electromgnetic rditions. If the shielding mteril is modertely conducting in nture, then
the dielectric permittivity hs been tken into considertion since such mterils exhibit dynmic
dielectric nd/or mgnetic loss when electromgnetic wves strike on their surfce.
Most commonly metls were used s EMI shielding mterils, but becuse they re prone to
corrosion nd due to their hevy nture, they cnnot be employed for certin pplictions. The
importnce of polymers comes t this juncture. They re lightweight in nture, corrosion-resistnt,
nd ble to exhibit multifunctionl properties when properly tilored. Since shielding is ssocited
with high electricl conductivity, the polymers should be conductive in nture. In order to mke
the polymers conductive, conductive llers like CNTs, crbon nnobers, grphene, crbon blck,
nd others re introduced into the polymers by dopting different processing techniques like melt
mixing, spin coting, solvent csting, in situ polymeriztion, nd the like. A combintion of llers
or hybrid llers cn lso be used to mke the polymers conductive. Coting the nnoprticles with
metls, the ddition of metl oxide nnoprticles like iron oxide, mong others, re lso lterntive
methods dopted to enhnce the conductivity of polymers.
Intrinsiclly conducting polymers (ICPs) with microwve non-trnsprency, inherent conductiv-
ity, nd exibility re good lterntives to mke better EMI shielding devices.21,22,23 The mixing of
ICPs with conductive llers hs been proved to show better conductivity nd shielding efciency
when compred to nonconducting polymers with conductive llers. Moreover, ICPs re esily pro-
cessble nd cn be comptibilized with other polymers ccording to the nture of the ppliction.
Designing polymer nnocomposites with complex rchitectures like foms, multilyers, hybrid mul-
tilyers or Slisbury screens, honeycomb structures, nd others is lso considered  good strtegy to
fbricte rdition shielding devices24,25 By using this strtegic pproch, the weight of devices, s
well s the reection loss, cn be reduced. They cn ct s better microwve bsorbers lso. In the
cse of fom-like structures, the inuence of ir inside the cvities helps in reducing the reection
loss to  gret extent, thereby decresing the permittivity vlues.
198 MXene-Filled Polymer Nanocomposites

10.4 MXene-BASED POLYMER COMPOSITES FOR EMI

SHIELDING AND MICROWAVE ABSORPTION
According to literture reports, 2D mterils with strong microwve ttenution cpcity cn
ct s good rdition bsorbers. Thus, MXene, with its excellent conductivity, diverse surfce
chemistry, nd better Young’s modulus, cn be used to fbricte better rdition shielding mte-
rils. A comprehensive literture review revels tht only 7% of works were communicted on
microwve ttenution nd rdition shielding studies in MXenes.26 Out of 28 types of MXenes,
only Ti- nd Mo-bsed MXenes (Ti2CTx, Ti3C2Tx, Mo2TiC2Tx, Mo2Ti2C3Tx) were utilized for EMI
studies hitherto. Among them, most of the works were bsed on Ti3C2Tx. This my be becuse
of the high inherent conductivity nd semiconducting nture of Ti3C2Tx nd Mo2TiC2Tx, respec-
tively. The ctive surfce functionlities, strong M-A bonds in MAX phses, etching conditions,
polriztion loss, nd so on re some of the chllenges tht hve to be ddressed in fbricting
MXene-bsed shielding mterils. MXenes surfce cn be engineered with grphene nd mg-
netite nnoprticles to get better EMI shielding properties. Very recently,  smrt EMI shielding
ctution system bsed on Jnus MXene/grpheneoxide lm ws developed by Li et l. using 
simple vcuum ltrtion method.27 According to them, the developed exible Jnus lm shows
n electromgnetic shielding efciency of 40 dB to 55 dB, with the thickness of MXene lyers
rnging from 1.5 to 4.5 micrometers. They hd developed  smrt ctutor system bsed on this
Jnus lm to regulte the trnsmission of microwve signls in which the mechnicl grippers
were employed for the lifting nd relesing of polymer fom (Figures 10.4 nd 10.4b). The

FIGURE 10.4 () Figure shows Stimuli-responsive electromgnetic interference shielding mteril mde of
 smrt Jnus lm ctutor. (b) Flexible Jnus lm used to regulte the lifting nd relesing of  polymer fom.
Source: Reprinted from Smrt MXene-Bsed Jnus lms with multi-responsive ctution cpbility nd high electromg-
netic interference shielding performnces, Vol number 175, Lulu Li, Si Zho, Xin-Jie Luo, Ho-Bin Zhng, Zhong-Zhen
Yu. Copyright (2021), Reproduced with permission from Elsevier.
Microwave Absorption and EMI Shielding Performance 199

interfcil morphology lso plys  pivotl role in deciding the overll properties of the system,
In prticulr, nnocomposites with  chrcteristic interconnected network of llers in the mtrix
cn provide fscinting properties.

10.4.1 MXENE-BASED AEROGELS, FOAMS, AND HIERARCHICAL

ARCHITECTURES FOR EMI SHIELDING APPLICATIONS
Recently, mechniclly robust, low-density polymer composites, nmely, erogels, hve gined sig-
nicnt interest becuse of their exceptionl properties. Aerogels re highly porous, lightweight
solid mterils with  continuous 3D network structure processed by replcing the solvent in  gel
with ir without disrupting the network structure of the gel body.28 They cn ct s excellent therml
insultors nd cn provide better shielding efciency s per the end requirement.29 Their low den-
sity, high surfce re, nd porosity mke them suitble for fbricting mterils for spce missions
like spcesuits, dust prticle bsorbers, nd the like.30,31 MXene erogels re  new clss of mteri-
ls with  3D network structure lighter thn ir.32 The literture reports indicte tht 3D MXene
rchitectures re good lterntives for electrochemicl energy storge nd conversion pplictions.33
High mechnicl strength, electricl nd therml conductivity,34 nd dsorption cpcity mke them
potentil cndidtes for mking rdition shielding devices, fuel cells, supercpcitors, nd more.
Recently, MXene/reduced Grphene oxide (rGO) erogel ws used to fbricte piezoresistive
sensors for werble device pplictions.35 According to Bin et l.36 fom-like structures cn bsorb
more electromgnetic wves due to impednce mtching, multiple reections, nd scttering phe-
nomen occurring within the pores. Bsed on this, Wng et l. synthesized  lightweight 3D porous
MXene/rGO erogel vi  hydrotherml-ssisted freeze-drying method with minimum reection
loss (31.2 dB t 8.2 GHz) for brodbnd microwve bsorption pplictions.37 Liu et l. synthe-
sized  hydrophobic, freestnding, exible fom mde of Ti3C2Tx nd compred its electromgnetic
shielding efciency with respect to the corresponding MXene lm.38 They found tht hydrophobic
fom exhibited  much higher shielding efciency of 70 dB when compred to MXene lm (53 dB).
According to them, the signicnt enhncement in the shielding efciency of the fom is due to the
presence of  porous network. The freeze-drying method ws dopted to prepre  conductive, re-
resistnt Ti3C2Tx erogel bsed on cellulose nnober nd mmonium polyphosphte. The erogel
mteril lso displyed  better shielding efciency of 55 decibels. The shielding mechnism, in this
cse, ws found to be bsorption-driven.39
According to Jing et l.,40 conducting polymer composites consisting of segregted networks,
double percoltion structures, lyer-by-lyer ssembly, fom-like structures or erogels, nd others
cn increse the electromgnetic bsorption to  greter extent. As discussed erlier, fom-like
structures exhibit bsorption-dominted shielding ttenution. The pores in the fom help to bsorb
 mjor mount of rdition flling on its surfce nd thereby ct s better shielding mterils.
Recently, Liu et l. synthesized  super-elstic, lightweight, highly therml resistnt, nd conductive
(4.0 Sm−1), MXene erogel with polyimide s the mtrix, which ccounts for lmost 80% of revers-
ible compressibility nd excellent microwve bsorption property.41 Wng et l. synthesized highly
conductive cellulose nnober– nd crbon fom–impregnted 3D MXene (Ti3C2Tx)/epoxy nno-
composites with n EMI shielding efciency of 74 dB nd 46 dB, respectively. According to them,
the bsorption fctor contributes more to the shielding mechnism due to the highly conductive
porous networks.42,43 A study conducted by Zho et l. stted tht MXene/rGO erogels cn lso be
used to fbricte epoxy nnocomposites with high electricl conductivity nd better EMI shielding
effectiveness (>50 dB).44 Similrly, Luo et l. prepred  nturl rubber (NR) ltex–Ti3C2TxMXene
composite with n interconnected interfcil structure, exhibiting good electricl conductivity nd
 better EMI shielding effectiveness of 53 dB (Figures 10.5 nd 10.5b) in the X bnd.45 According
to them, the composite displyed better shielding efciency due to the formtion of  continuous
conductive network s  result of the MXene nnoprticles nd NR ltex prticles. The increse in
the shielding efciency with respect to the increse in the mount of MXene is due to the inherent
200 MXene-Filled Polymer Nanocomposites

FIGURE 10.5 () Electricl conductivity of MXene-NR composites. (b) SE of MXene–NR composites t
vrious ller lodings. (c) Shielding mechnism in  continuous MXene network.
Source: Reprinted from Flexible, stretchble nd electriclly conductive MXene/NR nnocomposite lms for efcient
electromgnetic interference shielding, Vol number 182, Ji-Qi Luo, Si Zho, Ho-Bin Zhng, Zhiming Deng, LuluLi,
Zhong-Zhen Yu. Copyright (2021), Reproduced with permission from Elsevier.

electricl conductivity of Ti3C2Tx, the presence of surfce functionlities, nd the formtion of n
interconnected porous network between the ltex prticle nd MXene. Here the mechnism ws
found to be shielding due to bsorption.
Literture reports propose tht dopting severl strtegies like designing unique hierrchicl
structures cn improve the shielding effectiveness of the composite. A study conducted by Ling
et l. reports tht MXene erogel/porous biocrbon composites with “mortr–brick” microstructures
cn function s excellent EMI shielding mterils.46 Likewise, Liu et l. developed  multifunctionl
ncre-mimetic composite of Ti3C2TxMXene/polyurethne with better mechnicl properties nd
rdition shielding efciency.47 Recently, Lin et l. illustrted n ion-diffusion-induced geltion
method for fbricting sclble MXene foms with desired shpes nd properties for terhertz
shielding purposes.48 Wu et l. fbricted  compressible, ultr-high EMI shielding MXene/sodium
lginte erogel coted with PDMS by employing directionl-freezing ccompnied with freeze-
drying method (Figure 10.6). The fom exhibited excellent conductivity with  shielding efciency
of 53.9 dB (X-bnd) t 6.1 wt% of Ti3C2Tx. The polydimethylsiloxne-coted MXene fom, when
used s n EMI shielding gsket, continued to disply n efciency of 48.2 decibels even fter going
through 500 compression-relese cycles.49
The lyer-by-lyer ssembly of hybrid nnoprticle polymer systems with core lyer nd skin
lyers cn be used to fbricte mteril with better EMI shielding, electricl insultion, nd high
therml conductivity.50 Hence, Weng et l. prepred  semitrnsprent composite mde of MXene–
CNT with polyvinyl lcohol nd polystyrene sulfonte (PSS) using lyer-by-lyer ssembly rchitec-
ture with excellent shielding efciency nd conductivity.51 Hu et l.52 prepred n rmid nnober
Ti3C2Tx composite tht cn withstnd extreme environmentl conditions using lyer-by-lyer self-
ssembly. The composite showed better mechnicl properties nd cn function s  sensor s well
s  shielding device. The specic SE ws reported s 28,190 dB cm2/g t 40 wt.% of Ti3C2Tx. The
thickness of the composite ws 9 µm.
Microwave Absorption and EMI Shielding Performance 201

FIGURE 10.6 Compressible nd conductive PDMS-coted MXene foms from MXene–sodium lginte
erogels.
Source: Reprinted from Compressible, durble nd conductive polydimethylsiloxne-coted MXene foms for high-
performnce electromgnetic interference shielding, Vol number 381, Xinyu Wu, Bingyong Hn, Ho-Bin Zhng, Xi Xie,
Tingxing Tu, Yu Zhng, Yng Di, Rui Yng, Zhong-Zhen Yu. Copyright (2021), Reproduced with permission from Elsevier.

Very recently,  novel self-heling EMI shielding sponge bsed on MXene/melmine/PU ws
fbricted by M et l.53 They took porous melmine sponge nd impregnted it with MXene
nnoprticles through  dip-coting method so tht the MXene will get deposited into the sponge
skeleton nd cn function s shielding cpsules covering the porous structure to form membrnes.
PU provides the self-heling bility to the whole structure. During the shielding process, multiple
internl reections hppen t the interfces of these porewlls, mking the MXene/melmine/PU
sponge n excellent rdition shielding mteril. The spongy mteril exhibited  mximum shield-
ing efciency of 90.49 dB t only 0.82 vol% of MXene.
Over the lst few yers, dditive mnufcturing (AM) hs grbbed much ttention becuse it cn
be used to prepre complex microstructures, which re considered to be difcult to ccomplish with
usul polymeric processing methods like injection molding, extrusion molding, foming, nd the
like. The mjor dvntge of dditive mnufcturing is tht it cn be used for the development of
sclble btch-size productions. Among the different AM techniques, extrusion-bsed 3D printing
or direct ink writing is  cost-effective nd fcile route to design 3D structures or miniturized pro-
totypic models for high-performnce pplictions. Moreover, it cn be used to design honeycomb-
like microstructures bsed on 2D functionl nnomterils54 hving diverse surfce chemistry to
fbricte exible nd stretchble electronic devices.55,56,57 Recently, Orngi et l. reported the fb-
riction of high-energy-density micro-supercpcitors bsed on dditive-free Ti3C2TxMXene ink
using 3D printing technology.58 Literture reports lso ccount for the fct tht ordered hierrchicl
microstructures cn provide better mechnicl stbility to the mterils since they cn withstnd
the lod due to effective strin trnsfer.

10.4.2 THERMOPLASTIC MXENE NANOCOMPOSITES

Thermoplstic nnocomposites constitute  mjor prt of the industry nd ply n importnt role
in the designing nd mnufcturing of rdition shielding mterils becuse of their lightweight
202 MXene-Filled Polymer Nanocomposites

nd exible nture. Recent reserch work by Sun et l.59 describes the synthesis of  polystyrene/
MXene nnocomposite with excellent EMI SE. They synthesized Ti3C2Tx from Ti3AlC2 using LiF
nd HCl s etching gents nd prepred  corresponding MXene polystyrene nnocomposite by
electrosttic self-ssembly of Ti3C2Tx on polystyrene microspheres ccompnied by high-pressure
compression molding. As  result,  highly conductive network is formed between the MXene
nnoprticles nd polymer networks, imprting  better shielding property (62 dB) t  very low
MXene concentrtion of 1.90 vol%. According to them, the composite displyed better shielding
properties due to the formtion of  highly compct conductive network (1081 S/m) with Ti3C2Tx
t the interfces of polystyrene microspheres, mking the shielding mechnism more bsorption
oriented.
When compred to grphene, MXenes re hydrophilic in nture, nd s  result, it is very dif-
cult to fbricte MXene polyolen composites. By tking ccount of this, Xu et l.60 prepred 
polypropylene Ti3C2Tx nnocomposite with n EMI SE greter thn 60 dB in the X-bnd t  very
low percoltion threshold of 0.027 vol% of the ller. To fbricte this composite, they rst ctivted
the surfce of polypropylene using oxygen plsm tretment, then with polyethyleneimine in order
to mke it hydrophilic, nd then dip-coted it with Ti3C2Tx, followed by vcuum-ssisted compres-
sion molding. Here lso, the mechnism of shielding ws found to be more bsorption governed
becuse of the development of  highly conductive interconnected network of MXene nnosheets
in the pololen mtrix.
Go et l.61 prepred thermoplstic polyurethne films bsed on multilyered Ti3C2Tx with
high nisotropic therml conductivity, electricl conductivity, nd EMI SE (50.7 dB t 28.6
wt% of MXene) using  different pproch, clled the lyer-by-lyer sprying technique.
According to them, the better shielding efficiency is due to reflection, multiple internl reflec-
tions s well s bsorption of rditions between the multilyers of MXene. As the composite
shows high nisotropic therml conductivity, the uthors lso clim tht it cn ct s excellent
Joule heters, which is considered to be very significnt in the field of flexible nd werble
devices.
Polyvinylidene uoride (PVDF) is  thermoplstic polymer with excellent dielectric proper-
ties. MXene-incorported PVDF nnocomposites lso exhibit superior shielding properties.
The presence of  conductive network long with better het dissiption bility cn improve the
SE of the devices to  greter extent. Recent work by Rjvel et l.62 points out tht frequent
exposure to rdition cuses heting in shielding mterils, which will led to its deteriortion,
nd therefore, the devices must be designed in such  wy tht they must disply high therml
conductivity lso. So they fbricted  PVDF–MXene nnocomposite lm with good shield-
ing properties (pproximtely 48 dB t 22.5 vol% of Ti3C2Tx) nd therml conductivity (0.767
W/m/k). The shielding property incresed with n increse in Ti3C2Tx owing to the develop-
ment of  strong interfcil conductive network between MXene nd PVDF. The optimum
threshold vlue of the ller ws found to be 6.7 vol%. Similrly, Li et l.63 fbricted  PVDF
nnocomposite lm bsed on Ti3C2Tx with  hierrchicl brick-nd-mortr ssembly using
 blde-coting method. The specic shielding efciency of the composite ws found to be
19504.8 dB cm 2/g (thickness of the lm, t = 17 μm). They lso stte tht the nnocomposite cn
withstnd extreme environments like nneling, corrosion, deformtion, nd so on by keeping
the SE oting within 5%. In order to chieve better shielding prmeters t low ultr-low ller
content, double-percolted systems cn be pplied. For exmple, MXene-incorported PVDF
nd PS cn be used to construct  double-percolted system with lyered or rndom structure
through the solution-csting or hot-pressing techniques.64 The solution-cst lyered double-
percolted structure portryed  better SE of 55 dB t 12 wt% of MXene when compred to the
rndom double-percolted structure. This is becuse of the fct tht lyered PS/PVDF/Ti3C2Tx
structures cn reect most of the rdition striking it due to their better electricl conductivity,
the presence of  conductive network, multiple internl reections between the lyers, the pres-
ence of polr bonds, nd more.
Microwave Absorption and EMI Shielding Performance 203

The synergistic effect of MXene with its 2D nlogue grphene in polymers cn lso imprt bet-
ter shielding efciency to  mteril. Recent reserch work by Vu et l.65 incorportes both MXene
nd reduced grphene oxide in polymethylmethcrylte (PMMA) beds to form  3D structure
using hot compression method. According to them, the shielding efciency nd electricl, s well s
therml, conductivity cn be tuned to desired vlues by vrying the rtio of the llers in the mtrix.
At 2 vol% of the hybrid ller concentrtion, the PMMA nnocomposite exhibited  shielding ef-
ciency of 28–61 dB.
Wng et l.66 fbricted n electromgnetic shielding mteril bsed on polypyrrole (PPy) deco-
rted MXene/poly(ethylene terephthlte) textile, which is highly hydrophobic, conductive (1000
S/m), nd joule heting in nture. The shielding efciency of the silicon-coted hydrophobic textile
mteril ws found to be 90.3 dB. These mterils cn be used to design exible, smrt, nd rti-
cilly intelligent werble mterils.

10.4.3 THERMOSETTING PLASTIC MXENE NANOCOMPOSITES

Thermosetting polymers re minly used for high-performnce pplictions requiring stringent
conditions. Thus, they cn be used s n excellent bse mteril to fbricte rdition shielding
devices tht cn withstnd extreme environments like high tempertures, corrosion, nd the like.
The thermoplstic nnocomposites cn be bsed on epoxy resins, phenolic resins, polyesters, nd so
on. Owing to their low viscosity nd ese of processing bisphenol epoxies re most widely used to
fbricte nnocomposites. Wng et l.67 prepred n epoxy nnocomposite (bisphenol F) bsed on
few-lyered thermlly nneled MXene (Ti3C2Tx) with n EMI SE of41 dB. According to them, the
nneled nnocomposite displyed better electricl conductivity when compred to non-nneled
MXene/epoxy systems. For non-nneled systems, the electricl conductivity ws 38 S/m t 15 wt%
of MXene, but for nneled systems, the conductivity exhibited  shrp increse of 105 S/m with the
sme mount of MXene concentrtion. The increse in conductivity nd shielding prmeters cn
be ttributed to the formtion of interfces nd dipoles in nneled MXene, which further enhnced
multiple reections nd electron trnsport, mong other spects, through the mtrix. The shielding
mechnism ws found to be bsorption-dominted. The composite lso displyed better Young’s
modulus nd hrdness.
A similr study by Song et l.68 reports the fbriction of n epoxy nnocomposite using Ti3C2Tx/
reduced grphene oxide hybrid with  honeycomb structure for EMI shielding purposes. According
to them, though MXene with  3D porous structure cn provide good rdition shielding proper-
ties, it is  lborious tsk to control the size, shpe, nd distribution of cells. So they rst designed
grphene oxide with  honeycomb structure using Al2O3 s  honeycomb templte. Then Ti3C2Tx–
cetyltrimethyl mmonium bromide solution ws impregnted into the structure through electro-
sttic self-ssembly followed by therml nneling to prepre reduced grphene-oxide/Ti3C2Tx
honeycomb structure. It is then mixed with epoxy resin nd curing gent to get the corresponding
nnocomposite with better electricl conductivity nd EMI SE of 387 S/m nd 55 dB, respectively,
t 1.2 wt% reduced grphene oxide nd 3.3 wt% Ti3C2Tx hybrid ller rtio. The shielding mech-
nism ws bsorption-governed. They lso stted tht the honeycomb structured composites dis-
plyed  vefold increse in the EMI shielding vlue when compred to those without  honeycomb
structure with the sme mount of ller loding.
Wng et l.69 lso fbricted n epoxy nnocomposite with signicnt bsorption governed rdi-
tion shielding properties bsed on  3D Ti3C2Tx/C hybrid fom. They hve dopted  sol-gel method
ccompnied by freeze-drying nd therml reduction to prepre the hybrid crbon fom/MXene. A
mixture of resorcinol nd HCHO (formldehyde) ws used s the crbon source. The corresponding
bisphenol F epoxy nnocomposites were fbricted using  vcuum-ssisted impregntion method
using diethyl methyl benzene dimine s  curing gent. Owing to its highly conductive 3D network
the composite exhibited n excellent shielding efciency of bout 46 decibels in the X-bnd, which
ws reported to be 4.8 times higher thn the net epoxy system.
204 MXene-Filled Polymer Nanocomposites

10.4.4 ELASTOMER MXENE NANOCOMPOSITES

Elstomers re considered the workhorse of the industry, nd owing to their exible nd stretch-
ble nture, they hve ttined  signicnt position in the eld of electronics with the upcoming of
minituriztion technology, smrt werble devices, rticil robotics, sensors, nd more. A recent
work by Wng et l.70 investigted the inuence of different hierrchicl rchitectures on the rdi-
tion shielding nd tensile properties of NR/MXene nnocomposite. They hve prepred NR Ltex/
MXene composite lms bsed on both  honeycomb structure nd  brick-nd-mortr structure nd
concluded tht those with  honeycomb structure exhibited better mechnicl properties nd EMI
shielding (39.5 MP nd 63.5 dB, respectively) with respect to the brick-nd-mortr structure (57 dB
of SE with 28.5 MP tensile strength). The enhnced shielding property of honeycomb structured
ltex/MXene lm is due to the presence of isolted units which cn lso ct s polriztion res.
When the rdition strikes the surfce of the lm, these units help in reection, bsorption, nd
multiple scttering of the rditions.
Yng et l.71 fbricted  NR ltex composite bsed on hydrophobic MXene Ti3C2Tx exhibiting
excellent me retrdncy, mechnicl properties, nd SE. The lm displyed n SE of 47.8 dB
with 34 MP tensile strength. The mteril proved to possess excellent durbility nd shielding
efciency (32.8 dB) when subjected to multiple bending cycles even fter storing in wter for
2weeks.
Lu et l.72 prepred  nnocomposite bsed on ethylene propylene diene rubber (EPDM) nd
Ti3C2Tx with better electricl nd therml conductivity of106 S/m nd 1.57 W/m K, respectively.
They lso investigted the shielding effectiveness of the smple t 6 wt% of MXene in the X- bnd
nd Ku-bnd. The percoltion threshold reported ws 2.7 wt%, thickness, t = 0.3 mm, nd the
shielding vlues obtined were 48 dB nd 52 dB, respectively, in the corresponding bnds. The
mechnism of shielding ws more bsorption-oriented. It is reported tht 3 wt% of MXenes is
enough to fbricte shielding mterils for commercil pplictions in the industry.

10.4.5 INTRINSICALLY CONDUCTING POLYMER–MXENE NANOCOMPOSITES

As mentioned erlier, ICPs cn function s excellent shielding devices owing to their microwve
non-trnsprency, inherent conductivity, nd the like. Recently,  lightweight MXene–polyniline
ferromgnetic nnomteril feturing high conductivity nd  shielding efciency of21–23 dB ws
reported by Kumr et l.73 They lso prove tht the mteril possesses excellent microwve bsorp-
tion throughout the X-bnd since the shielding prmeters owing to bsorption, s well s reection,
re constnt. The lyered 2D structure of MXenes is considered  boon since it extends the pthwy
of rditions s  result of multiple scttering inside the lyers. Tong et l.74 fbricted  multilyered
polypyrrole MXene nnocomposite with better rdition bsorption properties. On incorporting
25 wt% of polypyrrole/Ti3C2Tx in prfn, the mteril displyed  reection loss of −49.2 dB t
8.5 GHz. According to them, the presence of dipoles, multilyered structure,  strong hydrogen
bonding interction between N-H groups of polypyrrole nd terminl toms (O/F) present in the
MXene were responsible for better shielding properties. Recently Bor et l.75 fbricted poly(3,4-
ethylenedioxythiophene)/poly(styrene sulfonte) (PEDOT:PSS)/Ti3C2Tx nnocomposite with n SE
of 41 dB t 50-µL loding of MXene. The robust interfcil bonding between the PEDOT:PSS nd
Ti3C2Tx nnosheets, high electricl conductivity, etc. were responsible for the bsorption governed
shielding mechnism. Similrly, Ji et l.76 fbricted  compressible PDMS/Ti3C2Tx polymer fom
bed composite foms with very low reection loss for electromgnetic shielding purpose. To pre-
pre the composite, they rst synthesized polypropylene fom beds nd then decorted it with
polyniline followed by dip-coting of MXene. The corresponding fom ws mde compressible by
incorporting PDMS. The composite exhibited n EMI SE of pproximtely 23.5–39.8 dB with 
very low concentrtion of Ti3C2Tx.
Microwave Absorption and EMI Shielding Performance 205

10.5 CONCLUSION
Although  lot of stoichiometric compositions of MXenes re known, most of the reserch works
bsed on shielding nd ttenution properties were concentrted only on Ti3C2Tx. So there re  lot
of reserch opportunities re vilble in unexplored MXenes. Also, the exct mechnism of shield-
ing in MXene-bsed composites still requires further clriction. Moreover, only limited studies
re conducted in MXene soft elstomeric erogels developed using extrusion-bsed 3D printing
technology for EMI shielding studies, s 3D printed structures of different microstructures re very
difcult to chieve using conventionl processing methods. The min chllenge in fbricting these
mterils is to introduce  continuous conductive network tht helps in the bsorption of rditions.
The concept of developing conductive inks for EMI shielding is lso not widely explored yet. The
concept of fbricting  suitble device to store nd convert the rditions for useful purposes is
lso in its infncy stge. The behvior of the mteril regrding mechnicl, rheologicl, nd other
physicl nd chemicl properties is yet to be investigted. So there re  lot of res nd fctors tht
still remin unexplored in the eld of microwve bsorption nd EMI shielding when MXene-bsed
polymer nnocomposites re tken into considertion.

NOTES
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 11 MXene–Polymer
Nanocomposites for Gas- and
Vapor-Sensing Applications
Vishal Chaudhary

CONTENTS
11.1 Introduction......................................................................................................................... 212
11.2 Gs nd Vpor Sensors........................................................................................................ 212
11.3 Sensing Chrcteristics....................................................................................................... 213
11.3.1 Three Essentil Ss................................................................................................. 213
11.3.2 Five Desirble Rs.................................................................................................. 214
11.4 Sensing Mterils................................................................................................................ 215
11.5 Fbriction of MXene–Polymer-Bsed Gs nd Vpor Sensors ........................................ 216
11.5.1 Ex Situ Approches............................................................................................... 216
11.5.2 In Situ Approches................................................................................................ 216
11.6 Suitbility of MXene–Polymer Nnocomposites Structures for Anlyte Sensing ............. 217
11.7 Sensing Mesurements of MXene–Polymer Nnocomposite-Bsed Sensors.................... 217
11.8 Monitoring of Anlytes through MXene–Polymer Nnocomposites ................................. 218
11.9 MXene–Polymer Nnocomposite-Bsed Ammoni Sensors ............................................. 218
11.9.1 M3X2-bsed MXene–Polymer Composites (M3X2Tx-Ps) ..................................... 218
11.9.1.1 Fbriction of M3X2Tx-P-Bsed Ammoni Sensors............................... 219
11.9.1.2 Structure of M3X2Tx-P Nnocomposites................................................ 219
11.9.1.3 Ammoni-Monitoring Mesurements.................................................... 219
11.9.1.4 Sensing Chrcteristics .......................................................................... 220
11.9.1.5 Effect of Vrition in Humidity nd Temperture on the
Working of Sensors................................................................................ 221
11.9.1.6 Monitoring Voltiliztion of Agriculturl Ammoni by
M3X2Tx-P Sensors .................................................................................. 221
11.9.1.7 Sensing Mechnism of M3X2Tx-P Sensors ............................................ 222
11.9.2 M2X-Bsed MXene–Polymer Composites ........................................................... 223
11.9.2.1 Nb2CTx/PANI Nnocomposite Ammoni Sensors................................. 223
11.9.2.2 Sensor Fbriction ................................................................................. 223
11.9.2.3 Sensing Mesurements........................................................................... 224
11.9.2.4 Sensing Chrcteristics .......................................................................... 224
11.9.2.5 Sensing Mechnism ............................................................................... 225
11.10 MXene–Polymer Nnocomposite-Bsed Crbon Dioxide Sensors ................................... 226
11.10.1 Fbriction of Sensors .......................................................................................... 226
11.10.2 Sensing Performnce ............................................................................................ 226
11.10.3 Sensing Mechnism .............................................................................................. 227
11.11 MXene–Polymer Nnocomposite-Bsed VOCs/Vpor Sensors......................................... 228
11.11.1 Sensor Fbriction ................................................................................................ 228
11.11.2 Sensing Performnce ............................................................................................ 228
11.11.3 Sensing Mechnism .............................................................................................. 229

DOI: 10.1201/9781003164975-11 211

212 MXene-Filled Polymer Nanocomposites

11.12 Conclusion nd Future Prospect ......................................................................................... 231

References...................................................................................................................................... 231

11.1 INTRODUCTION
Rpid industril nd technologicl dvncements hve not only contributed to development but
lso contributes to vrious globl ecologicl issues, including globl wrming, ir pollution, ozone
depletion, wter nd lnd pollution, nd scrcity of drinking wter. These re cused due to emis-
sion of vrious environmentl contminnts, including poisonous gses nd vpors, sewge, the
relese of hrmful chemicls, the production of nondegrdble wste nd electronic wste, nd
vrious ecologicl misblnces. Among ll, the primry concern is the relese of ir contminnts
in the form of gses, including mmoni, oxides of sulfur, oxides of nitrtes, nd oxides of crbon,
long with vpors (lcohol, hydrzine, cetone), nd other solid pollutnts such s prticulte mt-
ter (Chudhry et l., 2016, 2017, 2022c). Hence, monitoring nd controlling the relese of these
pollutnts re required to preserve the ecosystem (Bi et l., 2007). Monitoring the relese of ir
contminnts t ech emission site is done through gs nd vpor sensors.

11.2 GAS AND VAPOR SENSORS

A sensor system is n interfce device similr to the humn nervous system tht converts  chnge
in ny of its properties in the presence of nlyte into electric signls, which cn be further detected
using pproprite electronic circuitry (Bi et l., 2007; Bker et l., 2017). Generlly, gs sen-
sors consist of  mteril, which chnges its properties, such s electricl, opticl, cousticl, or
mechnicl, in the presence of ir contminnts (Bi et l., 2007; Chudhry et l., 2022b). The
vrition in ny property of the mteril intercting with ir contminnts is clled its sensing
prmeter. The vrition in ny property of mteril intercting with ir contminnts is clled its
sensing prmeter. Vrious sensing prmeters reported in the literture include electricl resis-
tnce, cpcitnce, reectnce, bsorbnce, dielectric properties, cpcitnce, resonnt frequency,
therml nd electricl conductivity, nd refrctive index (Bi et l., 2007). The vrition in sensing
prmeters in the presence of  specic nlyte hs been scribed to vrious physicl nd chemi-
cl phenomen, including dsorption, bsorption, swelling, nd chemicl rections (Anichini et l.,
2018). Sensors re clssied bsed on sensing prmeters, including electrochemicl, spectroscopic,
solid-stte, clorimetric, nd mss-sensitive sensors (Bi et l., 2007). Most of the reported gs nd
vpor sensors re solid-stte-type chemiresistor, in which  chnge in resistnce in the presence
of nlyte is tken s  sensing prmeter (Anichini et l., 2018; Bi et l., 2007; Chudhry et l.
2022d). Chemiresistor re consists of  sensing lyer, electrode system, substrte nd electronic
circuitry s shown in Figure 11.1. Vrious substrtes include exible nd nonexible substrtes

FIGURE 11.1 Schemtic of  chemiresistor.

Gas- and Vapor-Sensing Applications 213

such s glss substrte, indium tin–oxide (ITO) substrte, polyindole (PI), polyethylene terephthl-
te (PET), nd grphite ppers (Bi et l., 2007). The electrode system cn be simply two prllel
electrodes type or interdigitted-type electrodes to record  mximum chnge in sensing prmeter.
Minly highly conducting mteril contct electrodes such s gold re used to void ny ltertion
or noise in obtined sensing signl due to the Schottky effect (Bi et l., 2007). The electronic cir-
cuitry of sensors is mjorly bsed on the Whetstone bridge principle. Chnge in resistnce of one
of its rms leds to current ow, creting n lrming or detection signl. Since the nlyte detect-
ing performnce of  sensor depends on its sensing lyer mteril, the resercher’s primry concern
is dedicted to developing sensing lyer mteril for enhncing its vrious sensing chrcteristics.

11.3 SENSING CHARACTERISTICS

Vrious sensing chrcteristics essentil for the commercil development of  sensor include three
Ss (selectivity, sensitivity, stbility) long with ve essentil Rs (room temperture opertion, rnge,
reproducibility, response nd recovery time, repetbility).

11.3.1 THREE ESSENTIAL SS

Sensitivity or sensing response is the prime sensing chrcteristic tht determines the efciency of
 sensor. Generlly, it is dened s the percentge chnge or degree of chnge in sensing prmeter
in the presence of the nlyte (Chudhry et l., 2015, 2016). It depends on vrious topologicl nd
morphologicl properties, including effective morphology, dimensions, surfce re, roughness,
porosity, chemicl properties including chemicl structure, constituent components, nd physicl
properties including chrge crrier pthwy, bnd gp, nd conductivity (Bi et l., 2007; Bker
et l., 2017; Anichini et l., 2018). Thus, enhncing the sensitivity through ltering these prmeters
is the prime focus of the reserch community.
Degree in chnge (S) of sensing prmeter (R) is given by

S = ΔR/R. . . . ., (11.1)

where ΔR is the chnge in the resistnce of the sensor in the presence of nlyte (R−Rg), with Rg is
the vlue of the sensing prmeter in mbient conditions nd R is the vlue of the sensing prm-
eter in the presence of nlyte.
Percentge chnge in sensing response

S(%)= (ΔR/R) × 100 . . . . . (11.2)

A typicl sensing signl with few chrcteristics is shown in Figure 11.2.

The selectivity of  sensor is dened s the degree of detection of  prticulr nlyte in the
presence or bsence of other nlytes (Chudhry et l., 2017, 2022; Singh et l., 2022). A sensor
detecting mny nlytes my be regrded s  ‘verstile sensor’, but t the sme time, it is chl-
lenging to differentite the detected nlyte. Thus, selectivity towrds  prticulr nlyte in the
presence of other nlytes is  signicnt concern of  gs sensor. Since the sensing phenomenon
is the dsorption process mjorly, the selectivity is ttributed to the dsorption energies of vrious
nlytes over specic surfces nd the presence of specic rective functionl groups in sensing
mteril towrds  prticulr nlyte (Chudhry et l., 2015b, 2017). A selectivity test is done by
mesuring the sensing response of sensors in different nlytes nd compring them.
The stability of  sensor is required for its commercil development. A developed sensor must
be highly stble under different environmentl conditions, such s  chnge in humidity, pressure,
nd temperture. A stbility test includes recording sensing prmeters in vrying humidity nd
temperture conditions (Bi et l., 2007).
214 MXene-Filled Polymer Nanocomposites

FIGURE 11.2 Sensing signl with sensitivity, response, nd recovery.

Thus, the three Ss re the bsic requirements of  sensor for its commercil development.

11.3.2 FIVE DESIRABLE RS

The room temperature operation of  sensor is essentil for its economic nd ecologicl develop-
ment (Chudhry et l., 2017; Bi et l., 2007; Singh et l., 2022). A sensor tht cn be operted t
room temperture excludes micro-heting ssemblges tht reduce its production cost nd energy
requirement for its opertion (Chudhry et l., 2015c, 2022b). It lso verts the merge of inter-
prticle grin boundries of sensing mteril, which increses its lifetime nd performnce.
The ranges of detection include both the upper rnge (high concentrtion of nlyte up to which
it detects nlyte linerly nd efciently) nd lower rnge (minimum concentrtion of nlyte tht
cn be detected by designed sensor). Liner detection rnge is considered  criterion for the com-
mercil development of  sensor. Liner detection rnge test is done by linerly tting the sensing
response of sensor t vrious concentrtions of nlyte nd mesuring its regression vlue (Bi
et l., 2007; Chudhry et l., 2016). For the perfect liner rnge, the regression vlue must be equl
to unity, which is not experienced during mesurements.
The response and recovery time re dened s the 90% of elevtion curve nd the recovery
curve of the sensing signl (Chudhry et l., 2015). The response time depends on the time nd
degree of interction of the nlyte with sensing mteril. However, recovery time depends on the
degree nd time of desorption of nlyte molecule from sensing mteril. A suitble sensor must
possess  short response nd recovery time, which mens it must detect the nlyte rpidly nd
recover fst to its originl stte fter the removl of the nlyte.
A sensor must reproduce its results repetedly nd cn be reproducible without ny inuence of
ny externl environmentl fctor for its commercil development (Bi et l., 2007). A onetime high
response or  onetime possible fbriction of  sensor is of no use. Thus,  sensor must be repeat-
able and reproducible. These tests re done by mesuring the sensing response of the sensor for
mny cycles of nlyte exposure (Chudhry et l., 2017).
All the ve Rs, long with the three Ss, together set the criterion for  suitble sensor nd its
commercil development. Aprt from these chrcteristics, exibility (Anichini et l., 2018) nd
self-driven sensors using nnogenertors (Wu et l., 2020) re lso dditionl fetures for  sensor.
Gas- and Vapor-Sensing Applications 215

Flexibility cn be chieved by using exible substrtes such s PI or PET or self-sustinble lms
(Alrmmouz et l, 2018). The exibility test mesures the sensing response by bending the sensor
lm t different ngles nd for multiple folds (Alrmmouz et l, 2018). The mjority of devel-
oped sensing mterils reported in the literture re chrcterized bsed on these essentil sensing
chrcteristics.

11.4 SENSING MATERIALS

The centrl prt of  sensing device tht plys  vitl function in converting  chemicl or physicl
signl into  detectble electricl signl is its sensing mteril. Nnotechnology plys  vitl role
in designing sensing mterils with enhnced sensing chrcteristics (Bi et l., 2007). Since the
interction of the nlyte with sensing mterils is  surfce phenomenon, high effective surfce
re (due to lrge surfce-to-volume rtio) of nnomterils with enhnced porosity, chemicl nd
physicl properties mke them  promising cndidte in sensing technology (Khn et l., 2020).
An increse in surfce re surges the probbility of nlyte interction with the mteril, which
results in enhnced sensing chrcteristics (Khn et l., 2020). Due to the bundnce of nturl
mterils, vrious nnomterils hve been used to detect different nlytes (Khn et l., 2020).
Out of them, two-dimensionl (2D) mterils, including grphene nd its derivtives, borophene,
2D orgnic polymers, blck phosphorus, molybdenum disulde, nd MXenes, due to their high
surfce-to-volume rtio, verstile surfce chemistries, nd room temperture response, re widely
reserched for gs-nd vpor-sensing studies (Alrmmouz et l, 2018; Bi et l., 2007; Anichini
et l., 2018; Khn et l., 2020). Out of them,2D mterils, including grphene nd its derivtives,
brophene, 2D orgnic polymers, blck phosphorus, molybdenum disulde, nd MXenes, due to
their high surfce-to-volume rtio, verstile surfce chemistries, nd room temperture response
re widely reserched for gs-nd vpor-sensing studies (Anichini et l., 2018; Wng et l., 2021;
Sheth et l., 2022; Chudhry et l., 2022). On the contrry, MXenes re fmily of 2D trnsition
metl nitrides nd crbides, which exhibited inordinte sensing properties due to their lrge effec-
tive surfce re, good hydrophilicity, excellent electricl conductivity, high mechnicl stbility,
biocomptibility, nd bundnt surfce-terminted groups (–OH, –O, or –F) (Rizi et l., 2021).
However, the use of MXene-bsed sensors hs been limited to mostly reducing nlytes such s
mmoni (NH3) due to high conductivity with the moderte sensing response (Rizi et l., 2021;
Ho et l., 2021). Due to the high bsorption energy between MXene nd nlyte, the recovery time
is too signicnt or totl recovery is not chieved, limiting its commercil development (Wng
et l., 2021b). For commercil-scle development, MXene-bsed sensors must be produced in 
lrge quntity to keep their conductivity high, nd they must possess high mechnicl endurnce
nd exibility for mchine processbility (Rizi et l., 2021; Zmhuri et l., 2021). For detection nd
monitoring of oxidizing nlytes with efcient sensitivity, its conductivity needs to be controlled.
Thus, controlling the electricl nd mechnicl properties of MXene is  chllenge for sensor
development, which is ddressed by mking its nnocomposites with polymers (Rizi et l., 2021;
Crey et l., 2021). Nnostructured polymers such s polyniline (PANI), polypyrrole (PPy), poly-
vinyl lcohol (PVA), nd polystyrene (PS) hve shown signicnt sensing response with enhnced
room temperture–sensing chrcteristic towrd vrious reducing nd oxidizing nlytes (Wong
et l., 2020; Nzemi et l, 2019). They re esy to fbricte, cost-effective, environmentl- nd
user-friendly, nd energy-efcient. It hs lso been noticed tht MXene-polymer composites hve
shown tremendous performnce in energy storge pplictions due to multi-interctions, including
hydrogen bonding, electrosttic interctions, or vn der Wls forces (Go et l., 2020; Chudhry
et l., 2022b). Thus, to incorporte the merits of both types of mterils, 2D hybrid MXene–polymer
nnocomposites hve been evluted for gs-sensing performnce (Zhn et l., 2020; Chen et l.,
2021). However, there is dedicted literture on other inorgnic-polymer nnocomposites for gs/
vpor-sensing monitoring (Ary et l., 2020). Most reports on inorgnic-polymer nnocomposites
demonstrte enhnced gs-sensing performnce due to the formtion of heterojunctions mong
216 MXene-Filled Polymer Nanocomposites

the precursors. Nevertheless, the use of MXene s one of the precursors in nnocomposites mkes
it more unique nd more efcient for gs/voltile orgnic compounds (VOC) detection. MXene-
polymer hybrid systems show unique hetero-interfcil effects, which surges the synergistic effect,
interfcil chrge trnsfer, nd contct with trget nlyte molecules due to the presence of bun-
dnt surfce functionlities (Chen et l., 2021; Zhn et l., 2020). The inclusion of polymers into
MXene cn further protect its oxidtion if they possess  more considerble fnity towrd MXene
(Chen et l., 2021). These MXene polymers hve been reported to be fbricted using vrious ex
situ nd in situ pproches.

11.5 FABRICATION OF MXene–POLYMER-BASED

GAS AND VAPOR SENSORS
Nnocomposites re mterils possessing t lest one of the dimensions of  prent component in
 nnometric scle (<100nm) (Chudhry et l., 2021, 2015c). Nnocomposites cn be clssied
s into three ctegories bsed on their morphology including phse-seprted systems, interc-
lted systems, nd exfolited systems (Fu et l., 2019). MXene–polymer nnocomposites cn be
fbricted using n ex situ pproch, such s mixing two prents fter seprte synthesis, or by
in situ pproches, such s synthesizing both prents together or one prent in the presence of
others (Kusr et l., 2021; Crey et l., 2021). These techniques include solvent blending, in situ
polymeriztion, surfce etching, melt blending, nd RIR-MAPLE deposition (Chen et l., 2021;
Zhn et l., 2020).
In generl procedure, synthesis of MXene involves three steps etching (removing A element from
its MAX phse through etchnt including hydrouoric cid, hydrochloric cid, lithium uoride or
their combintion), wshing (reestblishing pH to neutrl vlue through decnttion, centrifugtion
or dispersion in fresh wter), nd delmintion (obtining single lyer MXene by ultrsoniction,
shking or dding interclnts; Ho et l., 2021). It is followed by n in situ or ex situ technique to
obtin nnocomposite (Crey et l., 2021). Furthermore,  sensing lm is mde on  exible sub-
strte (PET or PI) or nonexible (glss or ITO-coted glss slides) using vrious techniques such
s spin coting, electrospinning, nd wet spinning (Go et l., 2020b). Furthermore, two conductive
electrodes hve been deposited over sensing lm for further nlyzing the sensing performnce
(Wng et l., 2021b).

11.5.1 EX SITU APPROACHES

In the ex situ pproch, both the prent mteril (MXene nd polymer) re synthesized seprtely
nd then dissolved in the pproprite solvent (Crey et l., 2021; Zhn et l., 2020). The sensing
lyer is further fbricted using MXene–polymer mixture using pproprite processing techniques
such s electrospinning or wet spinning over the desired substrte or of self-stnding nture or drop-
csting (Crey et l., 2021). A nnocomposite-sensing lyer of wter-soluble polymer nd MXene,
which is hydrophilic, cn be fbricted by mixing them in wter to form n queous solution (Crey
et l., 2021; Rizi et l., 2021). The formed lyer is further dried in vcuum oven t  suitble tem-
perture dependent on the therml stbility of the prent constituents, speciclly polymer (Rizi
et l., 2021).

11.5.2 IN SITU APPROACHES

These synthesis techniques include synthesizing one prent constituent in the presence of nother
or synthesizing both the prent together (Crey et l., 2021). The most commonly used in situ
technique is in situ polymeriztion, in which the polymer is polymerized in the presence of pre-
synthesized MXene (Go et l., 2020). Furthermore, the sensing lyer of nnocomposite is formed
Gas- and Vapor-Sensing Applications 217

using suitble techniques such s dip coting, inkjet printing, or drop-csting (Crey et l., 2021). It
is followed by drying the formed sensing lyer or lm t  specic temperture s per prent con-
stituents (Crey et l., 2021).
Furthermore,  specic type of conductive electrode system, such s interdigitted electrodes or
prllel electrodes, is deposited over the sensing lyer for  sensing mesurement using n ppropri-
te technique such s inkjet printing, therml deposition, spin coting, or dip csting (Zhn et l.,
2020; Rizi et l., 2021).
Vrious fbriction techniques hve been used to design  sensor to detect  prticulr nlyte,
discussed in the subsequent section. The chpter is further divided in terms of reports present in the
literture for the detection of vrious nlytes.

11.6 SUITABILITY OF MXene–POLYMER NANOCOMPOSITES

STRUCTURES FOR ANALYTE SENSING
The inclusion of polymer into MXene prevents stcking of its lyers or sheets (Crey et l., 2021),
s shown in Figure 11.3. Due to the etching nd delmintion process, vrious functionl groups
including –OH, –O, nd –F re present on MXene sheets, which binds polymers vi electrosttic
interctions resulting in the formtion of the lmellr structure of MXene sheets with polymer
chins between them (Crey et l., 2021). Such  lmellr structure with polymer chins possesses 
high effective surfce re with lrge dsorption sites for nlyte molecules, resulting in enhnced
sensing chrcteristics.

11.7 SENSING MEASUREMENTS OF MXene–POLYMER

NANOCOMPOSITE-BASED SENSORS
Sensing mesurements for gs sensors re generlly recorded in  chemiresistive mode. A typicl
sensing pprtus consists of  sensing chmber, with the provision to insert  denite concentrtion
of nlyte molecules;  mesuring device, such s digitl multimeter, which records chnge in sens-
ing prmeter; computer interfcing with computer through softwre, such s Lb View; nd tem-
perture nd humidity controller system (Chudhry et l., 2015c, 2021b). Sensing mesurements
re done either in sttic mode or in dynmic mode. To test the sensitivity, the sensor is plced in n
ir-tight sensing chmber nd connected to  mesuring device, such s digitl multimeter to detect
the chnge in sensing prmeter. In sttic mode,  denite mount of nlyte in prts per million
(ppm) is inserted into the sensing chmber, nd the ltered sensing prmeter of the sensor is me-
sured fter its sturtion (Bi et l., 2007). In dynmic mode, continuous ow of denite mount
of nlyte is mde through sensing chmber, nd respective chnge is mesured (Chudhry et l.,
2016). Furthermore, ll sensing chrcteristics re obtined using the pproprite formultion, s
discussed in the coming sections.

FIGURE 11.3 Structure of MXene–polymer nnocomposites.

218 MXene-Filled Polymer Nanocomposites

11.8 MONITORING OF ANALYTES THROUGH MXene–

POLYMER NANOCOMPOSITES
MXene is generlized by  chemicl formul Mn+1XnTx, where M denotes n erly trnsition metl,
X denotes crbides or nitrides (with n = 1, 2 or 3) nd T denotes vrious functionl groups such s
–O, –F nd –OH (Gogotsi et l., 2019). Thus, bsed on the type of MXene (mjorly bsed on the
vlue of ‘n’), MXene–polymer nnocomposites cn be further clssied. Thus, we cn generlize
 formul for MXene–polymer composites s Mn+1XnTx-P, where P stnds for  type of polymer or
combintion of polymers. There re specic reports on MXene-bsed gs sensors with polymer
substrte (Chen et l., 2020; Aghei et l., n.d.; Lee et l., 2019; Hsn et l., 2021), which is entirely
different from MXene–polymer nnocomposites. Since, in the cse of nnocomposites, ll the pre-
cursors re n integrl prt of the hybrid. However, MXene deposited over polymer substrte does
not include polymer s one of the precursors nd is not termed  nnocomposite. In this chpter,
we hve restricted our discussion to MXene–polymer nnocomposite-bsed gs sensors. In this
section, we discuss ech type of nlyte one fter one detected through vrious MXene–polymer-
bsed nnocomposites in detil, including their synthesis route, sensor fbriction technique, type
of sensor, sensing performnce, nd sensing phenomen with their merits nd demerits in view of
literture. We lso discuss the importnce of monitoring specic nlytes for humn welfre nd
environmentl blnce.

11.9 MXene–POLYMER NANOCOMPOSITE-BASED AMMONIA SENSORS

Ammoni gs is extensively used s rw mterils in vrious chemicl industries including mnu-
fcturing units of plstics, nitric cid, textiles, pesticides nd explosives, refrigertion industries,
petrochemicl industries, nd mnufcturing industries of gllium nitrides nd silicon nitrides in
electronic industries (Chudhry et l., 2015, 2021b). The exposure limit for humns to mmoni is
25 ppm for 8 hours nd 35 ppm for 10 minutes s per Occuptionl Sfety nd Helth Administrtion
(Timmer et l., 2005). Beyond these prescribed limits, mmoni is hzrdous to humn respirtory,
olfctory, nervous, derml, nd excretory systems (Timmer et l., 2005). Exceeding the mmo-
nium slt in the humn body bove 200–500 mg/kg of body weight my cuse kidney filure, lung
edem, nd nervous disorder (Chudhry et l., 2015; Timmer et l., 2005). Thus, the monitoring
of mmoni is criticlly required nd done through mmoni sensors. There re vrious reports
in the literture for the detection of mmoni using vrious sensing mterils. Since mmoni is 
reducing nlyte, mterils with high conductivity re best suited for its detection due to their sig-
nicnt possibility of oxidtion in the presence of mmoni (Timmer et l., 2005). There re reports
on the detection of mmoni through MXene nd polymers seprtely in the literture (Ary et l.,
2020; Insusti et l., 2020; Ho et l., 2021). However, the inclusion of both mterils in  single sens-
ing lyer hs been reported to enhnce their sensing response through mny folds due to their merits
(Chen et l., 2021; Rizi et l., 2021). MXenes, due to their 2D structure, possess  high surfce-to-
volume rtio, which mplies the sensing signl due to more interction between the sensing lyer
nd mmoni molecules. In contrst, polymer provides stbility nd selectivity (Rizi et l., 2021;
Chudhry et l., 2021b). Vrious MXene–polymer nnocomposites hve been further discussed in
the succeeding subsection.

11.9.1 M3X2-BASED MXENE–POLYMER COMPOSITES (M3X2TX-PS)

Vrious studies on density functionl theory (DFT) clcultions (Xio et l., 2016; Kim et l., 2018;
Hjin et l., 2018) hd predicted tht MXenes hold specic selectivity towrd mmoni due to sur-
cil terminted groups on them. Thus, they hve been considered pt for the detection of mmoni.
Titnium crbide (Ti3C2Tx) ws the rst M3X2-bsed MXene, explored for its gs-sensing proper-
ties by Kim et l. (2018) nd Lee et l. (2017). This report ws followed by few reports on mmoni
nd other vpor detection through M3X2-bsed MXenes (Kim et l., 2018).
Gas- and Vapor-Sensing Applications 219

However, it hs been noticed tht the sensing responses of M3X2-bsed MXenes re poor towrd
mmoni (Kim et l., 2018; Zho et l., 2019). Thus, vrious reserchers combined these MXenes
with polymers including polyniline (PANI) nd Poly 3,4-ethylenedioxythiophene (PEDOT) to
form M3X2-bsed MXene–polymer composite nd investigted them for mmoni-sensing chr-
cteristics (Jin et l., 2020; Rizi et l., 2021; Li et l., 2020; Aghei et l., n.d.). Jin et l. (2020)
hve reported the use of poly 3,4-ethylene dioxythiophene: poly (4-styrene sulfonte)/titnium cr-
bide (PEDOT:PSS/Ti3C2Tx) composite for enhnced mmoni sensing performnce. Li et l. (2020)
reported exible mmoni sensor bsed on polyniline (PANI)/Ti3C2Tx for griculture mmoni
voltiliztion monitoring. The two reports were similr in detecting mmoni t different ppm
levels to nlyze vrious mmoni sensing chrcteristics. However, Li et l. (2020) used PANI-
M3X2-bsed MXene sensor to mesure mmoni voltiliztion in griculturl pplictions through
specilly designed simultions.

11.9.1.1 Fabrication of M3X2Tx-P-Based Ammonia Sensors

M 3X 2Tx-P nnocomposites re generlly fbricted by in situ pproch (Rizi et l., 2021), in
which desired polymer is polymerized in the presence of pre-synthesized M 3X 2Tx. Jin et l.
(2020) reported the synthesis of PEDOT:PSS/Ti3C2Tx nnocomposites using in situ polym-
eriztion of EDOT over pre-synthesized Ti3C2Tx in the presence of PSS. The prepred nno-
composite ws dip-coted on  PI surfce possessing interdigitted electrodes. Furthermore,
the prepred sensing lm ws dried in  vcuum desicctor to nlyze mmoni monitoring.
Li et l. (2020) fbricted PANI/Ti3C2Tx,  chemiresistive-type exible mmoni sensor, using
in situ polymeriztion of PANI in the presence of pre-synthesized Ti3C2Tx nnosheets on PI sub-
strte. Initilly,  mixture of niline nd pre-synthesized Ti3C2Tx ws prepred. Furthermore,
n pproprite mount of oxidnt APS (mmonium persulfte) nd hydrochloric cid (dopnt)
ws dded under constnt stir. On chieving ple yellow color of solution, indicting polymer-
iztion of niline, PI substrte with Au-interdigitted electrodes ws dip into it, to form sensing
lm. The lms were further dried in vcuum oven nd further nlyzed for mmoni sensing
performnce (Li et l., 2020).

11.9.1.2 Structure of M3X2Tx-P Nanocomposites

Li et l. (2020) reported forming  hierrchicl structure of Ti3C2Tx nnosheets nd PANI nnopr-
ticles ccompnied by PANI dendritic nnoberson nnoprticles. The presence of dendritic nno-
bers increses the gp between the lmellr structures incresing the higher effective surfce re
for the dsorption of mmoni molecules (Li et l., 2020). They hve lso observed the formtion of
core–shell type nnocomposite with Ti3C2Tx nnosheets wrpped by PANI sheets (Li et l., 2020).
Jin et l. (2020) observed tht the inclusion of PEDOT: PSS between Ti3C2Tx nnosheets incresed
their interlyer spcing, which supports  higher dsorption of nlyte molecules. Thus, the hier-
rchicl lmellr structure of M3X2Tx-P nnocomposites mkes them  promising cndidte for
nlyte sensing due to higher interlyer spcing.

11.9.1.3 Ammonia-Monitoring Measurements

Jin et l. (2020) reported mesurements done in sttic mode in which the nlyte ws introduced in
n ir-tight sensing chmber through  micro-syringe. The chnge in resistnce ws recorded using
 digitl multimeter until the sensor’s resistnce becme stble in the presence of the nlyte. The
sensing mesurements were done t room temperture (25 ± 5°C) nd in reltive humidity of 55 ±
5%. Sensing response ws dened s the degree of chnge in resistnce of the sensor in the pres-
ence of n nlyte using Eqution11.2. However, Li et l. (2020) used typicl sensing pprtus nd
performed dynmic mode mesurements under controlled vrying temperture nd humidity with
exposure to different ppm levels of mmoni.
220 MXene-Filled Polymer Nanocomposites

11.9.1.4 Sensing Characteristics

Ammoni sensing chrcteristics of M3X2Tx-P nnocomposites depend on the structure, form-
tion of interfces, conductivity, nd concentrtion of prent constituents (Rizi et l., 2021). The
enhncement in inter-plnr spcing nd the presence of vrious functionl groups improves the
mmoni sensing performnce of M3X2Tx-P nnocomposites compred to their prent constitu-
ents (Rizi et l., 2021). Similr observtions hve been mde in the cse of PEDOT:PSS/Ti3C2Tx
nd PANI/Ti3C2Tx nnocomposites in terms of improved sensing response compred to tht of its
prents’ constituents (Li et l., 2020; Jin et l., 2020). Jin et l. (2020) lso reported the vrition
in sensing response, response time nd recovery time of composite with the increse of Ti3C2Tx
concentrtion s listed in Tble 11.1.
It ws observed tht with n increse of Ti3C2Tx content in the nnocomposite, its mmoni-
sensing chrcteristics increse up to 15 wt% nd decrese further (Jin et l., 2020). Hence,
PEDOT:PSS/Ti3C2Tx composite sensor shows the best sensing chrcteristics towrd mmoni for
15 wt% nnocomposites. The reson ws scribed to higher conductivity of 15wt% nnocomposite
compred to tht of others (Jin et l., 2020). The higher conductivity provides higher chnces of
oxidtion of nnocomposite in reducing mmoni, which enhnces the sensing response (Pndey,
2016). Consequently, response time nd recovery time were found to decrese. The reson hs lso
been ttributed to optiml interlyer spcing t15 wt% of Ti3C2Tx, which provides  lrger effec-
tive surfce re nd more dsorption sites (Jin et l., 2020). They further nlyzed the 15 wt%
nnocomposite for other sensing chrcteristics (Jin et l., 2020). However, Li et l. (2020) reported
the mmoni sensing performnce of prepred nnocomposite without vrying the concentrtion
of Ti3C2Tx. A comprtive nlysis of mmoni-sensing performnce of both studies is listed in
Tble 11.2.
The sensitivity of PEDOT:PSS/Ti3C2Tx ws mnifold less thn tht of PANI/Ti3C2Tx-bsed
mmoni sensor (Tble 11.2). It cn be scribed to dendritic growth of nnobillr PANI, which ws
not found in cse of PEDOT:PSS/Ti3C2Tx. Among ll the polymers, PANI hs been most studied for
its mmoni sensing chrcteristics due to its redox nture nd tunble conductivity (Kumr et l.,
2020; Tnguy et l., 2018). Thus, the presence of PANI in PANI/Ti3C2Tx nnocomposite hs been
ttributed to its mplied sensitivity nd lower detection limit compred to tht of PEDOT:PSS/
Ti3C2Tx. However,  PANI/Ti3C2Tx-bsed sensor lcks response nd recovery process, which cn
be scribed to slow desorption of mmoni through nnocomposite nd possess chnces of future
dvncements. Both the sensors hve shown selectivity trits towrd mmoni compred to other
nlytes, which cn be scribed to the dsorption energy of mmoni, nd the presence of structurl
defects nd surfce functionl groups, which ct s specic dsorption sites for mmoni (Lee et l.,
2017; Yu et l., 2015; Ding et l., 2018).

TABLE 11.1
Variation of 100 ppm Ammonia-Sensing Characteristics with Change in Ti3C2Tx
Concentration in Nanocomposite (Jin et al., 2020)
Weight Percentage Conductivity Sensing Response Response Time Recovery Time
of Ti3C2Tx (%) (S/cm) (%) (s) (s)
0 (Pure PEDOT-PSS) <0.01 ~5–7 ~160 130
8 ~0.02 ~12–15 ~158 ~100
11 ~0.02–0.25 ~20–25 ~140 ~80
15 ~0.07 36.6 116 ~40
20 ~0.03 ~20 ~120 ~70
25 ~0.02–0.28 ~15–18 ~120 ~100
100 (Pure Ti3C2Tx) Not Mentioned ~10–12 ~180 ~180
Gas- and Vapor-Sensing Applications 221

TABLE 11.2
Ammonia-Sensing Characteristics of M3X2Tx-P Nanocomposites
PEDOT:PSS/Ti3C2Tx PANI/Ti3C2Tx
Sensing Performance (Jin et al., 2020) (Li et al., 2020)
Lowest Detection Limit 10 ppm 25 ppb
Detection Rnge 10–1000 ppm 0.025–50 ppm
Sensitivity 4.94% 33.1% ~60% ~95% 0.05 % 400%
(10 ppm) (100 ppm) (500 ppm) (1000 (25 ppb) (50 ppm)
Ppm)
Response Time 116 s for 100 ppm ~600s
Recovery Time 40s for 100 ppm ~1400s
Liner Regression vlue 0.957 for 10–100 ppm rnge 0.983 for 100–1000 0.997 for 2–10 ppm
ppm rnge
Stbility ~33% t 100 ppm for 4 weeks 88% for 35 dys
Temperture 27°C for ll mesurements 10–40°C Vrition
Humidity 20–90% RH 20–90% RH
Repetbility 3 cycles 4 cycles
Selectivity 1.2% 4.6% 14% 3.4% ~10% 5% ~8% ~8%
100ppm 100ppm 100ppm 100ppm 10ppm 10ppm 10ppm 10ppm
toluene Ethnol Methnol Acetone HCHO H2S CO SO2
Flexibility ~33% t 100 ppm for different bending ngle ~22% t 10 ppm for bending ngle (20,
(60°–240°) 30, 40)° nd bending for 100, 200 nd
500 times.

11.9.1.5 Effect of Variation in Humidity and Temperature on the Working of Sensors

The sensitivity of M3X2Tx-P nnocomposite sensors towrd mmoni increses with surge in rel-
tive humidity, which is scribed to formtion of NH4OH or NH3∙H2O (due to rection of moisture
with mmoni; Abdull et l., 2015; Moger wt l., 2014). Since the dsorbed wter molecules over
PANI surfce cptures electron from it nd form H3O+ ions, which increses ionic conductivity of
PANI, enhncing its sensing response (Abdull et l., 2015). On exposure to mmoni, the form-
tion of NH4OH or NH3∙H2O tkes plce, which further cptures protons from PANI, resulting in 
higher sensing response (Moger wt l., 2014). However, Li et l. (2020) reported tht on incresing
the reltive humidity (RH) from 40% to 90%, the sensitivity of PANI/Ti3C2Tx sensor decreses nd
is found to be lowest t 90% RH. The reson cn be ttributed to the ccumultion of  thin lyer of
wter over the lm t dsorption sites, promoting the formtion of H3O+ ions (Abdull et l., 2015).
The excessive dsorption of thin wter lyer hinders the dsorption of mmoni molecules nd
limits the sensitivity (Li et l., 2020).
With the rise in environmentl temperture, the sensing response of M3X2Tx-P towrd mmoni
generlly decreses linerly. It is due to desorption of H3O+ ions from the polymer surfce nd com-
petition between desorption nd exothermic dsorption of mmoni on polymer surfce t elevted
temperture (Mtsuguchi et l., 2002). Li et l. (2020) studied the mmoni-sensing performnce
of  PANI/Ti3C2Tx sensor in temperture rnge of 10–40°C. The temperture rnge ws chosen s
it best suits griculturl pplictions (Li et l., 2020). The response ws found to decreses linerly
with surge in temperture.

11.9.1.6 Monitoring Volatilization of Agricultural Ammonia by M3X2Tx-P Sensors

Since the mesurement of voltiliztion of mmoni is essentil in griculture (Wei et l., 2018),
it is required to evlute the fesibility of M3X2Tx-P sensor for detecting the sme. It is generlly
222 MXene-Filled Polymer Nanocomposites

done by compring the sensing response of sensor with the conventionl sulfuric cid dsorption
method (SAAM) nd Drger nitrogen tube method (DTM) (Li et l., 2020). For generl procedure
(Li et l., 2020), in SAAM, 1 kg of fresh soil is plced in  lrge vessel nd cultivted under  drk
environment t  temperture round 20°C nd humidity bout 60%. Furthermore,  mixture of
ure in wter (in 1:2 rtio) is uniformly spryed over soil. After fertiliztion, 15 mL of sulfuric cid
in  smll beker is plced in  vessel contining soil, nd the concentrtion of NH4+ produced due
to rection of soil nd sulfuric cid is recorded by ow nlyzer in every 24h. In DTM (Li et l.,
2020),  drgger nitrogen tube is lso plced in similr vessel. The produced mmoni on enter-
ing this tube rects with the regent present in  tube nd turns its color to blue from yellow. The
coloring length of the tube is n indictor of the concentrtion of mmoni produced. For mmoni
voltiliztion mesurement, mmoni sensor is plced in vessel ner the soil, nd mesurements
were recorded. Li et l. (2020) compred the response of fbricted PANI/Ti3C2Tx sensor to verge
of results obtined from DTM nd SAAM. They noticed tht with incresing time (in dys), the fb-
ricted sensor gve mmoni trends ccording to n verge of DTM nd SAAM, which suggests
the fesibility of  PANI/Ti3C2Tx sensor towrd unttended monitoring of griculturl mmoni
voltiliztion (Li et l., 2020).

11.9.1.7 Sensing Mechanism of M3X2Tx-P Sensors

M3X2Tx-P sensors re generlly semiconducting in nture due to surfce termintion nd nture
of M, X, or polymer (Hjin et l., 2018). The mmoni-sensing mechnism generlly includes
redox rections between sensing mteril nd nlyte, chrge trnsfer, nd synergistic effects (Li
et l., 2020; Jin et l., 2020). The sensing phenomen of M3X2Tx-P sensors cn be scribed to two
mechnisms.

11.9.1.7.1 Chemisorption of Oxygen

At room temperture, M3X2Tx-P composite bsorbs the oxygen lyer nd converts it into oxygen
nions through trpping electrons from its conduction bnd (Thirumlirjn et l., 2014; Gund
et l., 2019). It cuses the cretion of n electron depletion lyer with more excellent resistnce. On
exposure to mmoni, electrons of oxygen ions re relesed bck to the composite conduction bnd
(Go et l., 2020b). It results in  decrese in the electricl resistnce of the composite sensor. On
reinstting ir to the sensing chmber, oxygen ions replce mmoni over the sensor surfce, nd
the originl resistnce vlue is restored (Jin et l., 2020). Jin et l. (2020) hve lso reported the
similr phenomen for PEDOT:PSS/Ti3C2Tx composite nd summrized it in the following chemi-
cl rections:

O 2 + e - → O 2-
4NH3 + 5O2- → 4NO + 5e- + 6H2O

However, t room temperture, the conversion of oxygen into oxygen nions is very less, this mech-
nism contributes very little to the sensing phenomen (Jin et l., 2020).

11.9.1.7.2 Physisorption of Ammonia Molecules

It is predominnt phenomenon in mmoni sensing through M3X2Tx-P composite (Li et l., 2020;
Jin et l., 2020). The electrons t surfce of M3X2Tx-P composite interct with mmoni nd result
in n increse of number of chrge crriers (Jin et l., 2020). This decreses the resistnce of the
sensor nd surges its conductivity. This phenomenon is lso found to be predominnt in other con-
ducting polymers nd their composites (Wu et l., 2013). Jin et l. (2020) proposed dding Ti3C2Tx
into PEDOT:PSS lso increses the π–π interction, leding to  lrge number of chrge crriers
nd surfce dsorption sites, which, in turn, enhnces its sensing response. However, Li et l. (2020)
extended this view to forming  smll Schottky junction between p-type Ti3C2Tx nd p-type PANI
in PANI/Ti3C2Tx composite. Since the work function of Ti3C2Tx ws lower thn tht of PANI, 
Gas- and Vapor-Sensing Applications 223

hole-depletion lyer forms in the PANI region t interfces of PANI/Ti3C2Tx. On dsorption of

mmoni,  decrese in hole concentrtion widens the depletion region, resulting in incresed
resistnce of PANI, which explins the sensing phenomenon in terms of decrese in resistnce of
M3X2Tx-P composite on exposure mmoni (Li et l., 2020).
Thus, the mmoni sensor bsed on M3X2Tx-P nnocomposites re exible (due to solubility
nd lm formtion on PI), cost-effective nd energy efcient (due to room temperture opertion),
highly sensitive (optiml structure of nnocomposite due to the inclusion of  polymer between
MXene stcking), improved degree of protontion in polymers (due to the introduction of MXene
sheets), environmentl- nd user-friendly (exclusion of hevy metls or toxic substnces), rpid (fst
response nd recovery), nd pt for commercil development (liner detection rnge). However, 
lower level of mmoni, such s ppb mesurements with improved sensing chrcteristics nd rel-
time humn breth nlysis, is still required with profound sensing chrcteristics nd is the current
re of reserch. It cn lso be noticed tht these studies (Jin et l., 2020; Li et l., 2020) s  well
open  window towrd the detection of the lcohol group since the response towrd ethnol nd
methnol ws signicnt nd cnnot be ignored. However, the sensing phenomenon for the lcohol
group is different s compred to mmoni nd cn be esily picked out using electronic circuitry
(Chudhry et l., 2016).

11.9.2 M2X-BASED MXENE–POLYMER COMPOSITES

Nguib et l. (Nguib et l., 2013) proposed tht M2X-bsed MXenes hold  lrger specic surfce
re thn M3X2 or M4X3-bsed MXenes due to their fewer tomic lyers. Thus, such  high effective
surfce re mkes them promising, excellent cndidtes for gs sensing pplictions. Furthermore,
conducting polymers such s PANI cn enhnce their sensing chrcteristics due to n increse
in interlyer distnce in MXenes. The following section discusses vrious reports on M2X-bsed
MXene-conducting polymer nnocomposite for mmoni-sensing pplictions.

11.9.2.1 Nb2CTx/PANI Nanocomposite Ammonia Sensors

Niobium crbide–polyniline (Nb2CTx/PANI) nnocomposites were mostly used for mmoni
detection due to their lrge surfce-to-volume rtio nd high dsorption sites (Wng et l., 2021,
2021). There re two distinct reports on Nb2CTx/PANI nnocomposite-bsed mmoni sensors by
Wng et l. (Wng et l., 2021, 2021) In both the reports ctive prent mterils of nnocomposite
re Nb2CTx nnosheets nd polyniline nnobers. However, they differ in synthesis technique s
one of the nnocomposites is prepred through ex situ technique nd one by in situ technique.

11.9.2.2 Sensor Fabrication

Ex-situ Nb2CTx /PANI nanocomposite (E-NPC): In this method, 2-D ultrthin Nb2CTx nnosheets
were prepred using typicl method of hydrouoric cid (HF) etching nd tetrpropylmmonium
hydroxide (TPAOH) intercltion method (Wng et l., 2021). Polyniline nnobers were sep-
rtely synthesized over PI substrte with gold interdigitted electrodes through  typicl in situ
polymeriztion technique (Wng et l., 2021). Furthermore,  lyer of Nb2CTx ws spry-coted
over  PANI-coted PI substrte nd dried in n oven t 60°C (Wng et l., 2021). For sensing
mesurements, the E-NPC sensor ws coupled with  fcile triboelectric nnogenertor (TENG)
operted by  liner motor of xed frequency of 1 Hz, which cts s  power source to drive the
fbricted sensor (Wng et l., 2021).
In situ Nb2CTx /PANI nanocomposite (I-NPC): In this communiction (Wng et l., 2021),
the method for fbricting 22D ultr-thin Nb2CTx nnosheets is the sme s in the previous report
(Wng et l., 2021). However, the polyniline ws synthesized over Nb2CTx nnosheets using n
in situ polymeriztion technique (Wng et l., 2021). Furthermore, the nnocomposite ws spry
coted on PI substrte with gold interdigitted electrodes for sensing mesurements.
224 MXene-Filled Polymer Nanocomposites

Thus, both the synthesis routes for sensor fbriction were different nd used TENG nnogen-
ertor for the E-NPC sensor. For the comprison, pure PANI nd Nb2CTx-bsed sensors were lso
fbricted using typicl processes (Wng et l., 2021).

11.9.2.3 Sensing Measurements

In TENG-coupled E-NPC sensors, on vrying the mmoni concentrtion, the resistnce of E-NPC
sensor chnges, which, in turn, lters the output voltge of externl-loding E-NPC sensor driven
by TENG (Wng et l., 2021). The gs-sensing response for the E-NPC sensor ws dened in terms
of the rel-time output voltge of the sensor s the percentge degree of chnge in voltge in the
presence of mmoni given by Eqution11.2.
All the mesurements were done t room temperture (~25oC) under 87.1% reltive humidity
conditions (Wng et l., 2021). Thus, the percentge chnge in output voltge through the E-NPC
sensor is the sensing prmeter during sensing mesurements. For I-NPC sensor (Wng et l., 2021),
the percentge chnge in resistnce in the presence of mmoni is tken s  sensing prmeter
given by Eqution11.2 t room temperture, pressure, nd humidity conditions (62% RH). The rel-
time monitoring of breth nlysis is further done to illustrte the commercil signicnce of the
prepred sensors.

11.9.2.4 Sensing Characteristics

For E-NPC sensor (Wng et l., 2021):

Wng et l. (Wng et l., 2021) designed four E-NPC sensors with different concentrtion of Nb2CTx
in terms of spry volume i.e. E-NPC-1 (0.05 mL), E-NPC-2 (0.1 mL), E-NPC-3 (0.15 mL), E-NPC-4
(0.2mL) nd compred it with pure Nb2CTx nd PANI sensor. The sensing response towrds 100 ppm
of mmoni for E-NPC-1, E-NPC-2, E-NPC-3, E-NPC-4, Nb2CTx nd PANI sensor ws found to be
197.20 %, 301.31 %, 108.36 %, 48.90 %, 8.15%, nd 128.81 %, respectively. Thus, the E-PNC-2 sen-
sor possesses the highest sensing response compred to other sensors due to its full dsorption sites
vilble to mmoni molecules. On further incresing the concentrtion of Nb2CTx, the dsorption
sites were hindered, limiting the sensing response. In terms of output voltge of sensor driven through
TENG, the response of E-NPC-2 sensor ws found to be highest mongst ll (2.57% per ppm) with
lest response time (105 s), which ws ttributed to the synergistic effects due to p-n junction effect
mongst Nb2CTx nd PANI. E-NPC-2 sensor ws found to exhibit signicnt liner response with R2 =
0.9655, with lowest limit of detection s 1 ppm of mmoni with sensitivity 2.87%. E-NPC-2 sensor ws
lso found to be stble in vrition with temperture nd humidity with consistent sensitivity towrds
mmoni. Further, the response is found to be recoverble, repetble nd reproducible for mny cycles.
The response is found to be signicnt nd mnifold enhnced compred to tht of sensor reports bsed
on PANI-MWCNT-TENG (255% t 100ppm), Ti3C2Tx (0.8% t 100 ppm), Ti3C2Tx-rGO (4.8% t 10
ppm) nd PANI-WO3 (121% t 100ppm). However, the report lcks in demonstrting the selectivity of
sid sensor.

For I-NPC sensor (Wng et l., 2021):

In in-situ synthesis, there is lwys possibility of formtion of heterojunctions mongst the prent
constituents, which further enhnces its sensing response compred to tht prepred by ex-situ
techniques. This observtion is gin vlidted by Wng et l. for I-NPC sensor. The fbricted
sensor possessed 29.95% sensitivity towrds 1 ppm of mmoni, which is lmost 14 fold enhnce
compred to E-NPC-2 sensor. The enhncement in sensitivity is dedicted to better 3-D morphol-
ogy nd interfce interction (heterojunctions) mongst PANI nd Nb2CTx. The fbricted sensor
is detects linerly with R 2 = 0.9619 in the rnge of 1–50 ppm of mmoni. Further, humid breth
mmoni monitoring ws performed nd the sid sensor demonstrted excellent sensitivity (74.68%
t 10 ppm), low detection limit (20 ppb), good liner detection rnge (R 2 = 0.9951), repetbility
(3 cycles), good response time (126s), long term stbility (tested for 35 dys), stbility in vrition
of humidity with poor recovery time (640s). Further, selectivity ws tested nd the I-NPC sensor
Gas- and Vapor-Sensing Applications 225

ws found to exhibit mximum sensitivity towrds 10 ppm of mmoni (74.44%) compred to tht
of sulfur dioxide (~9%), ethnol (2%), crbon monoxide (lmost negligible) nd hydrogen di-sulde
(~1%). However, s per reports in literture 9% sensitivity towrds sulfur dioxide is signicnt,
but it cn be differentited from response of mmoni using simple circuitry (Chudhry et l.,
2016, 2017, 2022, 2022b). This is becuse sulfur dioxide is n oxidizing gs, wheres mmoni is
 reducing gs, nd the sensing mechnism for both the nlytes is entirely opposite to ech other
(Chudhry et l., 2017). Thus, the study lso opens [the] window for sulfur dioxide sensing using
I-NPC sensor.

11.9.2.5 Sensing Mechanism

It is essentil to understnd the sensing mechnism of vrious constituents prior to exploring tht
nnocomposite.
For PANI:

Pure PANI undergoes protontion or deprotontion on dsorption or desorption of mmoni molecules

(Chudhry et l., 2015). Thus, there is conversion of PANI between its reducing nd oxidizing sttes,
which mens between emerldine slt nd emerldine bse. Adsorbed mmoni molecule lends n
electron to p-type PANI nd forms mmonium ion (NH4+), thereby decresing its resistnce due to
reduction in hole density (Liu et l., 2017).

For Nb2CTx:

Nb2CTx shows n n-type response towrds mmoni (Wng et l., 2021). It mens its resistnce
decreses in the presence of mmoni due increse in its electron density.

For Nb2CTx/PANI nnocomposites:

There re three mjor sensing phenomen of Nb2CTx/PANI nnocomposites for mmoni, which
includes the following.

11.9.2.5.1 Formation of p-n Junctions

Since Nb2CTx is n-type mteril nd PANI is  p-type mteril, it is speculted tht there is form-
tion p-n junction t the interfce of the two prent mterils in the cse of E-NPC (Wng et l.,
2021; Liu et l., 2017; Chudhry et l., 2015), which results into enhnced sensing response. Thus,
 thin depletion lyer forms t interfce due to diffusion of holes from PANI side nd electrons from
Nb2CTx side. On dsorbing the mmoni molecule, the resistnce of composite decreses due to 
decrese in hole concentrtion of PANI side, which brodens the depletion lyer (Wng et l., 2021).
It is due to the predominnce of PANI in the composite due to its high conductivity compred to
tht of Nb2CTx. A similr mechnism is seen in I-NPC; however, the formtion of smll p-n hetero-
junctions throughout the nnocomposite, including the interfce, enhnces its mmoni sensitivity
mnifold (Wng et l., 2021; Chudhry et l., 2021c).

11.9.2.5.2 Formation of Hydrogen Bonds

There is the formtion of bundnt intermoleculr hydrogen bonds mong PANI nd Nb2CTx. These
hydrogen bonds occupy mny hydrophilic functionl groups of the sensor, which reduces the ctive
sites for wter dsorption (Go et l., 2020; Wng et l., 2021).

11.9.2.5.3 Formation of Unique Hetero-Interfacial Functions

Using vrious DFT clcultions, it hs been found tht there is  formtion of unique hetero-inter-
fcil functionl groups t the interfces mong the precursors (Nguib et l., 2013; Go et l.,
2020b). Surfce functionliztion of MXene by vrious functionl groups (–OH, –F or –O) turns
them into semiconductors with  bndgp in the rnge of 0.05–1.8 eV (Go et l., 2020). This
226 MXene-Filled Polymer Nanocomposites

functionliztion surges interfcil chrge crrier trnsfer, further enhncing its sensing response
(Wng et l., 2021).
These three phenomen together contribute to the enhnced sensing response of M2X-bsed
MXene-conducting polymer-bsed mmoni sensors.
Thus, the studies on MXene–polymer nnocomposites re very less nd dedicted to mmoni
gs, which cn be scribed to the selectivity of these sensors towrds mmoni. The reson cn
be ttributed to the specic dsorption energy of mmoni nd the presence of functionl groups
which re speciclly rective towrd mmoni. However, the studies lso show the potentil to
detect other gses, including sulfur dioxide nd nitrogen oxides (Wng et l., 2021). Thus, dedicted
studies re required nd re the current reserch topic, long with enhncing mmoni-sensing
chrcteristics of MXene–polymer nnocomposite-bsed sensors.

11.10 MXene–POLYMER NANOCOMPOSITE-

BASED CARBON DIOXIDE SENSORS
The emission of crbon dioxide (CO2) hrms the environment, crop production, nd humn helth.
Its monitoring t  low ppm level is the foremost concern of the reserch community (Mulmi et l.,
2020). Although the discovery of MXene hs lso opened  new window for room temperture
detection of CO2, reports on its sensing through MXene sensors re in scrcity (Zhn et l., 2020;
Ho et l., 2021; Kusr et l., 2021). Zhou et l. (2020) reported CO2-sensing performnce of ter-
nry nnocomposite of nitrogen-doped MXene, Ti3C2Tx (N-MXene), polyethyleneimine (PEI), nd
reduced grphene oxide (rGO) nd compred it with tht of pristine Ti3C2Tx, PEI, Ti3C2Tx-PEI,
rGO-PEI, Ti3C2Tx-rGO, nd N-Ti3C2Tx.

11.10.1 FABRICATION OF SENSORS

Ti3C2Tx ws prepred s discussed previously in M3C2Tx section through LiF/HF etching (Li
et l., 2020). N-Ti3C2Tx, rGO, PEI, rGO-PEI, Ti3C2Tx-rGO were prepred using typicl processes
reported by Zhou et l. (2020). Ti3C2Tx-PEI ws prepred by ex situ technique by simply mixing
pre-synthesized constituents in deionized wter under nitrogen ow. For the synthesis of ternry
N-Ti3C2Tx-PEI-rGO (NTPG) nnocomposite, pre-synthesized Ti3C2Tx, rGO, nd PEI were mixed
under constnt ow of nitrogen for 2hours. Furthermore, sensors were fbricted by spry-coting
the trget solution on silicon oxide (SiO2)/Si substrte with plnr interdigitted electrodes (Zhou
et l., 2020). The fbricted sensors re chemiresistive-type sensors with response dened by
Eqution 11.1.

11.10.2 SENSING PERFORMANCE

The concentrtion of CO2 beyond 1000 ppm indoors is hrmful to humn helth (Hz et l.,
2014). Thus, the detection of CO2 t this limit is indeed required t indoor emission centers. Zhou
et l. (2020) nlyzed CO2 monitoring performnce of NTPG, Ti3C2Tx, PEI, Ti3C2Tx-PEI, rGO-
PEI, Ti3C2Tx-rGO, nd N-Ti3C2Tx sensors towrd 1000 ppm under 48% RH t 20°C. The sensing
response of Ti3C2Tx, N-Ti3C2Tx, nd Ti3C2Tx-rGO ws not unstble with high noise, nd the rest
were shllow, except the NTPG-bsed sensor (Zhou et l., 2020). Pure PEI is insulting, nd its
resistnce ws not mesurble below 36% RH (Zhou et l., 2020). However, with  rise in RH, the
resistnce of PEI decreses due to humidity-ctivted proton conduction phenomen. PEI-chieved
sturtion in resistnce t 62% RH (Zhou et l., 2020). Pristine rGO nd Ti3C2Tx do not show ny
chnge in resistnce t 62% RH. Thus, it hs been chosen to do further sensing mesurements (Zhou
et l., 2020). Furthermore, four ternry NTPG sensors were fbricted by vrying PEI concentr-
tion (0.0025, 0.005, 0.0075, nd 0.01 mg/mL). NTPG sensor with 0.01 mg/mL shows excellent
Gas- and Vapor-Sensing Applications 227

sensitivity of bout 7.4% towrd 40 ppm of CO2under 62% RH t 20°C. Further sensing chrcter-
istics re listed in Tble 11.3.
Zhou et l. (2020) observed no recovery or signicntly less recovery on removing CO2 in dry
ir. However, if ir supplied to the sensing chmber for evcution of CO2 ws wet with 2.1% RH,
the sensing response surges to 9% for 600 ppm nd recovery is chieved. It is ttributed to superior
proton-hopping conduction of PEI due to moisture in ir (Zhou et l., 2020). The response is found
to be repetble nd liner in two different rnges s listed in Tble 11.3. However, the response
decresed with the surge in temperture due to  reduction in dsorbed wter molecules. The sens-
ing response observed ws found to be signicnt s compred to the reports present in the liter-
ture on CO2 detection through zinc oxide (20% for 200 ppm t 250°C; Knprthi et l., 2019),
cesium oxide (110% for 150 ppm t 100°C; Zito ey l., 2020), Ru@WS2 (1.8% for 20 ppm t 25°C;
Rthi et l., 2020) nd Ag@Cuo/BTiO3 (120% for 100 ppm t 120°C; Joshi et l., 2017).

11.10.3 SENSING MECHANISM

PEI domintes the sensing mechnism in the ternry nnocomposite. PEI possesses primry
R-NH2, secondry R1R2-NH, nd tertiry R1R2R3-N mino groups (Don et l, 2014). Primry nd
secondry mino groups of PEI on exposure to CO2 result in cid–bse rections to give crb-
mtes, wheres tertiry mino groups result in crbonic cid by the dissolution of CO2 (Don et l,
2014). In the presence of humidity, bicrbontes re formed insted of crbmtes. N-MXene in
the nnocomposite due to its hydrophilic nture dsorbs wter molecules, which further protontes
PEI the chrge trnsfer (Srinives et l., 2015; Don et l, 2014). The presence of rGO in nnocom-
posite serves s rpid conduction chnnels for chrge trnsfer nd collection processes (Zhou et l.,
2020). Thus, when nnocomposite is exposed to CO2, the number of free mines decreses, nd the
mobility of protons reduces, which is mplied by the ction of MXene nd rGO, resulting in  net
increse in the resistnce of the sensor (Zhou et l., 2020; Srinives et l., 2015). Zhou et l. (2020)
scribed fst recovery in wet ir to hindrnce to cid–bse rection due to steric effects offered by
PEI. Thus, ll three constituents ply  vitl role in the sensing phenomenon.
Although the reported sensor is cost-effective with signicnt sensing chrcteristics to detect
CO2, improvement to enhnce response nd recovery still requires ordinte ttention for commer-
cil development of these sensors.

TABLE 11.3
CO2-Sensing Characteristics of NTPG Sensor
NTPG Sensor
Sensing Performance (Zhou et al., 2020)
Lowest Detection Limit 8 ppm
Detection Rnge 8–600 ppm
Sensitivity ~1% for 8 ppm
Recovery Time ~9 min for 600 ppm
Liner Regression vlue 0.974 for 8–40 ppm rnge 0.984 for 40–600 ppm rnge
Stbility ~8% t 600 ppm for 50 dys
Temperture 20–50°C for ll mesurements
Humidity 32–64% RH
Repetbility 4 cycles
Response Time ~8.8 min for 600 ppm
Selectivity No signl 0.5% 0.3% 0.18%
(8 ppm of H2S) (8 ppm of SO2) (40 ppm of HCHO) (8 ppm of NH3)
228 MXene-Filled Polymer Nanocomposites

11.11 MXene–POLYMER NANOCOMPOSITE-BASED

VOCS/VAPOR SENSORS
VOCs hve been extensively used s rw mterils in vrious industries nd possess dverse effects
on humn helth nd the environment (Tung et l., 2017; Tng et l., 2017). Thus, the monitoring
of VOCs, such s methnol, ethnol, nd cetone, which re highly mmble nd toxic, is indeed
required in the eld of mnufcturing industries, personl helthcre industries, nd biomedicl
pplictions (Tung et l., 2017; Wng et l., 2020; Jll et l., 2018). Although there re reports
on the sensing of VOCs through MXenes, they lck sensitivity due to fewer dsorption sites (Kim
et l., 2018; Chen et l., 2020; Li et l., 2021). However, polymer inclusion in MXene enhnces
dsorption sites nd chrge crrier trnsport for better sensing performnce (Crey et l., 2021; Rizi
et l., 2021). In literture, there re very few reports on MXene–polymer nnocomposites for VOC
detection (Wng et l., 2020; Yun et l., 2018; Zho et l., 2019; Zhn et l., 2020). However, these
reports re mjorly dedicted to M3X2Tx-P nnocomposites to detect vrious VOCs t room tem-
perture. Yun et l. (2018) reported the fbriction of 3D MXene–polymer frmework of Ti3C2Tx
poly-vinyl lcohol (PVA) nd PEI(3TPP) nd evluted it for detecting vrious VOCs, including
methnol, ethnol nd cetone. Wng et l. (2020) developed  dedicted sensor for methnol detec-
tion bsed on Ti3C2Tx/PEDOT:PSS nnocomposite. On the other hnd, Zho et l. (2019) reported 
dedicted ethnol sensor bsed on Ti3C2Tx- PANI nnocomposite.

11.11.1 SENSOR FABRICATION

The fbriction process of the sensor for VOCs sensing is quite similr to tht of the mmoni
sensor, s discussed previously. Zho et l. (2019) reported the synthesis of Ti3C2Tx- PANI nno-
composite t low temperture through in situ polymeriztion s discussed erlier (Li et l., 2020).
However, they hve kept the synthesis temperture very low (0–5°C) to get  high yield nd
limiting the dmge to the Ti3C2Tx structure during synthesis process. The structure of obtined
nnocomposite ws similr to the lmellr structure shown in Figure 11.2. A exible sensor ws
fbricted on interdigitted PET substrte. Wng et l. (2020) fbrictedTi3C2Tx/PEDOT:PSS
nnocomposite using ex situ mixing technique s mentioned in n erlier section (Jin et l.,
2020). They hve lso vried the rtio of PEDOT:PSS to Ti3C2Tx in nnocomposite, prticulrly
10:1,8:1,4:1, 2:1,1:1, nd1:2 nd mde sensing lms over interdigitted electrodes. However,
Yun et l. (2018) hve used  coupled electrospinning nd self-ssembly method to develop 
3TPP frmework. The 3D polymer frmework ws fbricted in  typicl synthesis by electro-
spinning the PVA/PEI mixture using sodium dodecyl sulfte (SDS). Fibers of PVA/PEI frme-
work were collected on interdigitted electrode-bsed PET substrtes through electrospinning nd
dipped in glutrldehyde overnight for crosslinking nnobers. Then, it ws immersed in MXene
solution nd dried to obtin  sensor.

11.11.2 SENSING PERFORMANCE

VOCs’ sensing performnce for ll the fbricted sensors ws mesured using  chemiresistive
mode. The sensing performnce of M3X2Tx-P nnocomposites were found to be enhnced com-
pred to their pristine prent constituents, which cn be scribed to the presence of lmellr struc-
ture with enlrged interlyer spcing, improved chrge crrier trnsport nd presence of specic
functionl groups (Zho et l., 2019; Wng et l., 2020; Yun et l., 2018). Wng et l. (2020)
lso observed tht the vrition in Ti3C2Tx concentrtion in nnocomposites chnges their sensing
response towrd methnol. They found the sensor bsed on mss rtio 4:1 showed the highest sens-
ing response towrd 300 ppm of methnol, ethnol, nd cetone mong ll sensors. It is scribed
to eliminting MXene-MXene connectivity due to the inclusion of PEDOT:PSS between MXene
lyers. However, in other combintion rtios, MXene–MXene connections re predominnt,
Gas- and Vapor-Sensing Applications 229

TABLE 11.4
Sensing Characteristics of M3X2Tx-P Nanocomposites toward Methanol
Ti3C2Tx/PEDOT:PSS
Sensor (4:1) 3TTP Sensor
Sensing Performance (Wang et al., 2020) (Yuan et al., 2018)
Lowest Detection Limit 180 ppm 50ppb
Detection Rnge 180–500 ppm 50 ppb—1.5 × 105 ppm
Sensitivity 0.4% t 180 ppm 2.7% for 5 ppm
Recovery Time >500s 1.7 min
Response Time ~280s 1.5 min
Temperture RT RT
Humidity Ambient Ambient
Repetbility Not mentioned 5 cycles
Liner Regression vlue Not mentioned 0.14 per ppm
Selectivity ~0.1% to ethnol nd cetone 3.6%, 4.4%, nd 2.7% for 5ppm of
cetone, ethnol, nd methnol
Flexibility Not mentioned Flexible for 1000 bending cycles

incresing the nnocomposite’s conductivity nd reducing its sensing response. They hve further
evluted sensing chrcteristics for 4:1 rtio Ti3C2Tx/PEDOT:PSS nnocomposite towrd meth-
nol s listed in Tble 11.4.
It ws observed tht 3TTP-bsed sensors possess more signicnt methnol-sensing chrcter-
istics thn tht of other M3X2Tx-P nnocomposites in terms of response, detection rnge, exibil-
ity, nd selectivity. However, it suffers from extended response nd recovery time, which possess
further improvement (Yun et l., 2018). Zho et l. (2019) recorded reltive chnge in the sensing
lyer’s current on exposure to VOCs insted of recording vrition in resistnce. They lso observed
tht the fbricted exible sensor is dedicted to detection of ethnol. The selectivity of fbricted
Ti3C2Tx/PANI sensors towrd ethnol ws evluted through DFT studies (Zho et l., 2019) nd
ws ttributed to smllest bond length for the dsorption of ethnol compred to tht of methnol,
mmoni, nd cetone. The sensor ws found to be rpid due to very smll response nd recovery
time, exible, nd highly repetble. However, studies of relted stbility cn lso be included to
propose its commercil development. Tble 11.5 compres the ethnol-sensing response of vrious
M3X2Tx-P nnocomposites.
Furthermore, cetone-sensing chrcteristics of M3X2Tx-P nnocomposites were compred nd
listed in Tble 11.6. It ws observed tht 3TTP-bsed sensors possess better cetone-sensing chr-
cteristics compred to others, which cn be ttributed to its 3D frmework–type structure with
high effective surfce re, more dsorption sites, nd lrge rective functionl groups (Yun et l.,
2018).
3TTP-bsed sensors possess signicnt sensing responses towrd methnol, cetone, nd eth-
nol with improved sensing chrcteristics owing to its structure nd surfce chemistry (Yun et l.,
2018). However, it suffers from slow response nd recovery process nd selectivity. Thus, it requires
more functionliztion for the formtion of dedicted sensors towrd specic VOCs.

11.11.3 SENSING MECHANISM

The sensing mechnism of M3X2Tx-P nnocomposites hs been explined in terms of its hydrogen
bonding cpbility due to functionl groups (Kim et l., 2018). M3X2Tx-P nnocomposites possess
functionl group over its surfce, which ttches to VOCs through electrosttic interction nd
hydrogen bonding (Kim et l., 2018; Rizi et l., 2021). Yun et l. (2018) observed  fscinting fct
230 MXene-Filled Polymer Nanocomposites

TABLE 11.5
Sensing Characteristics of M3X2Tx-P Nanocomposites toward Ethanol
Ti3C2Tx/PEDOT:PSS
Sensor (4:1) Ti3C2Tx- PANI Sensor 3TTP Sensor
Sensing Performance (Wang et al., 2020) (Zhao et al., 2019) (Yuan et al., 2018)
Lowest Detection Limit 60 ppm 1 ppm 50 ppb
Detection Rnge 60–500 ppm 1–200 ppm 50 ppb—8 × 104 ppm
Sensitivity 0.1% t 300 ppm 1.56% t 1 ppm 4.4 % t 5 ppm
Recovery Time ~500s 0.5s 1.7 min
Response Time ~280s 0.4s 1.5 min
Temperture RT RT RT
Humidity Ambient Ambient Ambient
Repetbility Not mentioned 140 cycles 5 cycles
Liner Regression Vlue Not mentioned 1.56% per ppm 0.17% per ppm
Selectivity Not selective to ethnol ~20% for 200 ppm of 3.6%, 4.4%, nd 2.7% for
methnol, cetone, nd 5ppm of cetone, ethnol,
mmoni nd methnol
Flexibility Not mentioned ~25–27% for 150 ppm for Flexible for 1000 bending
bending ngle (0–120)o cycles

TABLE 11.6
Sensing Characteristics of M3X2Tx-P Nanocomposites toward Acetone
Ti3C2Tx/PEDOT:PSS
Sensor (4:1) 3TTP Sensor
Sensing Performance (Wang et al., 2020) (Yuan et al., 2018)
Lowest Detection Limit 60 ppm 50 ppb
Detection Rnge 60–500 ppm 50 ppb—3 × 105 ppm
Sensitivity ~0.09% t 300 ppm 0.08% t 50 ppb
Recovery Time ~500s 1.7 min
Response Time ~280s 1.5 min
Temperture RT RT
Humidity Ambient Ambient
Repetbility Not mentioned 5 cycles
Liner Regression vlue Not mentioned 0.1 per ppm (50 ppb to 20 ppm)
3.7 × 10−3 per ppm (25–1.5 × 105 ppm)
Selectivity Not selective to Acetone 3.6%, 4.4% nd 2.7% for 5ppm of cetone, ethnol, nd methnol
Flexibility Not mentioned 2% for 20ppm for 1000 bending nd unbending cycles

tht the resistnce of 3TTP sensors ws found to increse in every VOC regrdless of their nture,
whether p-type or n-type. It cn be ttributed to the dominnce of MXene in the nnocomposite,
which possesses  metllic type of conductivity (Yun et l., 2018). They hve lso proposed 
mechnism for selectivity of VOCs due to their bility to form strong hydrogen bonding with more
electronegtive toms like oxygen toms nd electrosttic ttrction with MXene (Yun et l., 2018).
Thus, VOCs, such s cetone, methnol, nd ethnol, re esily detected by M3X2Tx-P nnocompos-
ites. However, polr orgnic molecules form wek hydrogen bonds nd nonpolr orgnic molecules
form no hydrogen bond, restricting their detection through M3X2Tx-P nnocomposites-bsed sen-
sors (Yun et l., 2018).
Gas- and Vapor-Sensing Applications 231

The sensing response of M3X2Tx-P nnocomposites sensor ws compred to other reports in
the literture nd found to be consistent nd enhnced in terms of sensing chrcteristics (Wng
et l., 2020; Zhn et l., 2020; Chen et l., 2020). Zho et l. (2019) explined the enhnced sens-
ing response of M3X2Tx-P nnocomposites in terms of three fctors, including incresed interlyer
distnce resulting in more dsorption sites, the dominnce of MXene nd its metllic conductivity,
nd hydrogen bonding nd electrosttic interction between VOCs nd the nnocomposite surfce
due presence of bundnt functionl groups. However, these reports lck the study of vrition in
sensing response with chnges in humidity nd working temperture. These studies lso miss one of
the 3Ss stbility studies. Thus, more dedicted reserch is required for the commercil development
of VOC sensors bsed on M3X2Tx-P nnocomposites.

11.12 CONCLUSION AND FUTURE PROSPECT

MXene–polymer nnocomposites-bsed sensors open  new window for detecting vrious gseous
nd vpor nlytes, including mmoni, sulfur dioxide, oxides of nitrogen, methnol, ethnol, nd
cetone t room temperture with signicnt sensing chrcteristics. The room temperture opertion
of MXene–polymer nnocomposite sensors mkes them energy- nd cost-efcient due to the exclu-
sion of micro-heting ssemblges. Due to the bsence of ny toxic mteril such s hevy metl,
these sensors re user-friendly, generting negligible toxic nno-wste. They re rpid in detecting
gseous nlytes. However, the response nd recovery in the cse of VOCs cn be further improved.
Due to the chemiresistive module, they cn be efciently designed, hndled, occupied, nd used t
every emission site, unlike sophisticted sensors such s electrochemicl or spectroscopic sensors.
However, the reports on monitoring VOCs nd gses through MXene–polymer nnocomposites re
in scred except for mmoni. More MXenes nd polymer combintions cn be explored for fbrict-
ing chemiresistor to detect vrious pollutnts nd hrmful vpors. MXene–polymer nnocomposites
possess prospects in the electronic nose nd sensor rrys due to their selectivity towrds prticulr
nlytes t room temperture. They re  potentil cndidte for the fbriction of intelligent, rpid,
energy-efcient, user nd environmentlly friendly, cost-effective, exible, miniture, esy to hn-
dle, nd portble gs nd vpor sensors with enhnced three Ss-nd ve Rs-sensing chrcteristics.

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 12 MXene-Based
Nanocomposites in
Energy Conversion and
Storage Systems
Dana Susan Abraham,
Margandan Bhagiyalakshmi,
and Mari Vinoba

CONTENTS
12.1 Introduction ........................................................................................................................... 235
12.2 MXene/Polymer Nnocomposites for Energy Storge nd Conversion Applictions .......... 236
12.2.1 MXene/Polymer Nnocomposites s Electrode Mterils in Supercpcitors ......... 236
12.2.2 MXene/Polymer Nnocomposites in Bttery Appliction ........................................ 240
12.2.3 MXene/Polymer-Bsed Electrode Mterils in Fuel-Cell Appliction ..................... 242
12.3 Conclusion............................................................................................................................. 243
References...................................................................................................................................... 243

12.1 INTRODUCTION
Since the rst report on trnsition metl crbides—MXenes (Nguib et l., 2011) in 2011, the mjor
ppliction explored on MXene ws s electrode mterils in energy storge systems (ESSs). Well-
estblished ESSs re btteries nd supercpcitors whose performnce in terms of energy nd
power density re criticlly controlled by the electrode mterils employed. From the reports, the
MXene re uniquely known to possess metllic conductivity, lyered structure, nd lrge surfce
re tht llows diffusion/intercltion of ny molecules nd ionic trnsport nd dsorption on the
surfce, respectively. Over the decdes, MXenes re synthesized only through etching IIIA or IVA
group element lyers from bulk MAX powders; the desired new skeleton of MXenes structures cn
be obtined bsed on the choice of the prent MAX phse.
MAX phses re lyered compositions of erly trnsition metls (M), Al or Si (A), nd crbon,
nitrogen or  combintion of the two (X) in the nottion Mn+1AXn, where n 1–3 (Brsoum, 2000)
Until now,  vriety of combintions nd structures of MAX phse bout more thn 150 forms
re known (Sokol et l., 2019; Nechiche et l., 2017; Li et l., 2017; Liu et l., 2014). Generlly,
etchnts, such s hydrouoric cid (HF) or  mixture of LiF nd HCl slts in wter re employed for
removing luminum from the MAX phse to obtin MXene. Typiclly, Al is etched from the MAX
phse through three min rections upon HF tretment s shown:

Ti3AlC2 + 3HF → AlF3 + 3/2 H2 + Ti3C2 (12.1)

Ti3C2 + 2H2O → Ti3C2 (OH)2 + H2 (12.2)
Ti3C2 + 2HF → Ti3C2F2 + H2 (12.3)

DOI: 10.1201/9781003164975-12 235

236 MXene-Filled Polymer Nanocomposites

Eqution 12.1 shows the removl of Al, nd the rections, Equtions 12.2 nd 12.3, describe the
rectivity of the bre surfce of MXene with the environment to form O, OH, nd F on the surfces
(Nguib et l., 2011; Hope et l., 2016; Cffrey, 2018).
MXene-bsed energy storge systems, especilly supercpcitors, re well pprecited for their
high energy density. The lyered MXene mtrix is highly stble even fter 1,000 cycles of inter-
cltion nd de-intercltion of ions nd, hence, provides high energy (Luktsky et l., 2013;
Ghidiu et l., 2014; To et l., 2013; Fn et l., 2018; Wng et l., 2017). Here it is concentrted on
this prticulr property, which demonstrted tht MXene s potentil electrode mteril for ESSs.
Noteworthy, the mjority of the reports re on the ppliction of MXenes s electrode mteril due
to its isolted lyers stcked in n orderly mnner, forming heterostructures tht contribute to elec-
tric nd electronic properties.
Yet nother interesting property of MXene is the mechnicl robustness due to the highest
Young’s modulus (Liptov et l., 2018), which endows MXenes s potentil ller mterils in prep-
rtion of polymer nnocomposites. Also, the unique properties of MXenes hve mde them 
suitble nnoller for mking high-performnce polymer composites tht cn stisfy electricl,
therml, mechnicl, me-retrdnt, nd other requirements (Li et l., 2019). Reserchers in the
eld of polymers re ttrcted to the mechnicl property of MXene, nd s  result, severl exciting
developments on polymer nnocomposites with MXene nd MXene-bsed nnocomposites s ll-
ers re vilble for direct ppliction in vrious sectors (Go et l., 2020; Feng et l., 2018; Jimmy
nd Kndsubrmnin, 2020). The properties of polymers like sheer verstility, interfcil ten-
sion, corrosion resistnce, frcture resistnce, nd stiffness when combined with highly conductive,
mechniclly stble results in dvnced polymer–MXene nnocomposites, which re promising
cndidtes for energy conversion nd storge.
The MXene/polymer nnocomposites re generlly ctegorized s lled composites nd com-
plexes. In  lled composite, MXene is utilized s  ller or  component in  bulk mteril, while
MXene nd polymer re sprsely oriented with ech other in  complex. The most frequently
reserched mterils re lled MXene/polymer nnocomposites, thermoplstic, nd thermosetting
polymer mtrix (Crey nd Brsoum, 2021). This chpter discusses the ppliction of MXene/poly-
mer nnocomposites in energy conversion nd storge systems, emphsizing supercpcitors, bt-
teries, nd fuel cell pplictions.

12.2 MXene/POLYMER NANOCOMPOSITES FOR ENERGY

STORAGE AND CONVERSION APPLICATIONS
12.2.1 MXENE/POLYMER NANOCOMPOSITES AS ELECTRODE MATERIALS
SUPERCAPACITORS
IN

Supercpcitors re hooked on s long-life energy storge devices in the electricl power storge
industry. MXene-bsed electrode mterils hve gret potentil for supercpcitors in the light of
their outstnding metllic conductivity, high hydrophilicity, high pseudocpcitnce, nd ese of
prepring exible, freestnding electrode lms. The dvntge of MXene electrode mterils for
supercpcitors over conventionl electrode mterils is tht they re esily ssembled to produce
freestnding, exible electrodes nd devices without binding gents (Vhid Mohmmdi et l., 2018).
In situ pyrrole polymeriztion between MXene lyers ws illustrted by Boot et l. (2016),
leding to  pseudocpcitive electrode with good electrochemicl stbility. PPy/Ti3C2Tz compos-
ite exhibited  mximum volumetric cpcitnce of ≈1000 F cm−3, nd its 92% cpcitnce ws
retined even fter 25,000 cycles. The incorportion of polypyrrole lyer between Ti3C2Tz monoly-
ers resulted in enhnced electronic conductivity, fst ion trnsport, nd rpid redox rections due to
the shortened diffusion pthwy in PPy/Ti3C2Tz composite. The synergistic effect of Ti3C2Tz lyers
interclted with conductive PPy, nd the redox rections between PPy nd MXene-enhnced PPy/
Ti3C2Tz composite cpcitnce.
Energy Conversion and Storage Systems 237

Boot nd collegues (Boot nd Gogotsi, 2019) demonstrted symmetric pseudo-cpcitors
using conducting polymers (CP) nd MXene. MXene served s the node mteril for the pseudo-
cpcitor, nd reduced grphene oxide sheet conned with PPy, PANI, nd PEDOT cted s cth-
ode. All the CP@rGO//MXene offered impressive power nd energy densities, s well s excellent
cycling properties. PANI-contining symmetric device showed n extremely high energy density
of 17 Wh kg−1 nd the highest retention in cpcitnce of 88%, which is one of the best results for
both MXene-bsed nd PANI-contining symmetric devices.
Li et l. (2020b) engineered n symmetric nd exible pseudocpcitor from wvy-Ti3C2Tx//
rGO/CNT/PANI, s in Figure 12.1. For the fbriction of negtive electrodes, the sheets of MXene
were initilly mixed in wter contining sub-microspheres of polystyrene (PS). PS spheres were
then removed by heting in Ar tmosphere t 450°C, developed initilly s  freestnding, stretch-
ble, nd porous lm, which ws lter compressed into  compct wvelike lm. Compred to
highly ligned Ti3C2Tx lm, the wvy Ti3C2Tx lm with poor lignment enbled improved trnsport
of ions, resulting in  signicnt volumetric cpcitnce of 1277 F cm−3. rGO/CNT/PANI electrode
ws used to complement the negtive MXene electrode. Asymmetric wvy-Ti3C2Tx//rGO/CNT/
PANI supercpcitors demonstrted 70 Wh L−1 of energy density nd 111 kW L−1 of power density.
Boot et l. (2017) explored the cpcitnce chrcteristics of MXene/PFD (polyuorene-
derivtive) nnocomposites s  supercpcitor electrode. A higher cpcitnce ws observed for
MXene/PFD with quternry nitrogen groups becuse of the intercltion effect, resulting in stron-
ger chrge trnsfer interctions t the MXene/PFD interfce. This improves proton ccessibility,
s well s pseudo-cpcitnce due to polymer. Moreover, they pointed out tht the improvement in
cpcitnce ws relted to the uniformity in dispersion, the polrity of the PFDs nd MXene. The
dispersion of molecules with more uniformity will hve  stronger interction with MXene, nd
the cpcitnce effect will be more noticeble. A mximum volumetric cpcitnce of 1026 F cm−3
ws delivered by MXene/PFDs electrodes. The grvimetric cpcitnce is more thn 1.5 times tht
of the pure Ti3C2Tz lm (245 Fg−1, 2 mV s−1) nd more thn twice tht of the Ti3C2Tz hybrid (Ling
et l., 2014).
Qin et l. (2018) utilized  solution processing technique to develop n ultrthin nd exible
supercpcitor, Mo1.33C MXene/PEDOT: PSS. It fetured n enhnced volumetric cpcitnce,
highpower, nd energy density of 568 F cm−3, 19470 mW cm−3, nd 33.2 mWh cm−3, respectively.
Upon tretment with H2SO4,  higher cpcitnce ws observed 1310 F cm−3. A pir of fctors is
responsible for the incresed cpcitnce nd stbility: the inclusion of conducting PEDOT between
the Mo1.33C MXene lyers resulted in greter interlyer spcing nd the interfcil redox processes.

FIGURE 12.1 Schemtic representtion of symmetric pseudocpcitor from wvy-Ti3C2Tx//rGO/CNT/

PANI nd its electrochemicl performnce (Li et l., 2020b).
238 MXene-Filled Polymer Nanocomposites

Zhng et l. (2021) described the benecil effects of trtric cid s n dditive to MXene
(Ti3C2Tx) nd in the MXene/polymer composite to form highly conductive nd stble functionl
composites for ultrfst supercpcitors. Trtric cid ws dded to MXene during its nneling,
resulting in “t-Mxene”. Figure 12.2 shows the effect of trtric cid on MXene/PEDOT: PSS com-
posite. It ws observed tht trtric cid ws ble to cp nd protect the Ti ctions present on the
defective edges from chemicl oxidtion, even when the tempertures were elevted. Acidic disper-
sion of MXene ws lso enhnced by trtric cid. In this study, t-MXene/PEDOT: PSS compos-
ites were synthesized using trtric cid tretment. Along with cpping the MXene surfce, trtric
cid lso induced crosslinking in the MXene/PEDOT: PSS composite, mintining its structurl
integrity. The composite lso exhibited storge stbility for 2 weeks. Along with its chemicl nd
structurl stbilizing effects, trtric cid incresed the electricl conductivity by four times, rising
to 2,240 S cm−1 for t-MXene/PEDOT: PSS from 552 S cm−1 of MXene/PEDOT: PSS.
Qin et l. (2019) investigted the polymeriztion of orgnic monomers EDOT nd pyrrole by
in situ electrochemicl polymeriztion (EP) using 2D MXene without employing conventionl elec-
trolytes to form exible solid-stte micro-supercpcitors. MXene colloidl solution ws observed
to serve s  high conductivity solvent during the EP process. Simultneously, self-ssemble into
polymer lms with  higher content of dopnts thn conventionl electrolytes, resulting in conju-
gted polymeric MXene lms t  moleculr level. The pseudo-cpcitnce nd ultr-high-energy
cpcity of these composite lms were found to be 47.4 mF cm−2 nd 20.05 mWh cm−3, respectively.
A signicnt improvement in both the stbility nd the rte of the micro-supercpcitors ws lso
chieved. An efcient symmetric micro-supercpcitors (AMSCs) were developed to improve the
energy density nd cell voltge with in-situ EP composite lms with MnO2; the high energy nd
power density were found to be 250.1 mWh cm−3 nd 32.9 W cm−3, respectively. Additionlly, the
AMSCs showed excellent cyclic stbility over 10,000 cycles.

FIGURE 12.2 Effect of trtric cid on MXene/PEDOT: PSS composites (Zhng et l., 2021).
Energy Conversion and Storage Systems 239

Wu et l. (2019) fbricted  new decentrlized conjugted polymer (PDT) using 2, 6- dimi-
nonthrquinone (DAQ) nd tetrkis(4-bromophenyl) methne (TM), which ws coupled with
lyered MXene by Buchwld–Hrtwig coupling. The so-formed electrode displyed n improved
rel cpcitnce of 284 mF cm−2. Furthermore, glvnosttic chrge–dischrge nlysis of PDT/
Ti3C2Tx lm reveled lmost 100% cpcitnce retention fter 10,000 cycles. The PDT/Ti3C2Tx lm
displyed excellent electrochemicl performnce stbility, which cn be utilized to develop  solid-
stte supercpcitor with cpcitnce of 52.4 mF cm−2 t 0.1 mA cm−2 over 100 cycles. It lso proved
to be exible nd could withstnd 10,000 cycles of sttic bending t 0–90°. The nlysis reveled
tht when the decentrlized chin of PDTs nd the Ti3C2Tx with better conductivity re combined,
electron conduction efciency, electrochemicl ctivity, stbility, nd exibility re incresed.
Ajnsztjn et l. (2020) integrted 2D Ti3C2Tx nnosheets with poly(9,9-di-n-octylourenyl-
2,7-diyl) (PFO) using  deposition technique, resonnt infrred mtrix-ssisted pulsed lser evpo-
rtion (RIR-MAPLE), to generte  trnsprent supercpcitor electrode mteril. This technique
eliminted the requirement of PFO being soluble in the medium in which nnosheets re suspended.
This lm composition displyed pproximtely 20 mF/cm2 of re cpcitnce t >75% trnsmis-
sion. The high cpcitnce cn be ttributed to Ti3C2Tx nnosheet nd high trnsmittnce by PFO.
Sho et l. (2018) developed werble supercpcitors using nnober-coted yrn (NCY) elec-
trodes with MXene/polymer composite (PET@MXene NCY). A modied electrospinning proce-
dure ws employed to self-wound MXene nnobers onto polyester (PET). PET@MXene NCY
demonstrted desired textile properties, including exibility, strength, nd fbricbility. A com-
prison between grphene nd crbon nnotube yrn supercpcitors reveled tht they hd higher
electrochemicl performnce. In ddition, yrn supercpcitors provided  high rel cpcitnce,
enhnced energy density, nd high power density of 18.39 mF cm−2, 0.38 μW h cm−2, nd 0.39 mW
cm−2, respectively. Furthermore, 98.2% of the specic cpcitnce ws retined fter 6000 cycles.
The high electroctivity of MXene nd good mechnicl properties of PET offered desirble prop-
erties to yrn supercpcitors.
Ren et l. (2018) reported PANI-modied 2D Ti3C2 composites by in situ polymeriztion nd
investigted the electrochemicl performnce. Incorporting PANI to Ti3C2 exhibited enhnced
electrochemicl performnce due to the presence of –NH groups in PANI tht fcilitted not only
fster ion trnsport nd incresed electric conductivity. Active interction between PANI nd
Ti3C2lso resulted in improved surfce wettbility. Hence, more ctive sites on PANI-Ti3C2 com-
posites enhnced the rte of frdic rections in the composite. PANI-Ti3C2 composites revel 
mximum specic cpcitnce of 164 F g−1 t the scn rte of 2 mV s−1 nd superior cycling stbil-
ity becuse of 96% retention of initil cpcitnce even fter 3000 glvnosttic chrge–dischrge
cycles.
Zhu et l. (2016) synthesized  uniform lm of l-Ti3C2, to which PPy ws interclted using
electrochemicl polymeriztion. They found tht when compred to the pristine PPy lm, the fbri-
cted supercpcitor showed  30% enhnced cpcitnce with  vlue of 406 F cm−3. Furthermore,
the PPy/l-Ti3C2 lm demonstrted improved cyclic stbility; even fter 20,000 chrge–dischrge
cycles, the cpcitnce ws lmost unffected. The incresed cpbility nd cycling stbility were
ttributed to MXene, which ws responsible for ssisting ion mobility nd chrge crrier migrtion
s well s strengthening the PPy bckbones. An ultr-thin ll-solid-stte supercpcitor ws lso
fbricted using this PPy/l-Ti3C2 lm, which mesured n excellent cpcitnce of 35 mF cm−2 nd
displyed both outstnding deformtion tolernce nd excellent cycling stbility.
Gund et l. (2019) reported porous MXene/conducting polymer hybrids Ti3C2/PEDOT: PSS elec-
trode hving n interconnected network structure for exible symmetric electrochemicl cpcitors.
The MXene/polymer nnocomposites exhibited  high cpcitnce of 24.2 F cm−3 t  high fre-
quency of 120 Hz. Additionlly, it hd long-term durbility of 30,000 cycles nd could function t
60–10000 Hz. The results of Bode nd Nyquist plots evidenced excellent responses to high frequen-
cies of Ti3C2/PEDOT: PSS hybrid electrode. The phse ngle t 120 Hz is one of the crucil prm-
eters to ssess its efciency s AC lter since n idel cpcitor hs  phse ngle of −90°. The
240 MXene-Filled Polymer Nanocomposites

phse ngles nd cutoff frequencies of Ti3C2/PEDOT: PSS (1:1 wt %) nd Ti3C2/PEDOT: PSS (1:2
wt %) were 76.1°, nd 79.1° t 120 Hz nd 1.60, nd 1.41 kHz t −45°, respectively. Ti3C2/PEDOT:
PSS electrodes exhibited  smller phse ngle t low frequencies due to the frdic effect in the
overll cpcitive property. The Nyquist plot shows n lmost negligible semicircle in the Ti3C2/
PEDOT: PSS electrode indicting the rpid ionic trnsport. The Ti3C2/PEDOT: PSS electrode lm
with excellent responses to high frequencies nd high volumetric cpcitnce cn be efciently used
in currently vilble devices s well. Tble 12.1 shows  comprtive study on the electrochemicl
performnce of vrious MXene/polymer composite mterils used in supercpcitor pplictions.

12.2.2 MXENE/POLYMER NANOCOMPOSITES IN BATTERY APPLICATION

However, despite its excellent electrolyte fnity nd electricl conductivity, MXene/polymer nno-
composites re underutilized in bttery pplictions compred to their ppliction in other pplic-
tions in the eld of supercpcitors. Nevertheless, reserchers hve explored their possible use in
whole bttery systems comprising electrodes, membrne seprtors, nd electrolytes (Chen et l.,
2021).
Polymer–MXene nnocomposites lso nd ppliction in lithium–ion storge performnce. Chen
et l. (2017) developed  combintion of d-Ti3C2Tz nd PEDOT to improve lithium-ion storge per-
formnce through enhnced ion trnsport with incresed interlyer spcing for improved lithium–
ion uptke. It is noticed tht the coulombic efciency of MXene/PEDOT improved considerbly by
53%, while pure MXene hd n efciency of only 38%. Even t 1000 mA g−1, the MXene/PEDOT
hd  cpcity of 71 mAh g−1, which ws higher thn the pure MXene cpcity of 9 mAh g−1.

TABLE 12.1
Comparison of Electrochemical Performance of Different MXene/Polymeric
Composite Materials
Specic/Areal/
Volumetric
Material Capacitance Retention Energy Density Power Density Ref.
PPy/Ti3C2Tz 1000 Fcm−3(VC) 92% – – (Boot et l., 2016)
Ti3C2Tx//PANI@ 57 Fg−1(SC) 88% 17 – (Boot nd Gogotsi,
rGO Wh kg−1 2019)
wvy-Ti3C2Tx//rGO/ 1277 F cm−3(VC) – 70 111 kW L−1 (Li et l., 2020b)
CNT/PANI Wh L−1
MXene/PFDs 1026 F cm−3(VC) – – – (Boot et l., 2017)
Mo1.33C MXene/ 568 F cm−3(VC) – 33.2 mWh cm−3 19470 mW cm−3 (Qin et l., 2018)
PEDOT: PSS
t-MXene/PEDOT: 1.5 F cm−3(VC) 98% – – (Zhng et l., 2021)
PSS
PEDOT-MXene 47.4 mF cm−2(AC) – 250.1 mWh cm−3 32.9 (Qin et l., 2019)
W cm−3
PDT/Ti3C2Tx 284 mF cm−2(AC) – 250.1 mWh cm−3 32.9 (Wu et l., 2019)
W cm−3
Ti3C2Tx/PFO 20 mF cm−2(AC) – – – (Ajnsztjn et l., 2020)
PET@MXene NCY 18.39 mF cm−2(AC) 98.2% 0.38 0.39 (Sho et l., 2018)
μWh cm−2 mW cm−2
PANI-Ti3C2 164 F g−1(SC) 96% – – (Ren et l., 2018)
PPy/l-Ti3C2 406 F cm−3(VC) 100% – – (Zhu et l., 2016)
Ti3C2/PEDOT: PSS 24.2 F cm−3(VC) – – – (Gund et l., 2019)
Energy Conversion and Storage Systems 241

FIGURE 12.3 Cyclic stbility of Ti3C2Tx–PEDOT: PSS hybrid (Li et l., 2020).

Probbly, PEDOT is lrgely  spcer for MXene lyers, enbling better mobility of ions. This report
is cler evidence tht d-Ti3C2Tz s  ller improved Li–ion uptke nd is suitble in Li–ion storge
devices.
Li et l. (2020) fbricted Ti3C2Tx–PEDOT: PSS hybrid to chieve high-performnce Li–S bt-
teries. Li–S btteries with PEDOT: PSS experienced incresed electricl conductivity nd signi-
cntly reduced Ti3C2Tx stcking. In turn, it promoted more efcient trnsport of Li+ ions s well s
more sulfur utiliztion. By incorporting PEDOT: PSS into Ti3C2Tx nnosheets, it ws lso pos-
sible to inhibit the shuttle effect nd improve the energy storge performnce of Li–S btteries.
Figure 12.3 shows the cyclic stbility ofTi3C2Tx–PEDOT: PSS hybrid. Consequently, Li–S btteries
with Ti3C2Tx–PEDOT: PSS seprtor offer superior electrochemicl performnce with  higher dis-
chrge rte of 1241.4 mAh g−1, longer cycle life, nd  low decy rte of 0.03% per cycle.
Chen et l. (2021b) synthesized  solid polymer electrolyte (SPE) composed of poly (vinylidene
uoride-co-hexuoropropylene) lled with poly (methyl crylte) grfted MXenes (denoted s
PVHF/MXene-g-PMA) for high-performnce zinc btteries. To fcilitte hydrogen bond formtion
with PVHF s  mtrix, the MXenes were grfted with PMA. At room temperture, the resultnt
SPE exhibited  conductivity (2.69 ×10 −4 S cm−1) three times greter thn tht of the PVHF mtrix.
A mjor dvntge of the development of SPEs is tht they provide signicnt shelf life for Zinc Ion
Btteries. The storge stbility studies by glvnosttic chrge–dischrge cycle illustrted the stble
cpcitnce delivered by PVHF/MXene-g-PMA even fter 90 dys t  high or low temperture.
Dong et l. (2018) fbricted exible nd integrted sulfur cthode (-Ti3C2-S/d-Ti3C2/PP) using
lklized Ti3C2 MXene nnoribbon with S/polysuldes host (-Ti3C2-S) nd delminted Ti3C2
MXene (d-Ti3C2) nnosheets s interlyer on polypropylene (PP) seprtor, for Li−S btteries. The
fbricted electrode chieved  higher cpcitnce of 1062 mAh g−1 t 0.2 Coulomb. Here MXene-
bsed cthode eliminted the need for Al current collector, thus gurnteeing the possibility for
next-genertion exible energy storge devices.
Songs et l. (2016) improvised the performnce of Li–S btteries by coting Ti3C2Tx MXene
nnosheets on polypropylene (PP; “Celgrd”) membrne. Figure 12.4 represents  schemtic di-
grm of Li–S cell with porous PP seprtor nd MXene-modied seprtor. Powered by improved
electricl conductivity nd effective trpping of polysuldes, MXene-functionlized lithium–sulfur
btteries performed exceptionlly well, with  high dischrge cpcity of 550 mAh g−1 fter 500
cycles with  cpcity decy of only 0.062% per cycle t 0.5 Coulomb. MXenes re thus  prime
cndidte for improving the electrochemicl efciency of lithium−sulfur btteries. Tble 12.2
describes  comprtive study on the cpcitnce of vrious MXene/polymer composites in  bt-
tery ppliction.
242 MXene-Filled Polymer Nanocomposites

FIGURE 12.4 Schemtic digrm of Li–S cell with  porous PP seprtor nd MXene-modied seprtor
(Song et l., 2016).

TABLE.12.2
Comparison of the capacity of Various MXene/Polymer Composites in Battery Application
Capacitance
Material (mAh g−1) Ref.
d- Ti3C2Tz/PEDOT 71 (Chen et l., 2017)
Ti3C2Tx–PEDOT: PSS 1241.4 (Li et l., 2020)
PVHF/MXene-g-PMA 72.3 (Chen et l., 2021b)
-Ti3C2-S/d-Ti3C2/PP 1062 (Dong et l., 2018)
Ti3C2Tx- PP 550 (Song et l., 2016)

12.2.3 MXENE/POLYMER-BASED ELECTRODE MATERIALS IN FUEL-CELL APPLICATION

Fei et l. (2017) reported the proton conductivity of the Ti3C2Tz -PBI composite membrne, nding
n ppliction in polymer electrolyte membrne fuel cells. Figure 12.5 shows tht Ti3C2Tz incor-
ported into the PBI membrne hs enhnced proton conductivities. The conductivity of 3 wt%
Ti3C2Tz -PBI membrnes is in the rnge of 4.5 × 10 −3–1.4 × 10 −2 S cm−1, which is higher thn the
pristine PBI (8.1 × 10 −4 –5.1 × 10 −3). A high ctivtion polriztion loss of 0.25 V t 0.1 A cm−2 nd
 fuel-cell voltge loss of 0.6 nd 0.4 V from 0.22 to 0.52 A cm−2, ws reported for Ti3C2Tz–PBI
membrnes. The conductivity of Ti3C2Tz–PBI membrnes with respect to the fuel-cell performnce
ws clculted to be 0.0091 S cm−1. The power density of the 3 wt% Ti3C2Tz–PBI-bsed fuel cell
is 135 mW cm−2 nd 209 mW cm−2 t 120°C nd 150°C, respectively. This study demonstrted
the efciency of Ti3C2Tz-MXene s  potentil ller to obtin Ti3C2Tz–PBI-bsed polymer com-
posite membrnes, nd its ppliction in PEMFC operted t intermedite temperture fcilittes
enhnced proton conductivity.
For the PEM wter electrolysis, Wribm et l. (2021) incorported crosslinked sulfonted
polyether ether ketone (C-SPEEK) with vrying mounts of MXene/potssium titnte nnowire
(MKT-NW), which cted s  ller for the PEM wter electrolysis. Proton conductivity nd ion
exchnge cpcity for 12% MKT-NW/C-SPEEK were found to be 0.9971 S cm−1 nd 1.88 meq g−1,
respectively. About 0.180566 mmol of hydrogen gs ws produced within 5hours with the 12%
MKT-NW/C-SPEEK membrne.
Energy Conversion and Storage Systems 243

0.014 PBI DP=3.43

3 wt.% TI3C2Tx-PBI DP=3.31

0.012
5 wt.% TI3C2Tx-PBI DP=3.23
Proton Conductivity/S cm-1

0.010
10 wt.% TI3C2Tx-PBI DP=3.32

0.008

0.006

0.004

0.002

0.000
100 110 120 130 140 150 160 170
Temperature/°C

FIGURE 12.5 Proton conductivities of pure PBI nd Ti3C2Tz-PBI membrnes (Fei et l., 2017).

12.3 CONCLUSION
Polymer nnocomposites re widely employed in our dily lives. Compred to the polymer mtrix,
the chrcteristics of polymer nnocomposites my be customized nd substntilly enhnced by
incorporting 2D nnollers. Among vrious 2D nnollers, MXene cn bestow polymer mtrices
with fvorble trits to meet the growing need for  wider vriety nd diversity of functionl poly-
mers. The prticulr focus on Ti3C2 MXene-bsed polymer nnocomposites in energy conversion
nd storge of most of the reports reveled enhncement in electrochemicl performnce by dding
MXene. Thus, it ws evident tht polymer MXene nnocomposites hve  gret del of potentil in
supercpcitor pplictions. Although mny genuine reports re vilble on the polymer–MXene
nnocomposites, the remrkble properties of these composites, keeping open mny opportunities
to extrct its mximum use for humnkind. Nnocomposites with MXene nd polymers hve been
explored sprsely for bttery nd fuel-cell pplictions. There hs been  vst discovery of conduct-
ing polymers nd proton exchnge polymers, which cn be utilized to incorporte in MXene to
expnd its eld of bttery nd fuel-cell pplictions. Another chllenge tht still exists is how to
imprt the electrochemicl dvntges of MXenes to polymer–MXene composites for industril
pplictions. The selection of polymers, synthesis process, nd modiction of MXenes could be
concentrted to unlock the full scientic potentil of these nnocomposites in studies relted to fuel-
cell nd bttery ppliction for indigenous deliverbles.

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WANG, J., TANG, J., DING, B., MALGRAS, V., CHANG, Z., HAO, X., WANG, Y., DOU, H., ZHANG,
X. & YAMAUCHI, Y. 2017. Hierrchicl porous crbons with lyer-by-lyer motif rchitectures from
conned soft-templte self-ssembly in lyered mterils. Nature Communications, 8, 15717 (2017).
WARIBAM, P., JAIYEN, K., SAMART, C., OGAWA, M., GUAN, G. & KONGPARAKUL, S. 2021. MXene
potssium titnte nnowire/sulfonted polyether ether ketone (SPEEK) hybrid composite proton
exchnge membrne for photoctlytic wter splitting. RSC Advances, 11, 9327–9335.
WU, X., HUANG, B., LV, R., WANG, Q. & WANG, Y. 2019. Highly exible nd low cpcitnce loss superc-
pcitor electrode bsed on hybridizing decentrlized conjugted polymer chins with MXene. Chemical
Engineering Journal, 378, 122246.
ZHANG, M., HÉRALY, F., YI, M. & YUAN, J. 2021. Multitsking trtric-cid-enbled, highly conductive,
nd stble MXene/conducting polymer composite for ultrfst supercpcitor. Cell Reports Physical
Science, 100449.
ZHU, M., HUANG, Y., DENG, Q., ZHOU, J., PEI, Z., XUE, Q., HUANG, Y., WANG, Z., LI, H. & HUANG,
Q. 2016. Highly exible, freestnding supercpcitor electrode with enhnced performnce obtined by
hybridizing polypyrrole chins with MXene. Advanced Energy Materials, 6, 1600969.
 13 Biomedical Applications
of MXene/Polymer
Nanocomposites
Nupur Garg and Farhan J. Ahmad

CONTENTS
13.1 Introduction ........................................................................................................................... 247
13.2 Biomedicl Properties ........................................................................................................... 249
13.2.1 Surfce-to-Volume Rtio........................................................................................... 249
13.2.2 Shpe nd Morphology ............................................................................................. 249
13.2.3 Hydrophilicity ........................................................................................................... 249
13.2.4 Conductivity .............................................................................................................. 250
13.2.5 Phototherml Conversion .......................................................................................... 250
13.3 Drug Delivery........................................................................................................................ 250
13.4 Bioimging............................................................................................................................ 251
13.5 Cncer Thernostics .............................................................................................................. 252
13.6 Antibcteril Applictions..................................................................................................... 253
13.7 Biosensing ............................................................................................................................. 253
13.8 Future Perspectives ............................................................................................................... 255
13.9 Conclusion............................................................................................................................. 255
Bibliogrphy .................................................................................................................................. 256

13.1 INTRODUCTION
In the clss of two-dimensionl (2D)-lyered mterils, MXenes hve shown immense potentil
in the eld of helthcre. Attributed to their excellent electricl, therml nd mechnicl proper-
ties, high surfce-to-volume rtio, nnoscle thickness nd exible surfce, they re pplied to the
biomedicl eld for innovting new methods in therpeutics like biosensing, phototherml or pho-
todynmic therpies, drug delivery, dignostic nd regenertive medicine. Their structure consists
of  mixture of different surfce functionl groups like hydroxyl (–OH), uoride (–F) or oxygen
(–O) groups, tht rise during the etching step of the synthesis, with exchngeble ctions like
wter. These give MXenes high hydrophilicity, surfce rectivity, good biocomptibility nd unique
electricl nd opticl properties. This pves the wy for stble MXene suspensions nd doping with
different hydrophilic polymers. The use of polymer-doped MXenes further increses their verstil-
ity to be pplied to therpeutics.
With the incresing demnd of helthcre nd biomedicl mterils nd methods, it is impertive
for reserchers to come up with innovtive techniques nd products. MXenes hve pved the wy for
wider reserch scope in therpeutic mterils. MXene/polymer nnocomposites (MX/P-NCs) hve
been utilized in the development of multifunctionl exible nd smrt fbrics nd devices, wound
heling dressings nd werble electronics. MXenes hve vrious surfce-ctive sites, which mkes
it esier to functionlize with different polymers to form polymer nnocomposites (MX/P-NCs) due
to which they disply high selectivity nd sensitivity. Depending on the choice of polymers, they
show high exibility nd cn further be developed into  vriety of sensors nd detectors. Mny

DOI: 10.1201/9781003164975-13 247

248 MXene-Filled Polymer Nanocomposites

reserch studies hve investigted the bctericidl properties of MX/P-NCs tht re discussed fur-
ther in this chpter. Severl mechnisms hve been proposed for their ntibcteril ction, including
the genertion of rective oxygen species (ROS) cusing oxidtive stress, interction with bcteril
protein nd nucleic cids to cuse cell deth, inhibition of electron trnsport, nd physicl stress
with their shrp edges resulting in mechnicl dmge of the cell membrne nd loss of integrity,
penetrtion nd lekge of the cell membrne (Rsool et l., 2016). They hve been crosslinked
with different polymers to cuse synergistic ction on their ntibcteril property due to chemicl
nd physicl effects. Polymer doping mkes the MXene moiety more biocomptible nd enhnced
interction with bcteril cell membrnes for better contct.
Aprt from these pplictions, they hve been used in dignostic imging techniques s contrst
gents for better medicl imge qulity tht shows disesed tissue in contrst with the norml tissue
bckground, in trgeted cncer chemotherpy through photoconversion mechnism nd ssocited
hypertherml tretment nd in severl on-site novel drug delivery systems by surfce ssocitions
of vrious types of receptor lignds, ntibodies, functionl groups nd rdicl toms. Their ther-
nostic pplicbility cn be understood by their phototherpeutic bility mjorly in cncer chemo-
therpeutics. The phototherml bltion tretment of cncer hs been proved to reduce the tumor
tissue prt from dignosing the cncerous prt. They cn be used simultneously for dignosing
the disesed prt of the body s well s the relese of the therpeutic gent t the trget site. Their
unique 2D structure is n dded dvntge to be explored by intercting with different types of
polymers nd nnoprticles, long with the ctive gent to form nnocomplexes. They re proving
to be sclble for industril pplictions despite their specic structure complexity being  chl-
lenge (Soleymnih et l., 2019). This chpter summrizes the importnt pplictions in the eld of
helth mngement nd biomedicl sector s depicted in Figure 13.1.

FIGURE 13.1 Biomedicl pplictions of MX/P-NCs.

Biomedical Applications of MXene/Polymer Nanocomposites 249

13.2 BIOMEDICAL PROPERTIES

MXene/P-NCs hve severl unique properties tht mke them importnt constituents to be used
in the biomedicl sector nd disese mngement. Attributed to their size, structure nd bility to
crosslink in different wys with different polymers, they present vrious possibilities to be utilized
in therpeutics. Figure 13.2 summrizes the mjor properties of MX/P-NCs tht could be hrnessed
for biomedicl pplictions.

13.2.1 SURFACE-TO-VOLUME RATIO

Bestowed with  high surfce-to-volume rtio nd lrge specic surfce re, surfce functionl-
iztion with desired groups is much esier nd provides  number of polymer crosslinking options.
MXenes behve s potent moieties if specic rective groups re ttched to its surfce, which helps
in its trgeted ction nd in formulting drug delivery systems.

13.2.2 SHAPE AND MORPHOLOGY

MXene nnosheets comprise 2D thin nd t structures with shrp edges tht result from n exfo-
lition of the lyers during synthesizing process. These help in cusing stress nd physicl dm-
ge to the bcteril cell membrnes. Nnocomposites with desired surfce modictions cn be
obtined by the homogeneous dispersion of exfolited sheets into desired polymer mtrix to rech
to the trget better. Vrious electron donors re present nd cn be doped with desired polymers
to chieve trgeted results. Their surfce morphology cts s  criticl fctor in therpeutic bility
(Soleymnih et l., 2019).

13.2.3 HYDROPHILICITY
The presence of their negtive surfce chrge, long with bundnt surfce functionl groups,
they cn esily interct with wter molecules. This surfce chemistry is responsible for rendering
MXenes hydrophilic due to which they cn be formulted to stble suspensions in wter or other

FIGURE 13.2 Biomedicl properties of MX/P-NCs.

250 MXene-Filled Polymer Nanocomposites

polr solvents tht too t neutrl pH. This mkes it esier to link nd interct with severl hydrophilic
polymers nd biopolymers, mking them biocomptible nd biodegrdble (Chen et l., 2021).

13.2.4 CONDUCTIVITY
Attributed to their high conductivity, MX-P/NCs re interestingly employed in severl bioengineer-
ing devices such s sensors, lms or fbrics. This property cn be exploited in bioimging nd ther-
nostic pplictions of polymeric nnocomposites. By trcking the metllic conductnce, surfce
functionl groups cn be identied to know the binding sites for nlytes. Gs sensors nd molecule
sensors cn be fbricted for highly sensitive nlyte determintion. They lso hve mny free chrge
crriers t their surfce due to which they cn reect electromgnetic wves before bsorption nd,
hence, used in detection nd imging. This behvior gives rise to the unique optoelectronic proper-
ties of MX-P/NCs, which is exploited in mny bioimging techniques (Crey nd Brsoum, 2021).

13.2.5 PHOTOTHERMAL CONVERSION

Phototherml therpy (PTT) is  novel pproch tht is done by trgeted heting of photothermlly
ctive nnocomposites t the cncerous site without dmging the helthy tissues. They ct by
bsorbing electromgnetic rdition in the ner-infrred (NIR) window nd killing cncer cells by
light-to-het conversion. The efciency of PTT is bsed on the size nd loction of the tumor nd
the het generted to reduce it. Severl studies hve been reported tht used MXene hyperthermi
s synergistic therpy long with other encpsulted nticncer gents for cncer tretment.
Similrly, photodynmic therpy (PDT) hs lso been explored for cncer tretment. This
therpy cts on cncer cells by generting rective oxygen species (ROS) from  prodrug using
 photosensitizing gent nd n ctivtion gent, resulting in cncer cell deth through oxidtive
photodmge. Generlly, PDT is used in conjunction with other cncer therpies like chemotherpy
or rdiotherpy (Lin et l., 2018).

13.3 DRUG DELIVERY

One of the mjor biomedicl pplictions of MX-P/NCs is their role in novel drug delivery sys-
tems. Delivery systems guided, controlled, sustined nd trgeted relese of drugs is inevitble for
mximum therpeutic effect with  minimum dose nd metbolism in disese therpy. This purpose
is ttined by exploring the exibility of MX-P/NCs for polymer–drug interctions. Mny types
of nnocomplexes cn ttck the trget disese cells efciently, nd MX-P/NCs further enhnce
the rech, efciency nd therpeutic efccy of the system by offering different pthwys for
drug–disese interctions. They hve been good crriers for delivering nticncer drugs in cncer
chemotherpy. Hn et l. investigted the use of SP-modied Ti3C2 nnosheet complexes s drug
crriers nd therpeutic synergistic gents for cncer therpy. These complexes, prt from pos-
sessing high drug-loding cpcity, lso provide pH-responsive nd lser-triggered drug relese
(Hn et l., 2018). Similr work ws done by Liu nd coworkers (2020) by prepring nnocrri-
ers of coblt nnowires with Ti3C2 for synergistic nticncer effect with doxorubicin long with
mgnetic controlled drug relese. A group of reserchers (Zhng et l., 2019) fbricted MXene/
polycrylmide nnocomposite hydrogel for higher mechnicl gel strength, high drug loding nd
better sustined relesed properties. The tumor-trgeted therpy using MX/P-NCs hve gined 
huge interest mong reserchers. A study group (Xing et l., 2018) developed  Ti3C2/cellulose
nnocomposite hydrogel tht combines the phototherml bility of MXene with incresed biocom-
ptibility nd sustined drug relese properties of cellulose. They reported  48-hour long-sustined
distribution nd relese of nticncer drug doxorubicin hydrochloride (DOX). This system shows 
synergistic therpeutic effect with phototherpy plus chemotherpy ginst tumor cells. Tble 13.1
presentsreserch done on employing MX/P-NCs in drug delivery systems.
Biomedical Applications of MXene/Polymer Nanocomposites 251

TABLE 13.1
Applications of MX/P-NCs in Drug Delivery
Delivery system Therapeutic Intervention Results Reference
2D Ti3C2 MXenes Tumor erdiction High drug loding, pH- nd lser- (Hn et l., 2018)
triggered relese, synergistic PT
Ti3C2 cobalt nanowires Chemo-phototherml therpy Mgnetic/pH responsive/NIR (Liu et l., 2020)
controlled relese, PT efccy
MXene-polyacrylamide Vehicle for enhnced drug High mechnicl strength, drug (Zhng et l., 2019)
hydrogel relese loding, exibility nd gel properties
Ti3C2/cellulose hydrogel Trgeting nd controlled Sustined drug relese, biocomptible, (Xing et l., 2018)
relese for cncer PT tumor scvenging bility with
chemotherpy doxorubicin

TABLE 13.2
Applications of MX/P-NCs in Bioimaging
MX/P-NCs Imaging Technique Results Reference
Ti3C2 polyoxometalates MRI/CT Hypertherml tretment, (Zong et l., 2018)
dignostic contrst gent
Ta4C3-MnOx-SP PTT/MRI/CT for tumor Phototherml hyperthermi, (Di et l., 2017)
contrst gent
MnOx/Ti3C2-SP PTT/MRI/CT for tumor Tumor hyperthermi (Di et l., 2017b)
Ta4C3-Fe3O4 PTT/MRI/CT for tumor Tumor erdiction, (Liu et l., 2018)
phototherml bltion
Ti3C2 QDs PTT for tumor Multicolor cellulr imging (Xue et l., 2017)
probes
Ti3C2 QD/Chitosan Stem cell–bsed therpy Inmmtion nd tissue repir (Reerd et l., 2019)

13.4 BIOIMAGING
The inherent physicochemicl properties of MX/P-NCs, including the conductivity, optic, elec-
tronic, mgnetic, nd the like, present the scope of exploiting them in imging techniques. Mgnetic
resonnce imging (MRI) is one such technique tht uses  contrst gent tht cn be guided in the
electromgnetic eld to give enhnced resolution imges. A contrst gent is used to increse the
bility of medicl imging to differentite norml nd disesed tissues by providing  bckground
contrst by ltering electromgnetism or ultrsonic bsorption. They improve the imge qulity
of the dignostic method. MXenes decorted with different types of mgnetic nnoprticles could
provide MRI contrsting long with their therpeutic performnce t the sme time. Few such
studies re compiled in Tble 13.2. Zong nd coworkers (2018) integrted the surfce of titnium
crbide (Ti3C2) MXene nnosheets with polyoxometltes to present MRI or computed tomogrphy
(CT) imging of tumor cells long with their inherent property of hypertherml ction on tumor
dening their thernostic pplictions. Di et al. chieved surfce functionliztion of tntlum
crbide (T4C3) nnosheets with mngnese oxide (MnOx) nnoprticles to perform s contrst
gents for CT/MRI nd showed phototherml hyperthermi in tumor suppression so s to use them
for PTT. Other work by the sme reserch group (Di et l., 2017b) showed the efciency of MnOx/
Ti3C2nnosheets s multifunctionl thernostic gents in MRI-guided tumor hyperthermi.
Supr-prmgnetic iron oxide nnoprticles hve been regrded s excellent contrst gents in
dignostic imging. Therefore, the surfce functionliztion of MXenes with these nnoprticles
252 MXene-Filled Polymer Nanocomposites

could be utilized to complement these nnosheets with MR-enbled bility. Reserchers (Liu et l.,
2018) hve explored the tntlum crbide MXenes with superprmgnetic iron oxide functionl-
iztion for brest cncer thernostic. Xue nd coworkers (2017) fbricted biocomptible photolu-
minescent quntum dots of Ti3C2MXenes (MQD) nd demonstrted their ppliction in multicolor
imging cellulr probes. Another ppliction of MQD ws shown by reserchers (Reerd et l.,
2019) by formulting  MQD-chitosn hydrogel with improved physicochemicl properties. They
demonstrted its scope in trnsltionl medicine for tissue repir in inmmtory nd degenertive
diseses.

13.5 CANCER THERANOSTICS

Severl reserchers hve explored nd pplied the phototherml properties of vrious types of
MX/P-NCs to cncer therpies mjorly by using the inherent hypertherml bility of the nnosheets
long with the therpeutic efccy of the nticncer drug nnoprticles. By incorporting the nti-
cncer drug in the polymeric 3D porous structure, high drug loding nd uptke cn be done. In
the pst couple of yers,  number of 2-D nnocomposites were developed for better dignostic
screening (PTT/CT/MRI) nd tretment of cncer. This hs been chieved due to severl merits tht
MX/P-NCs exhibit, nmely, nnosized for enhnced permetion through brriers, tumor penetr-
tion nd retention, nd incresed surfce re for  wide scope of surfce functionliztion with dif-
ferent therpeutic moieties. MX/P-NCs hve been widely reserched for oncologicl pplictions.
They could be used in different therpies like cncer chemotherpy, rdition therpy, phototherml
therpy nd photodynmic therpy (PDT). For dignostic purposes, MX/P-NCS hve been utilized
s contrst gents in severl techniques like MRI, photocoustic imging (PAI), CT imging nd
sensing. Also, they could be used in cncer thernostics s the delivery systems for nticncer drugs
nd contrst gents for imging nd tretment simultneously. Numerous reserch groups hve
developed specic MX/P-NCs for cncer dignostic imging, some of which re summrized in
Tble 13.3.
Lin et al. rst reported the phototherml bltion cpbility of ultr-thin MXene nnosheets
ginst cncer by developing soyben phospholipid–modied Ti3C2 nnosheets for intrvenous
dministrtion (Lin et l., 2017b). They lso demonstrted  similr effect in loclized tumor

TABLE 13.3
Application of MX/P-NCs in Cancer Therapies
MX/P-NCs Therapeutic Intervention Study Results Reference
SP-Ti3C2 Phototherml bltion High photoconversion (Lin et l., 2017b)
efciency
Al(OH)4- functionalized Chemotherpeutic/PTT/ ROS genertion, high drug (Liu et l., 2017)
Ti3C2-DOX PDT loding, ctive trgeting
Mo2C-PVA nanoakes Photonic tumor Biocomptible, intense NIR (Feng et l., 2019)
hyperthermi bsorption, deep tissue
penetrtion
Nb2C PVP Phototherml bltion with Low phototoxicity, high (Lin et l., 2017)
two NIR bio-windows biocomptibility, enzyme-
responsive biodegrdbility
Silica coated Synergistic chemotherpy High hydrophilicity, controlled (Li et l., 2018)
Ti3C2MXene nd hyperthermi in drug relese, ctive trgeting
heptocellulr crcinom
Ti3C2@Au-PEG Rdiotherpy, CT, High opticl bsorption, (Tng et l., 2019)
Photocoustic therpy cncer thernostics
Biomedical Applications of MXene/Polymer Nanocomposites 253

implntble Ti3C2/PLGA hybrid. The sme group (Lin et l., 2017) developed niobium crbide
MXene nnosheets for ner infrred rdition (NIR)–bsed PTT through two bio-windows NIR-I
nd NIR-II s shown in in vivo xenogrfts. Liu et l. synthesized multifunctionl system of surfce-
modied Ti3C2-DOX for PTT/PDT long with synergistic chemotherpy (Liu et l., 2017). The
reserch on synthesizing novel MX/P-NCs for cncer therpy hd gined vst interest in the pst
couple of yers. Feng et l.(2019) developed molybednum crbide (Mo2C) MX/P-NCs with polyvi-
nyl lcohol (PVA) through surfce engineering to increse the biodegrdbility nd biocomptibil-
ity of the system. They possessed PT-conversion efciency in both NIR bio-windows for photonic
tumor hyperthermi. Li et l. reported the tretment of heptocellulr crcinom through PTT nd
synergistic chemotherpy (Li et l., 2018). They synthesized receptor trgeted Ti3C2 MXene surfce
functionlized with  lyer of thin mesoporous silic. They showed trgeted nd controlled drug
relese, enhnced hydrophilicity nd scope for more surfce engineering for desired drug-trget
rech. The chemotherpeutic effect from the surfce functionliztion nd phototherml hyperther-
mi by the MXene core contributed to the erdiction of the tumor s shown by their in vitro nd
in vivo results. Tng et l. used gold for surfce modiction of Ti3C2 MX/P-NCs for incresing
stbility nd biocomptibility nd mintining low toxicity. This lso enhnced the imging prop-
erty using photocoustic nd CT nd could be used for rdiotherpy in cncer thernostics (Tng
et l., 2019).

13.6 ANTIBACTERIAL APPLICATIONS

The ntibcteril ctivity of MX/P-NCs hs been well reserched nd documented by severl
reserchers. The mechnisms, including both physicl nd chemicl fctors, re proposed to explin
their ntimicrobil properties ginst both grm-positive nd grm-negtive bcteri. The bcteri-
killing bility of MXenes is ttributed to the genertion of ROS, mechnicl dmge to the integrity
of bcteril membrne by the shrp edges of the 2D MX/P-NCs nnosheets structure, direct pen-
etrtion nd interction with the sulfur nd phosphorus groups of the bcteril protein nd DNA,
respectively. The high hydrophilicity my enhnce the surfce contct of bcteri with MXenes
leding to the inctivtion nd killing of bcteri by direct contct. These properties of MXenes
my contribute to their use in disinfectnt industry since they re biocomptible nd biodegrd-
ble lso. Rsool et al. investigted the ntibcteril ctivity of colloidl MXene ginst grm-
negtive Escherichia coli nd grm-positive Bacillussubtilis tht showed mechnicl dmge to
bcteril cells s well s ROS-dependent oxidtive stress to be the mjor resons of bcteril cell
deth (Rsool et l., 2016). Sme reserch group in nother study (Rsool et l., 2017) indicted
the bctericidl properties of titnium crbide-polyvinylidene uoride ginst E. coli nd B. sub-
tilis. Myerberger et l. prepred nontoxic biocomptible Ti3C2Tz/chitosn nnobers ntibcteril
wound dressing tht ws found to be effective ginst E. coli nd S. aureus nd showed wound hel-
ing properties of the sme (Myerberger et l., 2018). Polymers such s chitosn hd lredy been
explored (Chung nd Chen, 2008) s  nturl bctericide tht cts by intercting with the bcteril
membrne of E. coli nd S. aureus. They could be explored to hve  synergistic ction by combin-
ing with MXenes. As suggested by Li et al., bctericidl ction hs been shown by the production
of ROS by engineered metl oxide nnoprticles tht results in oxidtive stress to bcteri (Li et l.,
2012). Some of the studies done on MX/P-NCs to show their ntibcteril potentil re given in
Tble 13.4.

13.7 BIOSENSING
Severl MX/P-NC nnocomplexes hve been used to design sensors for detecting vrious helth
nd biologicl prmeters nd disese sttus by through detection of different nlytes, gseous
molecules, contminnts, physicl or motion stimuli, mong others. The mechnisms behind fb-
ricting MXene biosensors utilize their electrochemicl ctivity, which depends on the intensity
254 MXene-Filled Polymer Nanocomposites

TABLE 13.4
Applications of MX/P-NCs as Antibacterial Agents
MX/P-NCs Antibacterial Activity Results Reference
Colloidal MXene E. coli, B. subtilis Mechnicl dmge, (Rsool et l., 2016)
oxidtive stress
Ti3C2/polyvinylidene uoride E.coli, B. subtilis Dmge to bcteril cell (Rsool et l., 2017)
wll/genertion of ROS
Ti3C2Tz/chitosan nanobers E. coli, S. aureus Wound heling (Myerberger et l., 2018)
Ti3C2Tx MXene E.coli, B. subtilis Physicl interction, cell (Arbi Shmsbdi et l., 2018)
dmge

of trget signls. When MXene binds the biologicl trget or vice vers, its electronic properties
lter leding to genertion of current or chnges in  detector. With the introduction of high-
performnce nlyticl techniques, they hve emerged s n dvnced pltform for biosensing
pplictions. These hve been incorported into the comptible devices for rpid, esy nd sensi-
tive detection of specic biologicl chnge (Xu et l., 2020). Werble sensors hve been designed
to regulrly monitor bsic helth prmeters (Xin et l., 2020). With the use of different polymer
nnoprticles, their morphology cn be controlled nd developed to enhnce the sensing bil-
ity of MXene-bsed sensors. Rkhi et l. fbricted mperometric glucose biosensor using gold
nnoprticle–MXene (Au-NP-MXene) nnocomposite tht cts s the mtrix for immobilized
glucose oxidse enzyme through which mperometric detection could be obtined (Rkhi et l.,
2016). Similrly other reserchers (Wng et l., 2014; Liu et l., 2015) immobilized hemoglobin on
Ti3C2-MXene to develop peroxide nd nitrite meditor free biosensors. These types of biosensors
re used for environmentl nlysis of different types of nlytes. MXenes cn lso be used to
fbricte gs sensors to detect gses like mmoni or cetone to dignose diseses such s peptic
ulcers or dibetes, respectively. Kim et l. (2018) developed  highly sensitive detector of voltile
orgnic compounds tht helps in estimting their lrming levels in  disesed stte. Lorencov
et l. showed Ti3C2Tx /PtNP nnocomposites deposited on the electrodes cn detect smll mole-
cules, such s scorbic cid, dopmine, uric cid nd the like, in low limits implying tht these cn
be pplied for the development of enzyme-bsed biosensors (Lorencov et l., 2018). Severl body
biomrkers cn be identied using such sensors. MXene immunosensors bsed on ntigen–nti-
body interction hve lso been developed for high-throughput performnce of the nlyticl test
tht is cost-effective, portble, highly specic nd sensitive (Fng et l., 2020). Kumr nd cowork-
ers (Kumr et l., 2018) functionlized MXene nnosheets with minosilne to provide biorecep-
tor site for CEA (crcinoembryonic ntigen) binding for sensitive detection of cncer biomrker.
Tble 13.5 summrizes different types of biosensors developed using unique electrochemicl nd
morphologicl properties of MX/P-NCs.
Chen et l. developed  Ti3C2 quntum dots werble nnosensor for estimting intrcellulr
pH using  rtiometric luminescent probe (Chen et l., 2018). Detection of smll quntities of n-
lytes in blood cn be done esily through ffordble, point-of-cre nd rpid devices bsed on the
bility of MXenes to interct nd bind to different molecules. Zheng et l. (2018) fbricted n
MXene-bsed nnocomposite (MXene/DNA/Pd/Pt) to detect the levels of dopmine whereby DNA
is dsorbed on the Pd/Pt nnocomposite–MXene mtrix. MX/P-NCs doped with smll molecules
nd metl ions produce similr effect. Peng et l. fbricted  uorescent nnoprobe bsed on Ti3C2
nnosheets for nlysis of humn ppillomvirus, which is  custive pthogen of cervicl cncer
(Peng et l., 2019). Attributed to their unique conductive, opticl nd electronic properties, detection
nd nlysis in redble dt re esy to generte.
Biomedical Applications of MXene/Polymer Nanocomposites 255

TABLE 13.5
MXene Type of Biosensor Applications Reference
Au-NP-MXene Enzyme sensors Glucose detection (Rkhi et l., 2016)
Ti3C2Tx/PtNP Enzyme sensors Smll biomolecules like dopmine, (Lorencov et l., 2018)
uric cid, scorbic cid
Ti3C2-immobilized Enzyme sensors Meditor-free sensor for peroxide (Li et l., 2012, Arbiet l.,
hemoglobin or nitrite 2018)
Ti3C2-β-hydroxybutyrate Enzyme sensors Dibetic ketocidosis (Koyppyil et l., 2020)
dehydrogenase
Ti3C2Tx Gs sensors Voltile orgnic compounds (Kim et l., 2018)
Aminosilane-MXenes Immunosensors Anti-Crcinoembryonic ntigen (Kumr et l., 2018)
cncer biomrker
MXene-Ti3C2Tx Immunosensors Monitoring of blood components (Liu et l., 2019)
Ti3C2Tx and polyvinyl Strin sensors Physicl strin sensing (Zhng et l., 2019)
alcohol (PVA) hydrogel
Ti3C2Tx-polyacrylamide and Strin sensors Personlized helth monitoring (Lio et l., 2019)
polyvinyl alcohol
Ti3C2 quantum dots Werble sensors Monitoring intrcellulr pH (Chen et l., 2018)

13.8 FUTURE PERSPECTIVES

This is to understnd tht combining MX/P-NCs with vrious moleculr techniques for biomedicl
pplictions is still t its infncy. Numerous chllenges hve been seen in current reserch progress
on pplying them to helthcre systems. Their trnsltion pplictions still need to be exploited nd
fce chllenges, like industril pplictions or lrge-scle production, desired surfce engineering,
biosfety, controlling their behvior nd complexity, to nme  few. Due to their physicochemi-
cl properties, MXene–polymer blend optimiztion is inevitble. Multidisciplinry pproch in
their fbriction, to employ more specic, effective nd stble surfce modictions needs to be
ddressed in future reserch. To improve their performnces, tiloring nd controlling their unique
properties re necessry. They hve  wide scope in chemotherpeutics nd cncer thernostics,
which could be explored. Reserchers hve shown synergistic effects. Despite ll these chllenges,
MX/P-NCs hve shown gret potentil to be pplied in biomedicl techniques nd hve  wide
scope of reserch on their bench-to-bedside use.

13.9 CONCLUSION
MXene/polymer nnocomposites hve gined interest to be pplied to  number of biomedicl tech-
niques for better performnce, dvnced outputs, high-throughput efciency nd trget chievbil-
ity. Their exible nd tunble nture, unique electrochemicl nd mgnetic properties nd surfce
morphology hve mde them ttrctive components for pplictions in chemotherpy, biosensing
nd bioimging. Their ultr-thin 2D nnosheet structure hs opened severl doors to be explored
by modifying the surfce groups nd ttchments. Efcient linkge with severl types of biopoly-
mers hs mde them biodegrdble nd biocomptible, which dds nother merit in their use in
environmentl nd helthcre systems. This hs enbled them to ct s ntimicrobil gent. Their
hydrophilic nd swelling properties hve mde them excellent crriers in drug delivery systems.
The nnocomposites my encpsulte the desired ctive gent to be unloded t the trget site long
with the synergistic ction by the MXene moiety itself. This dded dvntge hs been explored in
chemotherpeutics. Phototherml conversion is nother unique property tht converts light to het
nd hs been efciently shown by vrious reserchers to reduce tumors. Aprt from the verstile
256 MXene-Filled Polymer Nanocomposites

pplictions of MX/P-NCs in thernostics, their pplicbility in biosensing systems hs pved the
pth for reserch in  wholly novel domin. Numerous types of biosensors hve been fbricted for
the detection of biomolecules, nlytes nd bio-chnges. In this wy, the development of these mul-
ticomponent nd multifunctionl systems hs been shown to chieve novel methods in biomedicl
nd helthcre systems.

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Colloidl Ti3C2Tx MXene Nnosheets. ACS Sustinble Chemistry & Engineering 6, 16586–16596.
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 14 Flexible and Wearable
Applications of MXene/
Polymer-Based
Nanocomposites
Heera S and Amal George Cheriyan

CONTENTS
14.1 Introduction to MXene/Polymer-Bsed Nnocomposites .................................................... 259
14.2 Clssiction of MXene/Polymer Nnocomposites ............................................................. 261
14.3 Applictions .......................................................................................................................... 261
14.4 Flexible nd Werble Applictions...................................................................................... 262
14.4.1 Generl Sensing Applictions ................................................................................... 262
14.4.1.1 Pressure Sensors (Piezoresistive Sensors) ................................................. 262
14.4.1.2 Strin Sensors............................................................................................. 263
14.4.1.3 Humidity Sensors....................................................................................... 266
14.4.1.4 Gs Sensors................................................................................................ 267
14.4.1.5 Epiderml Sensors ..................................................................................... 268
14.4.2 Electromgnetic Absorption nd Shielding Applictions ......................................... 269
14.4.3 Heter ........................................................................................................................ 271
14.4.4 Triboelectric Nnogenertors.................................................................................... 271
14.4.5 Werble Antenns.................................................................................................... 272
14.4.6 Textiles ...................................................................................................................... 272
14.4.7 Biomedicl Appliction............................................................................................. 273
14.4.7.1 Wound Heling Mterils .......................................................................... 273
14.4.7.2 Tissue Regenertion ................................................................................... 273
14.4.7.3 Drug Delivery ............................................................................................ 273
14.4.7.4 Biosensors .................................................................................................. 273
14.5 Conclusion............................................................................................................................. 274
References...................................................................................................................................... 274

14.1 INTRODUCTION TO MXene/POLYMER-BASED

NANOCOMPOSITES
A ctegory of nnocomposites with numerous distinctive properties is the MXene/polymer-bsed
nnocomposite mterils. MXene/polymer-bsed nnocomposites re generlly  mixture of bulk
MXenes together with rndomly dispersed MXenes nd polymer components with t lest one com-
ponent in the nno dimension. MXenes re hydrophilic two-dimensionl (2D) mterils with high
electronic density, which mkes them metllic. They re derived from the MAX phse or lyered
ternry Mn+1AXn, where ‘M’ is  trnsition metl, ‘A’ is  group IV–V element, nd ‘X’ is crbon
or nitrogen. Etching the lyer ‘A’ from the MAX phse gives MXenes. The formul for MXenes
is denoted s Mn+XnTz, where Tz denotes the surfce functionl group formed from etching. This

DOI: 10.1201/9781003164975-14 259

260 MXene-Filled Polymer Nanocomposites

functionl group enbles MXenes to form stble suspensions in polr solvents nd results in their
hydrophilic nture. The min functionl groups re  mixture of oxygen (O), hydroxyl (OH), nd
uorine (F). They id in the betterment of interction between the llers nd the polymer-bsed
mtrix in the nnocomposites. MXenes cn even be fbricted with mgnetic behvior. MXenes
offer  wide rnge of compositions nd hve ese of dispersibility. The lrge surfce re nd tun-
ble bundnt surfce functionlities of the MXenes promote their usge s nnollers. The high
electricl nd therml conductivity of MXenes mkes the mteril suitble for numerous sensing
pplictions. The drwbcks of MXenes, which include low exibility, poor stbility in n oxygen
tmosphere, nd esy restcking, re minimized or even mde unnoticed in combintion with poly-
mers, possessing high exibility nd stbility, in nnocomposites. Along with ll the other proper-
ties, their ntibcteril efciency, low cost, esy fbriction, nd tunble surfce termintions hve
promising benets in vrious MXene/polymer nnocomposite pplictions, especilly in werble
pplictions.
In situ polymeriztion, ex situ blending, nd solution blending re the most common preprtion
methods for MXenes/polymer nnocomposites. Hving the merits of chieving precise control over
the composition nd forming well-dened polymer structures, ex situ blending is more preferble
for fbriction. [1] They combine the spects of highly elstic-functionl polymers nd the eccentric
properties of MXenes, forming n ingenious group of nnocomposites. The superior mechnicl
nd therml properties, lightweight nture, exibility, nd incresed biodegrdbility hd led to
their utiliztion in  brod rnge of commercil werble pplictions.

MXenes Polymer

MXene/Polymer Nanocomposite

Energy Medical
Applicaons Purposes
Wearable
Applicaons
Sensors Antennas

Texles TENG
EMI
Shielding

FIGURE 14.1 Schemtic representtion of werble pplictions of MXene/polymer-bsed nnocomposites.

Flexible and Wearable Applications 261

14.2 CLASSIFICATION OF MXene/POLYMER NANOCOMPOSITES

MXene/polymer nnocomposites re clssied into lled composites nd complexes. In lled com-
posite mterils, MXene is used s  ller in  bulk mteril, owning to the rndom dispersion of
both MXene nd polymer with ech other. They re more studied nd include both thermoplstic
nd thermosetting polymers. In  complex mteril, the dispersion of MXene nd polymer is ppre-
cibly systemtic. They re put together with  specic mteril structure or s  specic mteril
product. MXene/polymer composite fbric, MXene-coted polymeric ber, nd MXene/polymer
composite erogel, sponge, or fom re ll termed s MXene/polymer complexes.

14.3 APPLICATIONS
With the enhnced chrcteristics of MXene/polymer-bsed nnocomposites, in comprison with
the norml composite mterils, they hve n extensive vriety of usefulness in diverse elds.
Biomedicl pplictions, sensing pplictions, electromgnetic bsorption nd shielding pplic-
tions, energy conversion, nd storge pplictions re only  few mong them. Ech of the pplic-
tions depends minly on the constituent components of the composite, their structure, their spect
rtio, the functionl groups nd the properties.
With the presence of  vriety of surfce end groups of MXenes, the nnocomposites give unique
surfce ctivity, good biocomptibility, hydrophilicity, nd exceptionl electricl nd opticl prop-
erties. MXenes improve the biocomptibility of polymers, thereby permitting vrious MXenes/
polymer nnocomposites to be used in drug delivery nd s ntibcteril substnces. The ntibcte-
ril property of the mterils enbles them to be used s bndges. The composites re lso used in
biosensing pplictions. Conventionl composite-bsed biosensors cn be effectively replced with
the new polymer technology in the biosensing pplictions.
The remrkble fetures of MXenes like low bndgp, esy functionliztion, good conductivity,
nd rich ctive sites enble the nnocomposites to be used in high-selectivity nd wide-rnge sen-
sors. There exists  number of sensors bsed on the MXene/polymer bsed nnocomposites. Gs,
electrochemicl, humidity, stress–strin, nd photoluminescence sensors re  few mong them. [2]
Excellent conductivity, enormous redox cites, nd lrge specic surfce re re the preferred
properties needed for energy conversion, storge, nd other pplictions. MXene/polymer nno-
composites possessing ll the essentil qulities cn be effectively used for the ppliction. Thus,
they hve been extensively used s supercpcitor, nd in bttery pplictions. MXenes, with their
dipole, crrier nd defect polriztion mechnisms nd multi-scttering property between lyers,
mke the nnocomposites suitble mteril for electromgnetic shielding pplictions. Among the
vrious trits of MXenes/polymer nnocomposites, the exible nd werble chrcteristics re of
primry interest nd re discussed in the following sections.

FIGURE 14.2 Pressure sensor ttched to the wrist.

262 MXene-Filled Polymer Nanocomposites

14.4 FLEXIBLE AND WEARABLE APPLICATIONS

The MXenes/polymer nnocomposites intertwine the exibility of polymers long with the vrious
properties of MXenes to engge the mteril in exible nd werble pplictions. [3] This exible
feture of the mteril drsticlly eliminted the use of vrious trditionl mterils in the respec-
tive elds. Werble devices minly focus on helth tretment nd monitoring, sensors, communi-
ction nd in the eld of sports.

14.4.1 GENERAL SENSING APPLICATIONS

14.4.1.1 Pressure Sensors (Piezoresistive Sensors)
The excellent properties of MXenes nd their homogeneous dispersion in  suitble polymeric
mtrix id the fbriction of highly sensitive werble MXene-bsed pressure sensors with  wide
tunble sensing rnge. These kinds of werble sensors re very effective in the detection of minute
bio-signls nd hence provide regulr helth monitoring. Among the vrious werble sensors, the
MXene-bsed pressure sensors re the most importnt, s the sensing cpbility of the exible nd
werble MXene/polymer-bsed nnocomposite pressure sensors re unffected with ny deform-
tions nd re very much effective in humn motion detection in the medicl dignosis.
In  pressure sensor, the pressure signl is converted to n electricl signl. Sensing mechnisms
minly depend on the chnges in piezoelectricity, cpcitnce, piezoresistivity nd triboelectricity.
Common types of pressure sensors re cpcitive, piezoresistive nd piezoelectric pressure sensors.
The resistnce chnges re minly ssocited with  combintion of mechnisms. In  piezoresistive
pressure sensor, the pressure signl is converted into resistnce signl output concerning the mteril
deformtion. Sensing mechnisms rely minly on the chnge in seepge pth, the tunnel resistnce
between llers, nd the chnge in the bnd structure of llers. Pressure sensors hve to respond
quickly nd must hve fst frequency response, ultr-high sensitivity, wide working rnge, nd high
cycle stbility. [4] They hve to sustin torsion deformtion, bending nd compression. The bility
of  pressure sensor to convert externl stimuli into electricl signls is termed its sensitivity It is
given by the eqution

°R
R
Sensitivity, S ˜ o .
°P

Guge fctor (GF) is dened s the rtio of the normlized resistnce chnge ΔR/R0 to the pplied
strin nd is used to evlute sensitivity. It is given by

°R
GaugeCoefficient, GF ˜ Ro ,
˛

where ΔR/Ro is the normlized resistnce chnge,

ΔP is the pressure chnge, nd
ε is the strin.

For werble pplictions, the sensor mteril must be highly sustinble, deformble, biocompt-
ible, nd extremely exible. The ide of stretchble conductors led to the development of MXene/
polymer-bsed pressure sensors. The sensors, under pressure, undergo  lrge distnce chnge,
cusing  reduction in the internl resistnce nd hence incresed conductivity.
Depending on the requirement of the pressure sensors in vrious werble devices, the fbric-
tion process vries. One-dimensionl single-wlled crbon nnotube (SWCNT), MXene sheets nd
Flexible and Wearable Applications 263

PVP re incorported together vi solvent evportion process to form MXene/single-wlled crbon
nnotube (SWCNT)/polyvinylpyrrolidone (PVP) composite lm. In the lm mteril, SWCNT nd
MXene sheets formed nisotropic bundles nd lmells, respectively. The PVP cted s n dhesive
connecting the components. The composite mtrix is then coted on  rubber substrte to form 
tctile sensor with superior sensitivity, low detection limit, nd cyclic stbility.
Another kind of werble pressure sensor is fbricted by directly coting MXene on  suitble
exible skeleton. This ide is further explored nd MXene is coted on  cotton textile by dip-
coting nd  drying method. Together with better electricl properties of MXene, the wvy net-
work nture of the textile substrte provided exibility nd in effect,  sensor with high sensitivity,
low response time, nd stble response is fbricted. MXene-textile-bsed pressure sensors cn be
further explored for their numerous pplictions s werble devices. Another choice for  exible
substrte is pper. Tissue pper, with its rough surfce, exhibits the properties required for func-
tioning s  good pressure sensor. Since the substrte is completely sfe, they re environmentlly
friendly nd biocomptible. This widens its ppliction in werble devices.
MXene-wrpped sponge with insulted PVA is nother sensor mteril, hving the dvntge
of low cost. Since the substrte, sponge, is common nd inexpensive,  high-performnce cost-
effective werble sensor device cn be fbricted with the mteril. The working principle of
the sensing mteril cn be explined such tht, when pressure is pplied to the mteril, the ir
spce between the microbers got reduced nd the contct points re incresed providing better
conductive pthwys. Thus, the chnges in externl pressure cuse chnges in resistnce of the
MXene-sponge nd thereby chnges in the conductivity. Sensing mterils bsed on mimicking the
interlocked humn skin structure lso proved to be efcient. The sensored signls re enlrged nd
trnsferred, leding to better sensing. The microspines on the humn skin re crefully mimicked
using n brsive pper to form rndomly distributed spines. MXene- nd nturl microcpsule
(NMC)–bsed exible biomimetic sensing mteril is designed under this mechnism for fbrict-
ing n effective MXene/NMC pressure-sensitive sensor.
One such sensor with higher conductivity nd stretchbility is obtined by tuning Ti3C2Tx struc-
ture to form  distinctive Ti3C2Tx MXene nnoprticle–nnosheet network. When subjected to pres-
sure, the nnoprticles migrte resulting in  lrge chnge in the resistnce nd the nnosheets
mintin the connectivity of the nnoprticles to the conductive network, thus mde cpble of
withstnding  lrge strin region. The Ti3C2Tx/PLA (polylctic cid)–bsed degrdble composites
form  werble pressure sensor with excellent cycle stbility, stble response even fter 10,000
compression cycles,  low detection limit, low power consumption, nd  wide rnge. They hve
wide pplictions in electronic skin nd humn–mchine interfces.
Aprt from resistnce-bsed sensors, cpcitive sensors re lso developed using MXene/
polymer composite s the exible dielectric mteril. The composite mteril enhnced the
sensing performnce by not only improving the dielectric constnt but lso by reducing the
compression modulus. MXene/poly (vinylidene uoride-triuoroethylene) (PVD-TrFE) compos-
ite functioned s the dielectric lyer nd poly (3,4-ethlenedioxythiophene) polystyrene sulfo-
nte (PEDOT:PSS)/PDMS lms plyed the role of n electrode in  werble cpcitive pressure
sensor.

14.4.1.2 Strain Sensors

The working principle behind  exible strin sensor is tht it trnsforms the tensile strin of the
sensor mteril into resistnce signl output. Components of  werble exible strin sensor need
to be highly exible, with lrge strin, superior dhesion, nd high sensitivity. These chrcteristics
of exible strin sensors id in their ppliction in mnufcturing werble electronic devices. A
strin sensor cn detect ny sort of deformtion by nlyzing the chnge in resistnce or cpcitnce
of the sensing mteril. The mechnism behind the sensing ctivity lies in the decrese in conduc-
tivity of the composite mteril with the ppernce of deformtions, like bending, becuse of the
formtion of microcrcks, which vnish when the externl pressure is relesed.
264 MXene-Filled Polymer Nanocomposites

Depending on the prerequisite of different pplictions in werble devices, MXene/polymer

nnocomposites cn be designed in different structures like lm structures; erogel structures, with
high porosity, low density, nd super elsticity; ber, textile, nd plnr structures, with lrge ex-
ibility nd mechnicl strength; nd sponge structures, with very lrge sensitivity. It is reported tht
the geometricl structurl rrngement of sensing mteril cn ffect the sensing rnge nd the
sensitivity of the strin sensors to  gret extent. This mde the scientists explore different structurl
designs of the mterils suitble for designing efcient werble strin sensors.
This observtion leds to the design of MXene/polyniline ber (PANIF) nnocomposite-bsed
sensing mteril with  tile-like stcked hierrchicl pttern. Being very vulnerble to getting bro-
ken nd becuse of their difculty to ssemble MXene microstructures in  hierrchicl pttern,
without compromising its conductivity nd mechnicl properties, negtively chrged MXene ly-
ers re combined with positively chrged PANIF to form the sensing mteril [5]. Aprt from the
trditionl single-lyered sensing mteril, here the structure is prepred by  lyer-by-lyer (LBL)
ssembly. Single-lyered pure MXene or pure PANIF sensors were found to hve  very low sensi-
tivity nd sensing rnge. This hppens becuse the single lyer forms more gps nd microcrcks
nd possesses reduced overlpped re due to lyer sliding. This cuses the resistnce to increse
nd hence reduces the sensing rnge nd sensitivity.
The resistnce of the multilyered structure of MXene nd bridged PANIF chnges s  result of
the chnge in the overlpped re cused by the reversible slipping of the djcent lyers. Good dis-
persion nd strong interction between the constituent prticles, required for the LBL coting, re
present for MXene nd PANIF, which mde them idel for fbricting multilyered sensor mteril.
The fbriction process involves spreding coting of delminted MXene nd PANIF, respec-
tively, on n elstic rubber substrte. The substrte is then stretched to produce microcrcks, upon
which further coting is crried out nd is then relesed. The mteril is then chrcterized nd is
found tht, with the presence of microcrcks, reversibly slippge of overlpped lyers nd spcing
propgtion, the tile-like hierrchicl pttern enhnced the overll sensing rnge, sensitivity, cyclic
stbility nd ultrlow detection limit of the strin sensor occur. The PANIF coted in between the
MXene lyers cted s  bridge between the MXene lyers to gurntee the existence of continu-
ous conductive pths nd, hence, improves the overll conductivity of the mteril. Becuse of the
strong bonding interction between MXene nd PANIF lyers, the proper ssembling of the con-
stituent prticles is mde possible, nd hence, the fbricted sensor mteril ws found to hve n
enhncement in stbility. With the esiness of fbriction, the nnocomposite cn be fbricted in
different composition rtios for specic pplictions.
The tile-like structure lso exhibits good response time nd recovery time nd hve better
cyclic stbility suitble for humn motion detection. With these enhncements in properties,
the sensor cn hve wide pplictions in werble devices. The specic structurl rrngements
mde the strin sensor precisely detect not only the minute movements like the pulse but lso the
lrge motions like bending. The sensor cn be directly ttched to the skin by medicl tpes to
detect the motions. This sort of werble MXene/polymer nnocomposite-bsed strin sensors
cn be effectively designed s communiction devices for those who re unble to communicte
by speking. The signls cn be trnsmitted wirelessly for effective communiction nd further
humn motion monitoring.

Fiber Structure
From the studies of Pu et l., the tem developed  good sensing mteril with ber structure using
 LBL dip-coting process. The multilyered silver nnowire (AgNW)/wterborne polyurethne
(WPU)-MXene ber is fbricted by  successive coting of AgNW/WPU lyers nd MXene ly-
ers on  stretchble substrte, nmed HPUF. The slippge of the multilyers nd the corresponding
crck propgtion on subjected to  strin resulted in the chnge in conductivity, thereby resulting
in strin sensing. This kind of ber cn be embedded in textiles or fbrics to fbricte numerous
werble devices like  werble electricl-responsive heter.
Flexible and Wearable Applications 265

Aprt from the LBL method, similr ber structures cn be synthesized from other techniques
like dip coting nd wet-spinning method. Ti3C2Tx MXene/polyurethne (PU) composite ber syn-
thesized from the wet spinning method ws found to possess ultr-high sensitivity. The bers cn
be woven together to form textiles with good strin-sensing cpbility, preferred for use in vrious
humn helth monitoring pplictions.

Film Structure
Vrious conductive MXene/polymer composite-bsed lms cn be fbricted by different synthesis
methods which re determined by the ppliction of the respective mteril. One such exmple is
the Ti3C2Tx MXene/CNT composite lm, fbricted by spry-coting technique. The lm uses n
elstic ltex rubber s the substrte upon which MXene nd crbon nnotubes (CNTs) re coted
successively. The mteril is chrcterized by  good detection limit of 0.1%, high sensitivity, nd 
sensing rnge. The mteril is designed s skin ttchble nd its elsticity cn be well employed for
widening its ppliction in werble devices. Another kind of lm, Ti3C2Tx MXene/grphene-bsed
composite lm uses vcuum ltrtion for its fbriction. As discussed erlier, the strin-sensing
mechnism of the mteril is bsed on the reltive motion of the djcent lyers of the mteril,
which resulted in continuous destruction nd mintennce of the conductive pth.

Hydrogels
With superior mechnicl properties nd other chrcteristics, MXene nnocomposite–bsed
conductive hydrogels re suitble cndidtes for being used s strin sensors in vrious werble
electronic devices. Conductive MXene hydrogel (m-hydrogel) with excellent self-dhesive bility,
exceptionl tensile strength nd outstnding self-repiring bility, is prepred by mixing MXene
nd PVA in  suitble fshion. The bsic interctions between the constituent components resulted
in exhibiting the superior properties of the mteril. When subjected to  strin, the m-hydrogels
undergo deformtion which results in chnging contct resistnce between the MXene sheets nd
hence the overll conductivity chnges. Hydrogels composed of  combintion of 1D nnowires
nd 2D nnosheets were found to hve extrordinry specictions, like fst responsiveness, better
linerity, very wide working rnge, tunble sensing mechnisms, resilience, nd superior reproduc-
ibility, suitble for ppliction in e-skin.
In contrst with the conventionl conductive hydrogels (MNH), which use wter s the disper-
sive medium, MXene-bsed orgnohydrogels (MNOH) use n orgnic solvent s the dispersion
medium. The solvent displcement mde in MNH enhnced the mteril with improved self-hel-
ing cpcity, durbility, superior mechnicl chrcteristics, nd long-lsting moisture retention
with excellent ntifreezing properties. With the presence of wter in the conventionl hydrogels,
they suffer evportion nd freezing t room temperture nd subzero tempertures, respectively,
thereby leding to poor shelf life. As n exmple, Wn nd coworkers developed  kind of MNH by
incorporting MXene nnosheets into polycrylmide (PAAm) nd PVA hydrogel. The nnosheets
cted s conductive llers in the hydrogel. The s-prepred MNH is soked in ethylene glycol
(EG) to synthesize MNOH. On immersing in EG, MNH replces  portion of wter molecules nd
becomes enhnced in its properties to form MNOH. The incorportion of orgnic solvent ids the
mteril to exhibit better exibility, self-heling bility, stble moisture retention for 8 dys nd n
ntifreezing property even t −40℃. Thus, certin werble devices, which hve to be performed
well even t low tempertures nd preferred to hve non-drying requirements nd good sensitivity,
cn be fbricted with MNOH.
High conductivity, stretchbility, nd  wide strin-sensing rnge of MXene/PDAC nnocom-
posite membrnes mke them  potentil cndidte for being used in strin sensors. Strin sensors
mde of MXene/polymer nnocomposite mterils cn be used in the mnufcture of werble
electronics to identify the extent of deformtion of their components, nd in biometric sensors.
These nnocomposites lso llow esy dhesion on other substrtes nd hence widen the rnge of
pplictions. [6]
266 MXene-Filled Polymer Nanocomposites

From the nite element method simultions (FEM) for designing piezoelectric pressure sensors,
it is observed tht the overll properties of the pressure sensor got improved by the introduction of
 biomimetic interlocked structure by ssembling the nturl micro-cpsules in Ti3C2 nnosheets.
This structure signicntly enhnced the sensitivity of the sensor. The improvement in the perfor-
mnce, exibility nd mechnicl deformbility rises from the resultnt force distribution djust-
ments in the biocomposite lms.

Gel
A kind of piezoresistive strin sensor is fbricted by the combintion of MXenes with  sponge
nd rGO erogel. The sensor ws found to hve  quick response time, brod sensing rnge nd
outstnding durbility over 10,000 cycles nd thus found pplictions in observing even the tiny
strin. The werble nd exible MXene-sponge/polyvinyl lcohol NW (MSP)–bsed strin sen-
sors on connecting series to  circuit ttched with  Bluetooth system re cpble of converting the
chnges in current nd resistnce into wireless electromgnetic signls. The device responds well to
rteril pulses nd cn detect vrious diseses.
The min chllenges in developing werble strin or pressure sensors lie in the development
of mterils with higher exibility, sensitivity, wide tunble strin nd low dimensions nd in the
ccurte integrtion of these mterils in the nnodevices. The werble sensors require mini-
turiztion of the device components, mechnicl durbility nd superior exibility. For werble,
long-time monitoring, self-powered sensors nd devices, the circuit must contin exible energy
storge units for the effective performnce of the devices. Such units compenste for the power
dissiption tht occurs in wireless devices. By overcoming these chllenges, werble strin sen-
sors with enhnced performnces cn be fbricted for nlyzing robotic systems, humn ctivi-
ties, nd mny more.

14.4.1.3 Humidity Sensors

Humidity sensors work on the principle of chnging the mteril properties of the nnocompos-
ites cused by hydrtion nd dehydrtion of wter molecules. With proper surfce functionliz-
tion, humidity or wter molecules cn be esily bsorbed by the mteril. With the multilyer
structure of MXene/polymer nnocomposites, the bsorbed wter molecules re inserted between
the lyers nd result in n increse in the thickness nd distnce between the lyers. This cuses 
chnge in the tunneling resistnce of the mteril lyers nd cn be mesured. This type of sensor
is of gret importnce since humidity gretly ffects the medicl eld, food industry, environ-
ment, fbric, nd much more. Thus,  werble humidity sensor will be very effective in min-
tining nd detecting the required mount of humidity in the surroundings. Only those mterils
with good responses under high nd low humidity must be chosen s the llers nd mtrices of
the nnocomposites.
This criterion is stised by, s for exmple, MXene/PAM (polycrylmide)-bsed humidity
sensors. They were found to hve  wide rnge of liner sensitive humidity sensing. [7] One such
suitble choice for  multifunctionl-exible humidity sensor is MXene/AgNWs-decorted com-
posite silk textile. The fbriction crried out by vcuum-ssisted LBL method initilly fbrictes
 lef-like nnostructure using MXene nd AgNWs. The structure provided the substrte mteril
with high conductivity nd lso mintined the ir permebility of the initil textile substrte. Aprt
from hving high sensitivity for wter molecules, the hybrid mteril shows good electromgnetic
interference (EMI) shielding cpbility, which mde them  very suitble cndidte for multifunc-
tionl werble pplictions.
Some composites help in monitoring humn brething, clerly help dignose the humidity vri-
tions nd help provide timely tretment. The humidity sensors hve hope in the fbriction of cer-
tin textiles with high sensitivity to humidity (Figure 14.3).
Flexible and Wearable Applications 267

FIGURE 14.3 Textile-bsed sensors.

14.4.1.4 Gas Sensors

MXene/polymer-bsed nnocomposites re lso very efcient in mesuring the presence of certin
hrmful gses in the tmosphere, thereby give n impliction of ny sudden ccidents. The lrge
number of surfce-ctive sites nd the bundnt terminl groups on the nnocomposite llow gs
dsorption. The gs dsorption/desorption cuses the crrier trnsfer between the composite sub-
strte nd the dsorbte gs. This kind of substitution of molecules cuses  resistnce chnge of the
sensor mteril, giving  suitble impliction of the externl conditions.
Mterils with much less response time nd recovery time,  wide detection rnge nd sensitivity
to  vriety of gses must hve opted for the sensor mnufcture. One such type of hrmful toxic
gs pollutnt is voltile orgnic compounds, VOCs. For sensing the presence of VOCs,  werble
MXene gs sensor is fbricted by  drop-csting method. The process involves pltinum sputter-
ing nd drop-csting of MXene on  werble polyimide lm. When exposed to VOCs, the numer-
ous terminl groups of MXene reduce the conductivity of MXene to the semiconductor level. The
fbricted gs sensor displys  p-type sensing behvior nd monitors  vriety of gses t room
temperture. Since NH3 molecules possess lrge bsorption energy, they hve the fstest response
time for detection.
Nonpolr gses like hydrogen nd methne cn be detected t room temperture by V2CTx/
polyimide-bsed gs sensors. The sensor fbriction involves the drop-csting of V2CTx MXene
solution on  exible polyimide surfce. The rich surfce oxygen groups of MXene solution in the
sensor mde them sense hydrogen nd methne, even if hving  low composition.
Ti3C2Tx MXene/GO composite ber cn be fbricted vi the wet-spinning method. The mteril
exhibits high sensitivity towrd NH3 gs. With its outstnding mechnicl strength, the mteril
cn be woven onto textiles, suggesting extended pplictions s werble devices. Similr NH3 gs-
sensing mteril cn be synthesized with ctionic polycrylmide (CPAM)/Ti3C2Tx MXene nno-
composites. Here, CPAM plys  dul role in forming hydrogen bonds with NH3 nd in enhncing
the mechnicl strength of the MXene composite lm. [8]
Ti3C2Tx-PVA/PEI MXene/polymer-bsed nnocomposites re cpble of engineering werble
gs sensors. Here, the MXene component helps in dsorbing polr molecules, through hydrogen
bonding while the porous structure of the polymer fcilittes  lrge specic surfce re for further
dsorption of the gs molecules. With the mutul benets of the MXenes nd the polymers, MXene/
polymer-bsed nnocomposites re very pprecible mterils for werble gs-sensing pplic-
tions. They cn lso be used in environmentl monitoring.
Yet nother type of werble gs sensor, which senses biomolecules, includes those used in
the medicl eld. Ti3C2Tx/polymer-bsed exible gs sensors monitor the presence of certin
268 MXene-Filled Polymer Nanocomposites

components in the humn brethe such s monitoring cetone for dibetic cre nd mmoni for
lung discomfort, thereby providing erly medicl dignosis nd better tretment.

14.4.1.5 Epidermal Sensors

MXene/polymer nnocomposites cn be designed s werble soft epiderml sensors for monitor-
ing humn ctions. The sensing response of the sensor is given by

sensing response ˜
˛ I ° I o ˝ ˙100% ˜ ˆI % ,
Io Io

where ΔI denote the chnge in current t  prticulr pressure nd

Io denotes the initil current without ny externl force.

Corresponding to ech pressure, the sensing response displys  distinctive nture. When the sen-
sors got pressed or their pressure incresed, the contct re of the sensor increses resulting in
shortening the conductive pthwy for ion trnsfer nd efcient electron trnsport. By this principle,
 minute or  lrge-scle humn motion cn be effectively detected nd monitored. This kind of
epiderml sensor cn be ttched to the wrist for monitoring hnd movements nd the pulse, for
monitoring chest muscle movements during brething, nlyzing ngers movements during bend-
ing, nd even monitoring the movements during swllowing. By connecting the werble sensor to
 wireless trnsmitter, the sensing reports re trnsmitted to  mobile phone, nd we cn utilize the
benets of wireless monitoring of humn motions. This type of sensor hs bundnt pplictions,
primrily in the eld of personl helth cre.
One such composite which cts suitble for the purpose is the MXene nnocomposite orgno-
hydrogel. The impressive self-dhesive, moisture retention, self-helble, nd conductive nture of
the composite serve s  suitble pplicnt for mny sustinble exible nd werble electronic
pplictions. The composite is  combintion of MXene nnosheet network nd polymers, in 
dispersion medium like wter/glycerol. The initil gel stte nd long-lsting moisture retention
properties cn be explined by the presence of glycerol in the polymer mtrix. As the mount of
glycerol increses, the rte of wter evportion decreses. Glycerol hs hygroscopicity nd low
vpor pressure nd forms hydrogen bonds with wter molecules, thereby hindering the evpor-
tion of wter from the mteril. With this property, the mteril cn cope with comprtively more
bending or twisting under norml tempertures without ny brekge. [9] The MXene nnocom-
posite orgnohydrogels show self-heling cpbility, which cn be ttributed to the presence of
dynmic PBA (poly(butyl crylte))–ctechol bonds in the mteril. The mteril properties of
the s-prepred nnocomposites nd the self-heled (fter cutting) nnocomposites do not show
ny lrge uctution. An epiderml sensor mde of similr mteril cn hve  long lifetime with
better ccurcy.
The nnocomposites lso possess  self-dhesive cpbility, resulting from the presence of ct-
echol groups in PDA nd the hydroxyl groups of glycerol. This bility supports the dhesion of the
nnocomposite on different surfces, but the dhesion strength vries with the selection of the sur-
fce. This property enbles the nnocomposite to get effectively coted on suitble substrtes nd
thereby increses the rnge of ppliction of the nnocomposite. All the properties of the MXene
nnocomposite orgnohydrogel fcilitte its fesibility of use s epiderml sensors, electronic
devices, soft robots, electronic skins nd the like. The cpbilities of exible nd werble sensors
cn be well explored in  good del of potentil uses like in textile, electronic products, electronic
skin, utomobiles, spcecrfts nd much more.
From the discussion, it cn be concluded tht most of the sensing mterils re biocomptible
nd re environment friendly. This mde the mteril to be pplied directly onto the skin or woven
into fbrics for werble pplictions. Werble devices, like smrtwtches, with  combintion of
different sensors, hve gret potentil in communiction nd in the medicl eld. E-skin developed
Flexible and Wearable Applications 269

using different sensors cn be very well exploited in future developments in the eld of robotics,
rticil intelligence, nd humn–mchine interction. Enhncement of ny sensing mteril bsi-
clly relies on improving its GF nd working rnge. Morphologicl chnges in the conductive net-
works mde by rtionl chnges nd structurl optimiztion re mjor fctors for enhncing the GF
nd working rnge of the sensing mteril. There re mny populr strtegies tht helps chieve bet-
ter GF. Different structurl geometries, like biomimetic interlocked micro/nnostructure, whisker
structure, hierrchicl structure, homogeneous strin distribution design, microcrck propgtion,
lyer slippge mechnism, overlpped re, length, density, crcked re nd width, re the mjor
fctors improving the GF. Another spect determining the performnce of  sensor is its working
rnge. The working window is mostly determined by the stretchbility of the mteril. The con-
stituents of the sensing mteril, the nture of microstructures, substrte, type of sensor nd even
the fbriction process inuences the stretchbility of the mteril. Stretchbility cn be dversely
ffected by the strong interctions between the MXene lyers. The incorportion of 1D conductive
nnomterils cn enhnce the stretchbility of strin sensors.
Aprt from high GF nd working window,  sensor must exhibit good dt linerity. Dt liner-
ity depends on the vrition of microstructure morphology when subjected to externl stimulus.
Once the microstructure undergoes  nonhomogeneous chnge in its structure upon stretching, the
dt will be responded to in  nonliner pttern. For  sensing mteril to be impressive, it must
hve high GF,  wide working rnge, nd pprecible dt linerity. Thus, the selection of composite
mteril, microstructure geometry nd the interctive forces mong the ctive mterils re the key
points to be noted while designing  sensor for  specic ppliction (Figure 14.2).

14.4.2 ELECTROMAGNETIC ABSORPTION AND SHIELDING APPLICATIONS

With the growth of the electronic industry, instrumenttion nd telecommuniction eld,  kind
of pollution clled EMI hs emerged. This cn tke plce even inside electronic gdgets densely
pcked with multiple electronic components. The unwnted interference from other rditions leds
to improper functioning of the devices nd degrde device performnce. EMI cn hrm not only the
gdgets but lso the humns, cusing mny helth issues. This demnds the need for proper shield-
ing from EMI. The blocking of electromgnetic rditions, either by reection or by bsorption
by suitble brrier mterils, is clled EMI shielding. The shielding mteril hs to be conductive
or mgnetic nd prevents the penetrtion of high-energy rditions [10]. The common reson for
EMI is electrosttic dischrge. EMI cn be hzrdous lmost in every eld, including utomobiles,
spcecrft, militry sfety nd even in common household systems.
The shielding mterils hve to be properly selected depending on the kind of rdition (depend-
ing on its energy, the device, etc.) for which the shielding is imprted on. Since MXenes re mte-
rils with n pprecible mechnicl strength nd heterogeneous lyer structure with vrious
electromgnetic wve loss mechnisms, they becme one mong the best cndidtes for electro-
mgnetic shielding. For the ppliction of electromgnetic shielding, MXene hs to be incorported
with certin reinforcing mterils to improve their properties. Polymers re  suitble choice for
reinforcing mterils since it not only improves the overll mechnicl property of the composite
but t the sme time lso enhnces its conductivity. On being used with polymers, the mteril
cn mke use of mny fvorble properties of polymers to form suitble exible nd werble
high-efciency electromgnetic bsorption nd shielding mterils. The high electricl conductiv-
ity nd multiple internl reection chrcteristics of the MXene/polymer nnocomposites resulted
in the high EMI performnce of the system. The surfce ctivity of the composites esily enbles
the incorportion of certin dditives used for incresing the conductivity. The strong bsorption
cpcity of the MXene is mde used in the composites to provide them with good electromgnetic
bsorption chrcteristics. Since reection cn gin increse the rdition pollution, mterils with
good bsorption re preferred for the shielding ppliction, which cn be well suited by the MXene/
polymer nnocomposites. [11] MXene/polymer nnocomposites, with their signicnt mechnicl
270 MXene-Filled Polymer Nanocomposites

properties nd noncorrosive nture, cn be  suitble mteril for shielding pplictions. The ex-
ibility, low fbriction cost, lightweight nture, high conductivity nd reduced corrosion mke the
nnocomposites  suitble lterntive for the hevy-weighted-corrosive metls. Not only does the
exibility of the composite permit its use in mny pplictions, but the biodegrdbility of the poly-
mer mtrix lso encourges its ppliction s n environment-friendly mteril.
The rditions re initilly reected from the composite’s surfce, creting  high impednce
mismtch t the ir–MXene interfce nd the remining got bsorbed by the composite mteril.
The interlyer structure of MXene enbles the rditions to undergo multiple internl reections.
During ech reection, the rdition is bsorbed by the composite becuse of the strong interction
with the high-electron-density MXene lyers nd the reection continues until most of the rdi-
tions re bsorbed by the composite.
Hving high bsorption nd internl reections of rdition, Ti2C/PVA nnocomposite mterils
re  good choice for the shielding ppliction. The preprtion methods lrgely inuence the con-
ductivity nd strength of the prepred nnocomposites. The dispersibility of MXenes in the poly-
mer mtrix cn be improved by in situ polymeriztion nd the conductivity by therml reduction.
On nneling MXenes, the MXene surfce groups get eliminted, cusing n increse in internl
dipole nd electron mobility. These, in turn, increse the electromgnetic energy dissiption cp-
bility of the nnocomposites. Thus, werble MXene/polymer-bsed nnocomposites with good
mechnicl properties nd bsorption nd high shielding efciency (SE) cn be chieved by inter-
twining the properties of MXenes, like high conductivity, interlyer reection between polymer nd
MXene, defect nd dipole polriztion conductnce loss nd of polymers, like corrosion resistnce,
lightweight, biocomptible nd exible nture.
MXene/PEDOT:PSS nnocomposites-bsed lm exhibits EMI SE of 42.10dB t 11.1µm. The
mechnism of wve ttenution lies primrily on the vrious polriztion processes hppening t
the interfce between MXene nd PEDOT:PSS. Similrly,  highly efcient, ultr-exible EMI
shielding mteril cn be fbricted by nnocomposite elstomer Ti3C2Tx MXene (m-MXene) bsed
mteril. The delminted, multilyered MXene for the purpose ws prepred by the selective etch-
ing of luminum using HCl/LiF solution from the Ti3AlC2 powder, followed by specic heting
nd soniction. Along with the superior conductivity, hydrophilic nture nd surfce rectivity, the
MXene network enhnces the EMI shielding by possessing high conduction loss, multiple internl
reections nd surfce polriztion effects on MXene networks, compred with other electroneg-
tive polymer-bsed nnocomposites.
Another such productive EMI shielding mteril developed by M nd his coworkers is bsed
on rmid nnober nd Ti3C2Tx MXene/silver nnowire (ANF-MXene/AgNW). The increse in
the nnocomposite composition increses the effective shielding of the mteril. The presence of
MXene lyers nd the corresponding ohmic losses drsticlly improves the shielding effect, even
t low composition, thn the trditionl counterprts. Hence, these mterils will immensely help
shield werble electronic devices from EM wves to  gret extent.
The MXene/polymer composite–bsed EMI shielding mterils cn be integrted on textiles for
better shielding pplictions. The textile fbriction cn be explined with the exmple of MXene/
polypyrrole (PPy): polyethylene terephthlte (PET)–bsed composite. PPy is synthesized vi in situ
polymeriztion method nd is used to prepre  stble PPy/MXene ink. A PET substrte is coted
with  PPy/MXene solution by dipping the substrte into the ink solution. The composite-coted
fbric is then treted with hydrophobic silicon. The dipping-drying process continues for 10 cycles,
nd the resulted product displys very high conductivity, pproximtely 1000 Sm−1, s needed for
n excellent EMI shielding. It is found tht, s the soking time increses, the EMI shielding effect
nd electricl conductivity lso increse further. The coting with hydrophobic silicon enhnces the
mteril’s durbility by providing it with  wter-resistive nture.
Werble EMI shielding devices bsed on different composite mterils were explored nd the
results compred. Using the LBL method, MXene/AgNW solution is spry-coted on  silk textile
nd formed  leike structure. The mteril with 120-µm thickness exhibits n EMI SE of 54 dB.
Flexible and Wearable Applications 271

Composite mterils with high EMI SE nd wter-repellent chrcter cn be synthesized by the sol-
gel method. Keeping in mind the need for lightweight, exible mterils for werble pplictions,
low density, hydrophobic, porous MXene-bsed fom nd erogel composite re suitble choices for
werble EMI devices. The fom is so fshioned by treting MXene lms with hydrzine. The pro-
cess involves the rection of hydrzine with the MXene hydroxyl group. During the process, CO or
CO2 gs is evolved, which supports pore formtion. The process expnds the MXene lyers, which
leds to the formtion of  lightweight fom possessing  well-dened cellulr structure.

14.4.3 HEATER
Excellent electricl conductivity nd exible nture of MXene-bsed composite promote its ppli-
ction s werble heters. With its superior electricl-therml het conversion efciency, Prk
et l. [19] developed n electric–therml heter vi  one-step coting process. The heter mteril
is bsed on MXene-coted PET threds, hving the properties of shpe dptble nture, smooth
processbility, dmirble mechnicl relibility nd good joule heting performnce. The ber cn
be sewed by  common commercil sewing mchine, which simplies the werble device fbri-
ction procedure, thereby extending the werble ppliction. The chrcteristic properties of the
mteril were found to vry with coting time. The increse in coting time resulted in  decrese in
ber resistnce by pproximtely 300 ohms nd n increse in mximum stedy-stte temperture
to 128.6℃.
Similrly, utilizing the high therml conductivity of MXenes, werble photo-to-therml heters
re developed with MXene composites. MXenes disply n internl light-to-het conversion ef-
ciency of lmost 100%. It is observed tht, even with ultr-low content of the hybrid mterils, the
temperture cn be incresed rpidly to pproximtely 111 ± 2.6°C. This result leds to the develop-
ment of AgNP/MXene hybrid mterils. The mterils cn be well exploited in fbricting photon
cptors, moleculr heters nd energy trnsformers.

14.4.4 TRIBOELECTRIC NANOGENERATORS

The nnogenertor technology dels with the conversion of mechnicl or therml energy to elec-
tricity. It is minly of three types, nmely piezoelectric, triboelectric nd pyroelectric nnogen-
ertors. Piezoelectric nd triboelectric nnogenertors convert mechnicl energy to electricity
wheres pyroelectric nnogenertors convert therml energy into electricity. Triboelectric nno-
genertors (TENGs) re bsed on coupled triboelectriction nd electrosttic induction for the
conversion of energy. It suitbly hrvests the kinetic energy of humns to produce electricity. For the
purpose, the two electrodes re mde in contct in different congurtions depending on the needs.
Consider  self-powered werble wristwtch, s n exmple of MXene-bsed werble nd
exible electronic device. The device is fbricted with  2D MXene-bsed TENG, integrted with
 micro-supercpcitor (MSC) long with  suitble encpsultion mteril-like silicone. The rst
step ssocited with the device working is the seprtion of chrges. Positive chrges re ccu-
multed on the humn skin while negtive chrges re induced on the silicon surfce. Thus, the
potentil difference induced between the two lyers ppers s the input of the ssocited bridge
rectier nd hence llows the electrons to ow from the silicone lyer to chrge the supercpcitor
integrted with the circuit. This self-chrging TENG unit powers the digitl wristwtch nd other
similr werble electronic devices.
To chieve this lrge potentil difference, mterils with high triboelectronegtivity re pre-
ferred for the mnufcture of TENGs. Since PTFE, the most triboelectronegtive mteril cn be
used in single electrode mode opertion only their ppliction is limited. With the emergence of
MXenes, possessing high electricl conductivity nd surfce electronegtivity, they becme  suit-
ble cndidte for being used not only in MSC but lso s the TENG mteril, which cn be oper-
ted in the two-electrode mode.
272 MXene-Filled Polymer Nanocomposites

The high exibility, trnsprency, stretchbility, nd biocomptible nture of polymers led to
them being ctively used in nnogenertors. To compenste for the lower triboelectronegtivity of
the polymers, the polymers re incorported with MXenes to form suitble composites, s required
by the nnogenertors. The high conductivity nd electronegtive surfce of MXene/polymer nno-
composites (from the negtively chrged functionl groups) encourge the composite to be used
in nnogenertors. The 3D-MXene/PDMS nnocomposites work s  negtive tribo-mteril in
the TENG device. The triboelectric performnce of  TENG ssembled with 3D MXene/PDMS,
shows  higher output voltge thn tht of pure PDMS-bsed TENG. Incorporting MXenes into the
PDMS mtrix induces micro-cpcitors in the dielectric PDMS polymer. With the inclusion of the
nnoller, the dielectric is constnt, nd hence, the cpcitnce of the nnocomposite get enriched.
This sort of improved dielectric constnt increses the cpcitnce nd surfce chrge density of the
composite thereby improving the TENG’s performnce. The 3D-MXene/PDMS composite–bsed
TENG gives  high output current, which is mny times greter thn tht of the pure PDMS, even
seven times t optimum conditions, which resulted from the signicntly lowered electricl resis-
tnce of the nnocomposite. Cpcitors cn be connected to the circuit nd re employed for electri-
cl energy storge. This implies the ppliction of TENG s mechnicl power source for driving
portble electronic devices. [12]
The superior electronegtivity of MXene-bsed composites is well exploited in the mnufcture
of werble TENG with high EMI shielding. This leds to the fbriction of PPUH-m-MXene
nnocomposite elstomer-bsed TENG [13]. The required TENG is synthesized by initilly prepr-
ing  PPUH polymer mtrix nd crosslinking Ti3C2Tx MXene, modied by PDAC polymer, on the
polymer substrte. The prepred TENG is designed to function like  self-powered, werble sensor
with intrinsic heling property, which cn sense even delicte physicl motions.
Improving the triboelectric chrge density of the TENG becme the min chllenge encoun-
tered while developing MXene-bsed TENGs. The triboelectric chrge density cn be enhnced by
improving the effective contct re. This cn be chieved by introducing nno- or microstructures,
like pyrmid rrys or nnowires, in the triboelectric mterils. Since TENGs produce irregulr AC
output pulses, they need to be stored for providing  stedy DC signl for functioning self-powered
werble electronic devices. Solving these chllenges will gretly inuence to improve the prcticl
self-powered pplictions of the TENGs. [14]

14.4.5 WEARABLE ANTENNAS

MXene/polymer nnocomposite-bsed exible printed ntenns re their infncy regrdings their
ppliction in werble electronics. This technique llows to “cot” ntenns even on the building
wlls. High conductivity nd exibility required for the ntenn mteril forced us to consider the
composite mteril s  good choice. Depending on the ppliction, the nnocomposite mteril
cn be spry-pplied, inkjet printed or screen-printed on suitble substrtes. Even with low mteril
quntity, n pprecible mount of communiction cn be chieved. The lightweight nture nd
exibility of the mteril do not scrice the device performnce, it is lmost comprble with their
trditionl counterprts. [15] The low cost, ese of fbriction, environmentl-friendliness of the
mteril, exibility, nd noncorrosive nture enble the mteril to be used in sustinble locl re
communictions. Stretchble ntenns bsed on S-MXene re  good choice s werble ntenns.
The ntenn’s resonnce frequencies re strin-dependent nd re ltered between 1.575 to 1.375
GHz. Bsed on the studies, MXene nd SWCNT (S-MXene)–bsed composites were found to hve
the bility for being used in EMI shielding nd for wireless communiction.

14.4.6 TEXTILES
Sensors printed on fbrics serve mny pplictions, like medicl monitoring or communiction.
For this, the electrodes of sensors hve to be suitbly plced in or on the textile. Printing of the
Flexible and Wearable Applications 273

electrode mteril llows to chieve the requirement. MXene/polymer nnocomposites cn be 

suitble choice for the electrode mteril with their high sensitivity nd exibility.
An effective wy to ssemble werble smrt devices is by 3D printing. MXene-bsed inks cn
be used for the printing process. On compring with the trditionl bers, these smrt bers re
multifunctionl, hve progrmmble ptterns, nd respond to numerous externl stimuli.

14.4.7 BIOMEDICAL APPLICATION

Being biocomptible, MXene/polymer nnocomposites hve immense pplictions in the medicl
eld. The vrious surfce functionl groups, hydrophilicity, biocomptible nture, nd mny other
remrkble fetures enble them to be used in the respective eld.

14.4.7.1 Wound Healing Materials

With  biocomptible nture, low cytotoxicity, ntimicrobil bility, nd good mechnicl proper-
ties, MXene/polymer-bsed nnocomposites cn be  very good choice for using s wound heling
mterils. They mostly include bndges nd sutures. The dhesiveness of the nnocomposites with
other mterils mkes the surge or the bndges to get esily nd completely ttched to the wound
nd provide better blood clotting. The exible nture nd dhesive properties of the nnocomposite
offer structurl rigidity to ensure the utmost sfety to the wounded re nd fster heling. The
Ti3C2Tx/CS nnocomposites re found to be very much effective ginst E. coli nd S. aureus.
These chrcteristics of the nnocomposite enble the composite’s service s werble bndges
nd surgicl sutures nd provide better tissue regenertion. [16]

14.4.7.2 Tissue Regeneration

A mteril used in tissue repir my hve to be plced inside the body for  certin period, so it must
not rect ginst the body tissues nd must not be toxic. Polymer nnocomposites with biodegrd-
ble polymers re more effective for the purpose. The MXene/polymer nnocomposite mteril,
with its mechnicl properties withstnds ny degrdtion of the nnocomposite, hence supports
its long life in the body. In the cse of providing bone support, the nnocomposites offer strength
similr to tht of the bones nd possess  biocomptible nture nd for this reson, the nnocompos-
ites frm to be one of the most suitble counterprts for the motive. Ti3C2Tx/PLA nnocomposite
membrnes re effectively used in bone regenertion.

14.4.7.3 Drug Delivery

A well-developing re in the medicl eld is trgeted drug delivery. This becomes very crucil in
the tretment of mny diseses, minly in cncer tretment. In trgeted drug delivery the drug will
rech or ct only t the specied re of infection nd does not ffect the surrounding helthy tissues.
With the presence of vrious surfce functionl groups, the MXene/polymer nnocomposites cn be
properly surfce modied nd functionlized with the drug mteril for the selected re drug deliv-
ery prctice. The interclted structure of the nnocomposites llows the esy loding of the drug in
the composite nd imprts them with good drug-loding cpcity. By mking use of the mgnetic
property of the nnocomposites, the drug ssimilted MXene/polymer nnocomposite cn be more
excellently tuned nd hence permits the controlled relese of drugs nd trgeted drug delivery.
Aprt from hving good tensile strin sensitivity, high conductivity, signicnt stretchbility nd
speedy self-repiring bility, MXene/PVA-bsed exible sensors excellently bond with humn skin.
The sensor cn esily perceive the postures, body movements nd fcil expressions, thus hving
the potentil to drsticlly improve the helth cre systems. [17,18]

14.4.7.4 Biosensors
Werble MXene-bsed electrochemicl biosensors mesure  wide vriety of biomolecules in the
body nd mke continuous evlutions for  long time for the proper monitoring of the body’s
274 MXene-Filled Polymer Nanocomposites

response to medicines nd of the ptient’s helth. For exmple,  werble swet-bsed biosensor
ptch composed of Ti3C2/PB composite nlyses biomolecules present in the swet. Similrly, 
novel bio-electrochemicl MXene-bsed sensor evlutes the humn body condition during hemo-
dilysis tretment. The sensor combines the initil dilysis of the whole blood with subsequent
detection nd mkes  conclusion regrding the ptient’s helth. Such MXene-bsed biosensors
simultneously determine the presence of lcetminophen (ACOP) nd isonizide (INZ) with bet-
ter efciency thn the conventionl ones.

14.5 CONCLUSION
MXene/polymer nnocomposites re of immense importnce becuse of their unique properties.
A gret number of studies veried their pplictions in  diverse vriety of elds nd proved to be
of immense help in improving humn life. Among mny other enhnced properties, the high con-
ductivity nd lrge surfce re drive extreme ttention for the mteril. This mkes the MXene/
polymer nnocomposites superior to ny other nnocomposite mterils. Werble technologies
hve promising potentil in next-genertion technologies. MXenes enhnced the electrochemi-
cl performnce of werble devices. Their exible nture permits its integrtion into portble
devices nd wireless communiction. The predominnt peculirities of the nnocomposites hd
veried its pplictions in exible nd werble device fbriction. Ech MXene composition hs
distinct chrcteristics nd enbles its usge in individul pplictions. Employing the MXene/poly-
mer nnocomposite mteril initited the successful fbriction of low cost-highly dvnced nd
sophisticted sensors, communiction systems, environmentl sfety monitoring devices, medicl
equipment nd so on.
Numerous chllenges tht hinder the further ppliction of MXenes hve to the suitbly elimi-
nted for hrvesting better utiliztion of the mteril. Suitble MXene-bsed electrode mterils
hve to the designed to improve the power density nd volumetric energy of MXene-bsed devices.
Further studies need to be crried out to understnd the physiochemicl chrcteristics of MXenes.
Only by understnding the physics behind the 2D structure, proper mnipultion of the MXene
structure cn be mde ccordingly. Reserch hs to be done to nlyze the esiest but efcient fb-
riction method to design exible-werble MXene-bsed devices. Studies bsed on reducing the
oxidtion degrdtion of the MXene-bsed composite hve to be explored further so s to improve
its durbility nd stbility. Since the complex structures strongly inuence  prticulr ppliction,
the mechnism behind those structures hs to be studied further for effective device fbriction;
tht is, the reltionship between microstructure nd device performnce; microstructure nd mte-
ril property, fbriction method nd ppliction, different fbriction methods nd more hve to
be explored further. Future developments must focus on different fbriction techniques, improved
comfortbility for humn wering nd effective humn–computer interction or wireless commu-
niction. The MXene/polymer-bsed nnocomposite mterils hve substntil vluble properties
nd hve to be studied further to inspect their more werble pplictions.

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 15 Theory, Modeling, and
Simulation of MXene/
Polymer Nanocomposites
Benjamin Tawiah, Sarkodie Bismark, and Charles Frimpong

CONTENTS
15.1 Introduction ........................................................................................................................... 277
15.2 The Concept of Modeling nd Simultion ............................................................................ 278
15.2.1 Denition of Terms ................................................................................................... 279
15.3 Theoreticl Models of MXene/Polymer Nnocomposites .................................................... 280
15.4 M & S of MXene/Polymer Nnocomposite .......................................................................... 285
15.5 Merits nd Demerits of M & S of MXene/Polymer Composites .......................................... 291
15.6 Conclusion............................................................................................................................. 292
References...................................................................................................................................... 292

15.1 INTRODUCTION
New two-dimensionl (2D) trnsition metl crbides clled MXene hold unlimited potentil for
future pplictions in mny science nd technology res. The unique chrcteristics of MXenes
such s conductivity, strength, hydrophilicity, nd electromgnetic interference (EMI) shielding
give  possibility to crete new high-tech multifunctionl composite mterils. As n exmple, con-
ductive MXene/polymer nnocomposites with these unique properties could be used for structurl
helth monitoring in n irplne wing or  wind turbine blde. The complexity in the degrdtion
process of composites lled with nno-inclusions brings  chllenge for experimentlists.
For mechnicl properties, the incorportion of MXene with polymeric mterils, such s epoxy
resins, exhibits n improved frcture toughness nd impct strength. The inuence of MXene on
the mechnicl, electricl, nd tribologicl properties of vrious polymeric systems hve been thor-
oughly investigted (Mlki nd Vrm, 2020; Wytt et l., 2021; Aghmohmmdi et l., 2021;
Ji et l., 2020). Prticulrly, the tensile strength nd moduli, exurl strength nd exurl moduli,
nd hrdness hve been investigted in  number of studies (Htter et l., 2020; Sliozberg et l.,
2020; Guo et l., 2019; Chen et l., 2021). The interest in MXene polymer composites is due to fc-
tors such s high surfce re nd the comptibility between such nnostructures. When compred
to plin polymers, this chrcteristic is thought to improve the mechnicl nd therml properties
of polymer nnocomposites, s demonstrted by greter tensile strengths nd tensile moduli. The
mechnicl properties of nnocomposites reinforced with MXene re known to be inuenced by the
suitbility nd rectivity of polymers nd other llers, s well s ssocited production procedures
nd processing vribles. The crosslinking density of the resultnt nnocomposites is improved by
the high comptibility between polymer mtrices nd other elements (Akyiir et l., 2020). Mtrix
nd MXene comptibility cn lso ffect dhesion nd interfcil bonding. By enhncing interf-
cil contcts between mtrices nd MXene interlyers, the MXene interlyers re ltered leding to
enhnced MXene comptibility (Akyiir et l., 2020; He et l., 2021).
Different modeling pproches hve been utilized to nticipte the outcomes of nnocompos-
ites in order to understnd the progression of dmge nd identify mechnicl chrcteristics.

DOI: 10.1201/9781003164975-15 277

278 MXene-Filled Polymer Nanocomposites

Such techniques include nite element (FE) modeling, which is useful in nding the mechni-
cl properties of  single MXene nnosheet nd interfce lyer between nnollers nd polymer
mtrix using  strtegy of inverse nite element modeling under sttic nd dynmic loding. The
chrcteriztion of modeling nd simultion is not simple becuse it encompsses knowledge in
 vriety of elds, including uid dynmics, composites, nd computer science to succeed. It hs
wide pplictions in energy systems, chemicl engineering, composite science, nd fbriction, s
well s mny res, including logistics nd socil mngement. The entire process my be viewed
s  microcosm of systems/control theory, numericl inquiry, computer science, rticil intel-
ligence, nd/or opertions reserch, depending on the context, modeling, nd simultion method.
Modeling nd simultion (M & S) grdully encompss ll of the forementioned elds. M & S
hve recently been tipped s the future computing rchetype. M & S chllenge covers the nly-
sis nd design of complicted dynmicl systems to the construction of bstrct models derived
inductively from rel-world observtions. In principle, M & S design models deductively derive
the bsis from prior knowledge to build  completely new system tht stises certin design
gols. Rel-world problems re frequently solved through n itertive combintion of nlysis
nd design. The tomic scle, microscle to mesoscle components of  nnocomposite, nd
their interctions re explored using M & S. M & S re primrily concerned with the behvior
of dynmic systems, including physicl nd nonphysicl systems. Mny other theoreticl nd
computtionl models pplied in polymer MXene nnocomposites hve been discussed in this
chpter.

15.2 THE CONCEPT OF MODELING AND SIMULATION

M & S re the physicl nd/or logicl representtions of vrious constituents within  system to
understnd their interctions nd trepidtions virtully to generte dt tht cn help determine
decisions or mke predictions bout systems. The model is generlly comprble to  rel system,
which ids the product design nlyst in predicting the impct of system modictions. To put it
nother wy, modeling is the process of developing  prole tht represents  system’s whole set
of ttributes. It is  digrmmtic representtion of individul units nd their interctions within
 component (system) tht is bsed on sound theory. This phenomenon could result in known or
inferred mteril properties tht could be further mnipulted by chnging the eqution vribles to
further enhnce the properties of the system (in this cse the composite). Simultion is the opertion
of  model in terms of time nd spce. A performnce nlysis of n existing or proposed system is
obtined when the model is subjected to vrible equtions within time nd spce. To put it nother
wy, simultion is the process of studying  system’s performnce using  model or testing some-
thing using  model.
M & S, ccording to Brtley et l. (2011), cn be described s the ct of driving  virtul prototype
system with pproprite inputs nd scrutinizing the resulting outputs. It hs been further dened s
the process of creting  model of  conceptul system nd utilizing it to run experiments in order
to understnd the system’s performnce nd/or ssess vrious mngement methods nd decision-
mking processes. The object of M & S includes, but not limited to, prediction, proof, discovery,
performnce ssessment, eduction, nd trining. Mnufcturing processes, socil systems, corpo-
rte orgniztions, government systems, computer systems, ecologicl nd environmentl systems,
nd other multifceted/complicted processes, systems, nd designs my ll benet from M & S.
This method hs been used in  vriety of multidisciplinry study res, including decision-mking
processes, integrted product tem mngement, new product cretion, nd generl orgniztionl
mngement. M & S for complex sociotechnicl systems hve recently emerged s  vible study
topic (Zhi et l., 2018)
In the grnd scheme of things, models serve two purposes. The rst is dignostic: In this sense,
the model is used to develop nd test the procedures/prctices tht explin the observtions in this
Theory, Modeling, and Simulation 279

system. In such  sitution, the model decides if the processes re well understood nd dequtely
represented. In generl, these models nd simultions re reserch tools used to gure out the nture
of unexplined phenomen or poorly dened processes.
The model’s second function is prognostic, which mens it is used to mke predictions. In these
roles, ny sort of model cn be utilized. M & S cn be pplied in mny different res in science
nd engineering. The vrious concepts nd clssictions of theoreticl models nd simultions of
MXene/polymer nnocomposites hve been outlined in this section. The rudimentry concept of
modeling nd simultion include the object, bse model, system, experimentl frme, simultion,
lumped model, veriction, nd vlidtion.

15.2.1 DEFINITION OF TERMS

Object: An object in M & S is  rel-world entity tht is nlyzed to help understnd how  model
behves. The gol of M & S opertions is reveled through the object.
Bse Model: A conjecturl expliction of object ttributes nd (their) behvior tht is vlid
throughout the model is referred to s  bse model.
System: A system is  cler thing tht exists under certin prmeters in the rel world.
Experimentl frme: It’s  rod mp for studying nnocomposite systems in  rel-world lbor-
tory. This frmework includes both the experimentl circumstnces nd the study ims. Two sets
of vribles mke up the bsic experimentl frme, tht is, frme input vribles (FIV) nd frme
output vribles (FOV), tht correspond to the model terminls. The FIV is in chrge of mtching
the inputs to the system or model, while the FOV is in chrge of mtching the output vlues. It’s
crucil to note tht n experiment my or my not ffect the opertion of the system (by inuenc-
ing its input nd prmeters). As  result, the experimenttion environment might be considered 
seprte system (which my, in turn, be modeled by  lumped model). Experimenttion lso entils
mking  mesurement-bsed observtion.
Simultion of  lumped model: This procedure follows  set of rules (s Petri net, differentil-
lgebric equtions, or bond grph). It produces simultion results with vrible input/output behv-
ior (Prk et l., 2004). In such circumstnces, both symbolic nd numericl simultion strtegies
cn be pplied. Virtul experimenttion is  simultion tht imittes rel-world physicl experi-
menttion nd llows one to offer nswers to importnt questions concerning the chrcteristics
of  nnocomposite. The System–Experiment/Model–Virtul Experiment sequence is more bsic
becuse of the homomorphic connection between the model nd the system. As  result, creting 
model of  rel system nd re-creting its properties should provide similr results to doing  rel-
world experiment followed by nlysis nd codiction of the ndings (Vngheluwe et l., 2002).
The gurntee tht results drwn from M & S cn be trusted is one of the most essentil criteri for
such  system. The two seprte processes of veriction nd vlidtion re linked to the cretion
of this condence.
Veriction: The process of connecting or compring two or more things (results) to ensure
their ccurcy is known s veriction. Veriction is generlly done in M & S by compring the
dependbility of  simultion progrm nd the lumped model. This is ccomplished by compring
experimentl dt to simultion ndings inside n experimentl frme. If the ndings do not mtch,
the model is declred invlid. The simultion model must be veried nd vlidted before it cn be
used in  rel-world sitution (Zhi et l., 2018).
Vrious vribles re utilized in M & S. The system stte vribles re one of these vribles;
they consist of  set of dt tht is used to represent the internl development of the system t
ny given moment in time. It’s vitl to keep in mind tht certin of the system stte vribles
don’t chnge over time. Although in  continuous-event model, the vlues chnge t predetermined
points. Differentil equtions re commonly used to specify system stte vribles, nd the vlues
of these equtions vry with time.
280 MXene-Filled Polymer Nanocomposites

15.3 THEORETICAL MODELS OF MXene/POLYMER NANOCOMPOSITES

The form of the MXene/polymer nnocomposite is determined by the interction between the poly-
mer entropy generted by the limittions between the two neighboring pltes nd the potentil
enthlpy gins. Any gins emnting from the uspicious interction between the polymer nd
llers interfce in most cses determine the morphology of the nnocomposite. Different polymers
hve different interctions with MXene; tht is, some fctors such s the polymer moleculr struc-
ture nd orienttion cn inuence the interctions with MXenes. In other words, MXene surfces
could form interclted hybrids with polymers bsed on their comptibility. Mny mens hve been
employed to modify polymers nd MXene to interct well to ttin the expected nnocompos-
ites (Zhou et l., 2021; Yu et l., 2021). Theoreticl pproches for explining how the interction
between the mtrix, MXene, orgnic lignds, nd cly surfces, s depicted in Figure 15.1, inu-
ences the nnocomposite’s phse behvior (Ginzburg, 2019).
For toms, molecules, nd clusters of units, the moleculr-scled pproch focuses on molecu-
lr dynmics, the Monte Crlo technique, nd moleculr mechnics. Micro-scled pproches re
utilized to bridge the gp in moleculr- nd meso/mcro-scled technologies. Structure formtion,
bulk mteril ow, nd the bonding interction between mtrices nd llers hve ll been shown
to be inuenced not just t the subtomic level but lso t the micro level. Micro-scled techniques
typiclly ll the gp between moleculr- nd meso/mcro-scled methods. In the development of
structures, the bulk ow of mterils, nd the bonding interfce between mtrices nd llers, it hs
been demonstrted tht elements within  composite re impcted not only t the moleculr level
but lso t the microscopic level. Brownin dynmics (BD), dissiptive prticle dynmics (DPD),
lttice Boltzmnn method (LBM), time-dependent Ginsburg-Lndu theory (TG-LT), nd dynmic
density functionl theories (DDFT) re some of the pproches for studying microscopic structures
nd interctions of composite elements within  system tht hve been estblished (Slmnd Dong,
2019; Quresimin et l., 2012).
Under the conditions of both moleculr nd nnomteril structures with homogeneity t vrious
scled levels, the continuous process is the most common technique mong the meso-/mcroscle

(a) Ag. Int.

T

U0

(b)

2
3 1
V

0 U0
U

FIGURE 15.1 A representtion of kink model of ller intercltion between polymer with  dimensionl
indiction () nd generted chrt in (b).
Source: Reprinted with permission from (Slmnd Dong, 2019b).
Theory, Modeling, and Simulation 281

pproches of modeling. This method exmines the deformtion of nnocomposite structures

cused by externl forces, s well s the effects on stress nd strin. Micromechnicl models,
equivlent-continuum models, self-consistent models, nd nite element nlysis re mong the
continuum pproches evluted through modeling nd numericl simultions. Slm et l. (Slm
nd Dong, 2019) hve done  lot of work on using micromechnicl models to predict the tensile
chrcteristics of nnocomposites bsed on the inuence of individul elements. The inuence of
individul components on the usge of micromechnicl models in estimting the tensile chr-
cteristics of nnocomposites hs been widely studied. Six theoreticl models hve been used to
determine the tensile moduli of vrious polymer nnocomposites, including the Voigt nd Reuss
models, Hirsch model, Hlpin–Tsi (H-T) model, modied H-T models, Hui–Shi (H-S) model, nd
lminte model. The Dnusso–Tieghi (D-T) model, Nicolis–Nicodemo (N-N) model, Lu model,
nd Turcsányi–Pukànszky–Tds (T-P-T) model re ll used to estimte the tensile strengths of most
nnocomposites (Slm nd Dong, 2019).
The rule of mixture (ROM) is the most essentil concept in micromechnicl modeling of poly-
mer prticle composite systems (Mustf et l., 2015). Filler properties such s shpe, morphology,
size, spect rtio, nd good interfcil dhesion my be trnsferred to llers nd mtrices using
ROM, which is bsed on the premise tht both llers nd polymer mtrices re linerly elstic [20].
The simple rule of mixture (SROM) does not give  correct extrpoltion for the trnsverse Young’s
modulus nd in-plne sher modulus, lthough it is one of the erliest nd the simplest technique of
micromechnics nlysis for estimting the mechnicl behvior of unidirectionl plies. Therefore,
the modied rule of mixture (MROM) proposed by Hlpin mnges to overcome this shortcoming
(Mustf et l., 2015; Mdn et l., 2020)
In generl, the Voigt nd Reuss models re used to study nd simulte composite systems, with
the upper nd lower boundries of ROM, respectively (Slmnd & Dong, 2019b). In wht is known
s  prllel model, the Voigt model (VM) includes the mlgmtion of totl individul compo-
nents in the composite subject to the verge elstic modulus nd the volume percentge of ech
component (Slm nd Dong, 2019; Rossikhin nd Shitikov, 2018). In ddition, the VM model
ssumes tht n isostrin condition exists in the upper bound for both llers nd mtrices, resulting
in  chnge in the modulus of the composites (Bulíček et l., 2012) s presented in Eqution 15.1:

EC ˜ Ep˝P ° Em (1 ˛ ˝P ). (15.1)

The Reuss or series model, on the other hnd, is known s the inverted ROM or lower bound ROM.
The Reuss model, unlike the VM model, is founded on the conjecture tht continuous stress rises
in both polymer mtrices nd llers. Equtions 15.2 to 15.4 represent the Reuss model:

Ep Em
EC ˜ (15.2)
E M˝P ° EP (1 ˛ ˝P )
WP
P ˜ (15.3)
WP ° ( ˙ P / ˙ M )(1 ˛ WP )˝

˜ blend ° ˜11 ˛ ˜ 2 ø 2, (15.4)

where ‘’ indictes the ller volume proportion in composites with Wp representing the weight frc-
tion of llers. The density of mtrix blends (ρblend) cn be determined s per Eqution 15.4, which is
usully subject to inuence by the reltive densities (ρ1 nd ρ2), nd the nlogous volume frctions
(1 nd 2) of the two components in the blended mtrices. More so, Ec, Em, nd Ep re the moduli
of composites, mtrices, nd llers, respectively. In such polymer blends (bio-epoxy blends) the
ndings must be estblished experimentlly using tensile testing on polymer blends with vrying
ller mounts.
282 MXene-Filled Polymer Nanocomposites

It’s worth noting, however, tht the elstic modulus of llers vries (Ep) cn differ bsed on dif-
ferent MXene dispersion sttuses in the polymer mtrix in the bulk nnocomposite. Also, in the
cse of interclted MXene structures, the pprisl of effective modulus of MXene will tke  dif-
ferent pproch from tht of exfolited compound mix MXene structures, which cn be determined
by pplying ROM in Eqution 15.5.

(Eintercalation ˜ EMMT ˝MMT ° Egallery (1 ˛ ˝MMT ), (15.5)

if Egallery << EMMT ’

° °d ˙ ˙˘ , (15.6)
˜ EMMT MMT ˜ ˝ MMT
˝˝ intercalation ˇ MMT ˇˇ
E E
˛ ˛ d002 ˆ ˆ

by which ϕMMT nd EMMT re the volume of MXene nnosheets nd the elstic modulus of MXene,
respectively, wheres Egllery is the interlyer modulus. Once the interlyer modulus is considerbly
less thn the MMT modulus (Egllery ≪ EMMT), the Egllery will hve n insignicnt inuence on the
modulus of the interclted MXene nnosheets.
As  result, eqution my be used to clculte the modulus of interposed MXene composites
(Eqution 15.6). The limited inuence of the reduced-order model (ROM) on the elstic moduli
nd volume frctions of the composite elements is  disdvntge. More so, criticl fctors like
MXene ller shpe, orienttion, nd ller 3D position re not of ny vlue to the system, which
more or less dents the qulity of elstic moduli pproch to evluting composite mterils. This
deciency cn, however, be tken cre of with the integrtion of modulus reduction fctor (MRF)
in the modied rule of mixture (MROM). This is  typicl occurrence when employing MRF with
 ller spect rtio (α), where irregulr ller lignment in composite mterils my be explined
using Eqution 15.7:

Ec ˜ EP ˝P (MRF) ° EM (1 ˛ ˝P ). (15.7)

As indicted in Equtions 15.8 through 15.10, MRF is clculted using two distinct types of ke-
like llers in nnocomposites: Riley’s rule, Pdwer’s rule, nd Beecher’s rule.

ln(u ˛1)
(MRF) ˜ 1 ° (15.8)
u
Pdwer nd Beecher’s rule:

(tanh u)
(MRF) ˜ 1 ° (15.9)
u

1 ˙P GM
u˜ (15.10)
˝ EP (1 ° ˙P )˛

The sher modulus of the mtrix is represented by GM, wheres α denotes the spect rtio of llers
in composite systems. In this instnce, the MRF of nnocomposites is investigted by tting similr
experimentl dt, nd it ws discovered tht MRF = 0:66 cn well mtch experimentl dt for
modulus prediction when the ller in the composite is less thn 6 percent by volume frction.
Hirsch proposed  model for determining the elstic modulus of nnocomposites tht ws bsed
on  simple combintion of the series nd prllel models given in Eqution 15.11 (Klprsd et l.,
1997; Hirsch et l., 2012):
Theory, Modeling, and Simulation 283

EP EM
EC ˜ x( Em (1 ° ˙P ) ˛ EP ˙P ) ˛ (1 ° x) , (15.11)
EM ˙P ˛ EP (1 ° ˙P )˝

where x is n experimentl constnt tht governs the stress trnsmission between nnollers nd
composite mtrices. This is bsed on the precision of curve tting with relistic investigtion dt
(0 ×1). In clculting the elstic moduli of nnocomposites bsed on the ller orienttion in the
nnocomposites, x is seen s n importnt constrint. With reference to volume frction, shpe, nd
orienttion of llers, the H-T model gives  relistic pproximtion for elstic moduli of unidirec-
tionl composites. This model is frequently used for constnt or frgmentry llers with  vriety
of lignments, such s ber or ke-like nnollers. The elstic modulus of composites is expressed
s follows:
1 ° ˝˙ L ˆP
EC ˜ E M , (15.12)
1 ˛ ˙ L ˆP

where EC, EM, nd EP re the elstic moduli of composites, mtrix, nd llers, respectively, nd ηL
is determined s follows:

EP / Em ˝1
˜L ˛ . (15.13)
EP / Em ˙ °

As  result, ξ is  constnt in composites, conditionl on the geometry nd spect rtios of the llers.
Alterntively, ξ cn lso be represented by the following formule:

˝lˇ
˜ ˛ 2° ˛ 2 ˆ  for loggitudinal modulus (E11 ) (15.14)
˙t˘
˜ ° 2 for transverse modulus (E11 ) (15.15)

The letters l nd t stnd for the length nd thickness/depth of dispersed llers in composites,
respectively. When ξ is very big (ξ⟶∞), the H-T model equls ROM, which is  prllel model,
s shown in Eqution 15.1. Once ξ is very smll (ξ⟶0), the H-T model trnsforms into n inverse
of ROM, which is the sme s the common series model found in Eqution 15.2. As  result, the
H-T model is believed to be exible when it comes to nticipting scenrios in which the ROM is
between lower nd higher bounds.
The Dnusso–Tieghi (D-T) Model proposes  link between rigid mtrix-bsed composite
mechnicl strength nd volume percentge. The D-T model posits tht the mtrices nd llers hve
no dhesion; therefore, there is no lod trnsfer from mtrices to llers. As  result, the overll lod
is considered to be the sme s wht mtrices lone cn crry. This pproch is used for regulr or
irregulr ller distribution. The strength of composites my be clculted using  simple eqution
given in Eqution 15.16:

˜ c ˛ ˜ m (1 ˝° ), (15.16)

where σc nd σm re the composite nd mtrix tensile strengths, respectively, nd ψ is the cross-
sectionl re frction. Becuse of the rndom orienttion of the llers in this model, the re frc-
tion of the mtrix must be constnt for every cross section cross the mtrix, implying tht the re
frction of the mtrix’s cross section is equl to the volume frction of llers (ψ ≈ ϕp; Slm nd
Dong, 2019).
284 MXene-Filled Polymer Nanocomposites

Bsed on the preceding D-T model, nother theoreticl model Nicolis nd Nrkis (N-N) substi-
tutes the volume frction with  power-lw function s follows:

˜ c ° ˜ m (1 ˛ a˝bP ), (15.17)

where a nd b re constnts in the composites tht re inuenced by prticle morphologicl chrc-
teristics. Under lbortory conditions, this cn be difcult to regulte, mking this model burden-
some. As  result, the N-N model hs been explored for cubic-shped llers with evenly dispersed
sphericl prticles, bsed on the premise tht no dhesion exists between the mtrix nd the llers.
In this model, it is ssumed tht the continuous phse’s minimum cross section is perpendiculr to
the pplied stress. As  result, the strength of composites is determined using Eqution 15.18:

˜ c ° ˜ m (1 ˛ 1.21˝2P/ 3 ). (15.18)

The N-N model is perfect for estimting composites’ lower-bound strength. As  result, the
strength of composite mteril might be ssumed to be the sme s tht of the mtrix or pristine
polymer (σc ≈ σm), which cnnot be the relity, nd therefore, this model is ineffective.
Other theoreticl models, such s the T-P-T model, provides  semi-empiricl eqution for
extremely resilient prticle-mtrix interfcil bonding using  simple hyperbolic function tht
describes the chnges in the ller cross section with ller concentrtion (Bhrth Kumr et l.,
2016). With this model, the exponentil component’s functionliztion is exposed to unforeseen
dependency on the mtrix strength nd ller volume frction with this pproch. As  result, the
T-P-T model cn only be used to represent composites contining sphericl nd nisotropic prticles.
Theoreticl models, in ddition to continuum nd tomic-scle computing methods, hve
contributed to  better pprecition of composite systems. The extended Tkyngi model, for
exmple, ws used to estimte the tensile strength of polymer/crbon nnotube nnocomposites
(PCNTs; Zre nd Rhee, 2019). To produce the predictions, this model ssumed tht the interphse
between the polymer mtrix nd nnoprticles ws strengthened nd the percolting efciencies
were high. The model ws ble to properly predict the verge levels of the percoltion threshold,
interphse thickness, nd strength for the two typicl PCNTs bsed on this informtion (Beher
et l., 2019). To further vlidte the model, mthemticl frmeworks were pired with n ctul
reserch using trnsmission electron microscopy to nlyze nd decrese the risk of gglomertion
in nnocomposites by crefully chnging the volume frction, spect rtio, nd specic surfce
re of nnoprticles (Zre nd Rhee, 2019b). Another reserch extended the Tkyngi model
into two versions, ssuming tht the system hd networking nd dispersion of components bove
the percoltion threshold (Loos nd Mns-Zloczower, 2013). The enlrged model ignored the cru-
cil reinforcing nd percolting impcts of interphse zones in the modulus becuse it ignored the
interphse res round distributed nd networked nnoprticles. As  result, the nnocomposites
reinforcing the effectiveness of the networked nnoprticles were found to be over the percoltion
threshold (Beher et l., 2019).
The interphse res round the dispersed MXene nnosheets re given greter weight in the
expnded model. To put it nother wy, the expnded Tkyngi model closely resembles the
ller network’s reinforcing efciency (Zre nd Rhee, 2020; Zre nd Grmbi, 2017) s shown in
Eqution 15.19.

˝ N (1 ° ˝ f )Ed E N ˛ ˝ N (˝ f ° ˝ N )Em E N ˛ (1 ° ˝ N )2 Ed E M
E˜ (15.19)
(1 ° ˝ f )Ed ˛ (˝ f ° ˝ N )Em

The tensile modulus of the nnocomposites is determined by  tensile test nd is denoted by the
letter E. The volume frctions of nnoller nd networked prticles re represented by the letters f
Theory, Modeling, and Simulation 285

nd N, respectively, while the tensile moduli of the dispersed nnoller, ller network, nd polymer
mtrix re represented by the letters Ed, EN, nd E m, respectively. It’s worth noting tht the sum of f
nd N lwys equls to one (Zre nd Rhee, 2020).
To estimte the tensile moduli nd strength of nnocomposites,  mthemticl frmework of
H-S lminte model nd H-T models hs been proposed. According to this hypothesis, the content
of components tht cn inuence the nnocomposites re ller type, dispersion sttus, orienttion,
morphologicl fetures, nd ller-mtrix interfcil bonding (SlM & Dong, 2019b; Affdl nd
Krdos, 1976). Regrdless of the model employed, the orienttion of the individul components nd
their mnner of interfcil contct with the polymer mtrix hve n essentil inuence in determin-
ing the composite’s chrcteristics. In generl, the rndom orienttion of dispersed llers hs  big
inuence in forecsting nnocomposites’ elstic moduli. Interestingly, there were some chnges
between the two models used, lthough they were not signicnt. The ndings of experimentl
work t  prticulr percentge of ller inclusion were reected in the H-S model, but the H-T model
reveled vlues tht were similr to those of the experimentl study.

15.4 M & S OF MXene/POLYMER NANOCOMPOSITE

In reserch nd industril contexts, computtionl pproches bsed on electronic to continuum
levels re frequently used to investigte vrious mteril rections in dened surroundings nd
spce. While M & S re well-developed elds in metllurgy, cermics, nd polymeric mterils, the
science of simulting composites is still in its erly stges. The chllenge in using computtionl
tools to exmine composites stems mostly from the fct tht

(1) composite mterils re mixtures of two or more different mterils with similr or dis-
similr properties (e.g., metl/cermic, metl/polymer, cermic/polymer), necessitting
precise designtion of not only the discrete constituents in the model but lso their com-
plex interfcil interctions, nd
(2) the limitless potentil for developing unique composite mterils by combining severl
conventionl mterils, which necessittes precise mteril knowledge nd the pproprite
prmeters to ssure redolent computtionl insight into ny composite product chnges.
(Beher et l., 2019; Stukowski, 2014)

With the continuum modeling pproch, nite element modeling (FEM) is frequently used to
simulte composite mterils depending on the length nd time scle (Beher et l., 2019). Other
modeling pproches, including tomic-scle methodologies, DFT, nd moleculr dynmic (MD)
simultions, re utilized to ensure  complete knowledge of experimentl systems nd to develop
better mteril models for greter length nd time-scle simultions.
FEM is effective for resolving constitutive reltions in dynmic structures tht re susceptible to
 vriety of solid-stte processes. For nlyticl systems tht re constrined by vrious geometricl
restrictions, FEM is more benecil. The bility to ddress complicted geometries ssocited with
different mteril chrcteristics in the vrious components of the system being built is  benet
of FEM-centered simultion. In t rolling, the constitutive equtions relte primrily to the mte-
ril’s stress nd strin rtes, with the ltered mteril ssumed to be homogenous nd isotropic. In
this scenrio, FEM is primrily used to generte detiled stress nd strin proles in the unit cell
(mtrix, prticle, nd the contct between them), which re essentil to understnding the mechni-
cl behvior of the composites. In  study by Jkšić et l. (2020), the electromgnetic eld distribu-
tion in polymeric composite structures, s well s the spectrum distribution of their reection nd
bsorption coefcients were determined using FEM. The theoreticl model ws compred to n
experimentl result nd the originl models for the nnocomposites, nd the results re shown in
Figure 15.2. The result revels the effectiveness of the simulted model in predicting the output of
nnocomposites.
286 MXene-Filled Polymer Nanocomposites

(a) (a)

3 3.5

Experiment Experiment
Developed model (Eq. 11) 3 Developed model (Eq. 11)
2.5 Original equation (Eq. 1) Original equation (Eq. 1)

2.5
2
ER

ER
2

1.5
1.5

1 1
0 0.2 0.4 0.6 0.8 1 0 0.5 1 1.5 2
MWCNT (wt %) MWCNT (wt %)

(c) (d)

3.5 3

Experiment Experiment
3 Developed model (Eq. 11) Developed model (Eq. 11)
Original equation (Eq. 1) 2.5 Original equation (Eq. 1)

2.5
2
ER
ER

1.5
1.5

1 1
0 1 2 3 4 5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
MWCNT (wt %) MWCNT (wt %)

FIGURE 15.2 Reltive modulus experimentl dt, s well s clcultions of originl nd derived models
for nnocomposites.
Source: Reprinted with permission from Jkšić et l. (2020).

Some models re built on the ssumption tht the constituents deform elsticlly in response
to the restricted effective stress level delivered to the system. The spring stiffness lyer pproch
might be used to mimic  typicl impirment in  unidirectionl nnocomposite, including interfce
de-bonding. This could be used to simulte the interfce of mtrix-nnomteril reinforcement.
When the nite lyer is replced in the spring lyer model by  short thickness interfce, which in
this context denotes the trnsition between different phses, such s MXene nd polymer mtrix,
the MXene nnosheets’ interction with the mtrix is thought to be extremely stble nd semless,
llowing for the trnsfer of ny stress nd strin level. FEM ws utilized to simulte 3D hybrid
nnocomposites to test this theory, nd it ws conrmed tht stress ws trnsferred from the mtrix
to the MXene polymer interfce (Mghsoudi-Gnjeh et l., 2019). Similrly, To Hung et l. (2019)
emphsized the usefulness of FEM in exmining stress–strin perturbtions in nnocomposite
studies (Beher et l., 2019). Kilikevičius et l. (2021) investigted composite mterils composed
of n epoxy mtrix nd 2D nnosheets of grphene nd MXenes. The grphene–mtrix interphse
properties used in the computtionl nlysis were studied using n inverse modeling pproch.
A computer model bsed on the micromechnicl nite element technique ws creted to explore
the mechnicl chrcteristics of such hybrid polymer composites reinforced with grphene nd
Theory, Modeling, and Simulation 287

MXene nnosheets (Beher et l., 2019). In this system, geometricl models of 3D representtive
volume elements (RVEs) with different volume percentges of grphene nd MXene inclusions were
used, hving different spect rtios, nd diverse lignment congurtions creted using Digimt-FE
(Extreme Engineering, MSC. Softwre GmbH, Munich, Germny). The RVEs ssess the effects of
prticles’ spect rtio, shpe, clustering, orienttion (rndomly rrnged or ligned), volume frc-
tion in totl, nd, seprtely for different prticles, on the mechnicl behvior of nnocomposite.
The RVEs with rndomly plced inclusions could be built s cubes, while the RVEs with ligned
inclusions could be built s rectngulr cuboids, ligning the inclusion in the x–z plne. As MXene/
polymer mtrix interfce hs  momentous effect on the mechnicl behvior of composite mteri-
ls reinforced; therefore, the pproch of effective interfce models could be dopted where the thin
lyer, surrounding the MXene inclusions, is formed with specic properties. Typicl RVEs used in
Kilikevičius et l. (2021) nd Zelenikiene et l. (2018) reserch re presented in Figure 15.3.
The creted RVEs re then imported to the commercil nite element softwre Abqus FEA
(Dssult Systemes, Vélizy-Villcoubly, Frnce) to develop  computtionl model nd crry
out the simultion tsks. The periodic boundry conditions re opted in Digimt-FE (Extreme
Engineering, MSC. Softwre GmbH, Munich, Germny) nd imported long with the geometri-
cl models to Abqus FEA (Dssult Systemes, Vélizy-Villcoubly, Frnce). The RVEs re then
subjected to unixil tensile loding long the x-xis direction. The RVEs re meshed using the 3D
4-node liner tetrhedron element (C3D4) type. The experimentl stress–strin curve of epoxy is
inserted in the progrm, nd the multiliner hrdening plsticity model is considered to dene the
response to the mechnicl loding.

FIGURE 15.3 Some of RVEs of MXene/grphene/epoxy polymer composites: rndom 0.1% (); ligned 1%
(b); ligned 0.2% (c).
Source: Reprinted with permission from Zelenikienė et l. (2018).
288 MXene-Filled Polymer Nanocomposites

To investigte the impct of MXene/epoxy interfce chrcteristics on the suggested nnocom-

posite’s strength, severl vlues of the young modulus (EMX) nd strength of the interfce could be
pplied. The optimum principl stress benchmrk is usully pplied for the simultion of mtrix
nd interfce crcking with different vlues. In this regrd, the effect of the MXene inclusion in the
nnocomposite towrd the resistnce or dmge of the nnocomposite during the simultion would
be reveled, delivering relible nd stble results. Figure 15.4 shows  computtionl model of the
effect of rndomly plced MXene, nd epoxy on the stress distribution studied (Kilikevičius et l.,
2021) demonstrtes crck upon n increse in strin, while Figure 15.5 shows the stress distribution
on ligned MXene/polymer nnocomposites model.
Also, bsed on the computtionl model, the dmge evolution of the MXene/polymer interfce
could be obtined. Such evolution in the RVEs ws identied in Kilikevičius et l. study (2021). As
observed in Figure 15.6, in the beginning, the MXene/epoxy interfces strt to fil (Figure 15.6e).
High-stress concentrtions t the edges of the nno-reinforcements were detected s shown in

FIGURE 15.4 Stress distribution inside RVEs demonstrting crck formtion nd propgtion (cut views):
() RVE with rndomly plced inclusions t  strin of 0.026, (loclized crcking is indicted by the blck
rrows); (b) t  strin of 0.029; (c) t  strin of 0.031; (d) completely frctured t  strin of 0.038.
Source: Reprinted with permission from Kilikevičius et l. (2021).
Theory, Modeling, and Simulation 289

FIGURE 15.5 Stress distribution inside () the RVE with ligned MXene inclusions t  strin of 0.032,
(loclized crcking is indicted by the blck rrows) t  strin of 0.036; (b) t  strin of 0.039; (c) t  strin
of 0.041; (d) completely frctured t  strin of 0.045.
Source: Reprinted with permission from Kilikevičius et l. (2021).

FIGURE 15.6 Dmge evolution in the RVEs (dmge is highlighted in red). (–d) The RVE with rndomly
plced inclusions (the interfce lyers re hidden for better crck visuliztion, the MXenes re shown in
trnsprent green, while the grphene inclusions re shown in trnsprent blue): () t  strin of 0.016; (b) t
 strin of 0.026; (c) t  strin of 0.029; (d) t  strin of 0.038; (e–h) the RVE with ligned inclusions (the
MXenes re shown in green, while the grphene inclusions re shown in blue): (e) t  strin of 0.011; (f) t 
strin of 0.036; (g) t  strin of 0.039; (h) t  strin of 0.045.
Source: Reprinted with permission from Kilikevičius et l. (2021).
290 MXene-Filled Polymer Nanocomposites

Figures 15.4 nd 15.5e resulting in the formtion of loclized crcking t the edges of the nno-
reinforcements in both RVEs (see Figure 15.6–e). In the RVE with rndomly plced inclusions,
mtrix dmge ws observed t  strin vlue of 0.016 (Figure 15.6). As the strin increses, the
min crck begins to form s shown in Figures 15.4b nd 15.6b nd propgtes to the form shown
in Figures 15.4c nd 15.6c. A complete frcture of the RVE with rndomly plced inclusions ws
observed t  strin of 0.038 (Figure 15.4d). In contrst, in the cse of the RVE with ligned inclu-
sions, it ws observed t  strin of 0.045 (Figure 15.5h). Finlly, it ws observed tht upon complete
frcturing of the composite model (Figure 15.6d, h), the stress dropped, nd crck pinning, nd
deection of the epoxy mtrix were noted in the frctured RVEs (Figures 15.4d nd 15.5h).
Figure 15.7 shows tht ligned MXene nd grphene inclusions hve better effective Young’s
modulus nd tensile strength due to the geometricl orienttion of the inclusions. Furthermore,
s shown in Figure 15.7b, the inuence of the spect rtio of ligned inclusions revels distinct
effective Young’s moduli corresponding to different spect rtio vlues of the MXene nnosheets.
Figure 15.8 indictes tht the MXene/epoxy interfce hs no effect on the effective Young’s modu-
lus of the nnocomposite, but it does enhnce the tensile strength in both ligned nd rndomly
inserted MXene composites.
For the nnoscle computtionl work, moleculr dynmics (MD) simultions could be per-
formed using the open-source like LAMMPS softwre pckge (Sndi Ntionl Lbortories,
Albuquerque, NM). The MD modeling procedure ws initilly built using  xed-bond force eld
to perform crosslinking rections of epoxy monomers (Al Mhmud et l., 2021). Subsequently,
 trnsition simultion into n efcient rective force eld with the prmeteriztion ws conse-
quently performed to ll the M & S models, followed by equilibrtion to prepre for the mechni-
cl property prediction t the nnoscle level (Liu et l., 2011). Three-dimensionl periodicity ws
considered for ll the M & S models to mimic the bulk behvior of the mteril. To nlyze the
mechnicl nd other essentil spects of complex polymer nnocomposite structures, multifc-
eted modeling design nd nlysis, including unit cell modeling nd homogeniztion pproch, re
commonly used. The moleculr nd physicl reltionships between the nnomteril llers nd
the neighboring polymer mtrix should be given specil considertion becuse the interfce plys
 signicnt role in stress trnsfer from most polymers to nnomterils nd thus hs the potentil

FIGURE 15.7 The inuence of () geometricl orienttion of the inclusions t ρG = 500, ρMX = 125, fG = 0.1%,
fMX = 1.6%, nd EMX = 0.5E m; (b) the spect rtio of ligned MXene inclusions t ρG = 500, fG = 0.1%, fMX =
3.2%, nd EMX = 0.5E m.
Source: Reprinted with permission from Kilikevičius et l. (2021).
Theory, Modeling, and Simulation 291

FIGURE 15.8 The inuence of the MXene/epoxy interfce mechnicl properties () rndomly plced
MXenes, ρG = 500, ρMX = 125, fG = 0.1%, nd fMX = 1.6%; (b) ligned MXenes, ρG = 500, ρMX = 125, fG = 0.1%,
nd fMX = 6.4%.
Source: Reprinted with permission from Kilikevičius et l. (2021).

to hve  substntil inuence on the mechnicl properties. In this context, inverse modeling hs
been used to ssess the interfcil properties of 2D nnomterils such s grphene nd vrious
cly vritions in nnocomposites (Monstyreckis et l., 2020; Kumr et l., 2020). However, there
hven’t been ny modeling studies tilored towrd scrutinizing the stress trnsfer t the MXene/
polymer interfce currently (Monstyreckis et l., 2020b).
M & S re resercher’s method of mnging nd investigting complex systems before prcticl
experimenttion in certin cses. Tody’s comprehensive models nd simultions re so compli-
cted tht they require tems of scientists to prticipte in modeling ctivities in order for them to
be effective. In computtion nd interprettion, the consequences of model complexity re relized.
Almost ll modeling ndings, prticulrly theoreticl models, re mtched with experimentl dt
in composite design to evlute the vibility of relevnt theoreticl models used s  guide for lrge-
scle mnufcture.

15.5 MERITS AND DEMERITS OF M & S OF MXene/POLYMER

COMPOSITES
M & S hve wider dvntges, especilly over experimentl work, which hs gretly brodened its
usge in mny different elds. Simultion llows for  thorough evlution of items, systems, nd
structures in order to mke the necessry modictions before they re physiclly creted (Johnns
et l., 2013). The mthemticl model’s elements cn be substntilly modied in order to exmine
the mny fcets of the process. Model restrictions cn lso be chnged such tht the simultion
produces the most exct copy of relity s possible. The simultion lso serves s  mechnism for
postulting or nlyzing future enhncements. They enble comprehension of how  system should
behve without working on rel-time systems, llowing problems to be solved before rel systems
re deployed. M & S llow the ltertion to the system nd its inuence on the output without hv-
ing to engge with rel-time/rel-world systems (Robinson, 2008). Different congurtions could
be pplied to determine the best system requirements for the chievement of optimum results. They
lso enble the performnce of tilbck nlysis tht my cuse  dely in the experimentl work
process. M & S llow reserchers to understnd ll the interctions of the vrious constituents in
 nnocomposite nd nlyze their effects, unlike certin complex systems tht re not esy to
292 MXene-Filled Polymer Nanocomposites

understnd their interction t  time. Becuse the rel product is not ctully processed, mth-
emticl or computtionlly creted M & S cn minimize the cost representtion of  system entity,
phenomenon, or risk of life-cycle ctivities. Furthermore, new policies, processes, nd procedures
my be tested independently of the rel-world system.
Notwithstnding the vst dvntges of M & S, they present some disdvntges. Simultion
cn be time-consuming nd sometimes difcult to trnslte into the prcticl experimentl world.
The simultion process cn be costly in terms of computtionl resources nd their vilbility.
Furthermore, creting  usble model is n rt tht necessittes subject expertise, trining, nd expe-
rience. In ddition, due to the limittions in computtionl resources used for moleculr dynmics
modeling, computtionl studies re usully constrined to  few nnoseconds for type moleculr
dynmics models of orgnic mterils ( few thousnd toms). This could led to signicnt uncer-
tinty in the predicted mteril properties due to the smll sttisticl smpling of the moleculr
structure nd the presence of signicnt therml uctutions t nonzero tempertures.

15.6 CONCLUSION
Some theoreticl or computtionl models employed in simultion experiments t the tomic to the
mesoscle level of nnocomposites were discussed in this chpter. Mny theoreticl pproches
with  series of equtions hve been devised to simulte relistic system nnocomposites. M & S
hve been estblished s  veritble strtegy for predicting the outcome of  nnocomposite, which
could be veried nd vlidted with other modeling methods or the rel experimentl dt to ensure
the ccurcy of virtul experimentl dt obtined in the simultion. As there is limited literture
on M & S of MXene/polymer nnocomposites, the exploittion of the effect of MXene, polymer,
nd other constituents in nnocomposites on their properties or functionlities would be  pltform
for extensive exmintion of newly developed MXene/polymer nnoprticles. In comprison to
experimentlly produced nnocomposites, this might broden the understnding of MXene/poly-
mer nnocomposites’ behvior nd pplictions in  short spte of time.

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 16 Future Perspective of
MXene-Filled Polymer
Nanocomposites
Y C Goswami and Bhavya Pandey

CONTENTS
16.1 Introduction: An Overview of the Current Sttus of Polymer Nnocomposites ................ 295
16.2 MXene-Bsed Polymer Nnocomposites Applictions: An Outline .................................. 296
16.3 Existing Applictions nd Future Perspectives of MXene–Polymer
Nnocomposites.................................................................................................................. 297
16.4 Future Scope of Conductive Applictions .......................................................................... 297
16.5 Future Scope of Tribologicl Applictions ......................................................................... 298
16.6 Future Scope for Sensing Applictions............................................................................... 299
16.7 Future Scope for Energy Storge Applictions................................................................... 299
16.8 Future Scope of MXene-Polymer Nnocomposites in Biomedicl Storge
Applictions........................................................................................................................ 299
16.9 Future Scope for Werble Smrt Devices Storge Applictions....................................... 300
16.10 Future Scope for Membrne Seprtion ............................................................................. 300
16.11 Chllenges in the Development of Applictions................................................................. 301
16.12 Conclusion .......................................................................................................................... 301
Acknowledgment ........................................................................................................................... 301
References...................................................................................................................................... 303

16.1 INTRODUCTION: AN OVERVIEW OF THE CURRENT

STATUS OF POLYMER NANOCOMPOSITES
The moderniztion of the world brings  lot of chllenges ssocited with sustinble develop-
ment, energy-efcient systems, optimiztion of the use of mterils, wste mngement, issues of
potble wter, nd environmentl problems, mong others [1–2]. Such chllenges lwys moti-
vte us to develop new dvnced energy-efcient mterils, s  solution. As  result, the begin-
ning of the 21st century witnessed the growth of mny dvnced mterils t the nno level [3–4].
Zero- (0D), one- (1D), nd two-dimensionl (2D) nnomterils re being developed with  lot
of hope to be used in mny dy-to-dy pplictions. Of course, such mterils hve their specic
chrcteristics tht were explored with limited dimensions. However, such developments still
hve enormous potentil to incorporte more mterils nd combintions of mterils. Among
other mterils, very recently discovered new mterils MXenes, is  new clss of 2D nnostruc-
ture mterils tht exhibit exceptionl kind of conductivity, hydrophilicity. MXenes’ heterostruc-
tures re mde up of more thn  single element (e.g., C nd Ti, in the cse of Ti3C2Tx, nd Ti,
Mo, nd C, in the cse of double-trnsition metl crbides similr to grphene, which consist of
only one type of element, i.e., crbon) with rndomly distributed functionl groups on the sur-
fce. MXenes’ heterostructures re represented by the Mn+1XnTx, where M is trnsition metl, X
is nitrogen/crbon, nd T is  functionl group like uorine, hydroxyl, or oxygen. MXenes re
lyered ternry metl crbides, crbonitrides, nd nitrides. At Drexel University, titnium crbide

DOI: 10.1201/9781003164975-16 295

296 MXene-Filled Polymer Nanocomposites

(Ti3C2) ws the rst MXene discovered, nd since then, studies re going on to understnd the
different spects of MXene. MXenes cn replce mny existing mterils [5]. It hs found its
ppliction in conversion, environment nd ctlysis, seprtion membrnes, energy storge nd
conversion, electronics, medicine, nd optics [6].
Recently, vrious polymer nnocomposites hve lso been developed nd emerging s n impor-
tnt clss of mterils with  lot of future promises for high-performnce potentil pplictions nd
hence ttrcted intensive reserch interest. Polymer-bsed nnocomposite mteril consists of more
thn one discontinuous phse, distributed in one continuous phse. They hve  gret impct on the
eld of engineering due to their interfcil tension nd orienttion of dispersed phse inclusions like
prticles, kes, lmintes, nd bers [7].
Polymer nnocomposites hve gined  lot of ttention recently, due to their dvntge of being
used in combintion with functionl polymers with vrious types of nnollers such s cly, inor-
gnic/orgnic prticles, silic, metls, nd crbon-bsed nnoprticles s  ller [8–9], However,
despite their excellent properties, polymer nnocomposites hve limittions of nonuniform distri-
bution, high viscosity, nd fst gglomertion, which need to be ddressed in future developments
[10]. Recently, polymer-bsed composites lled with MXene hve lso been reported with  high
potentil to enhnce the properties nd functionlities of nnocomposites [6]. The MXene-lled
polymers provide gret strength nd conductivity due to n increse in surfce termintion in the
process of recombintion. MXene-lled polymers re gining  lot of ttention in tody’s world
due to their highly ttrctive electrochemicl nd electricl properties compred with other 2D
mterils like grphene [11]. High electricl conductivity ccelertes the heterogeneous electron
trnsfer rte. Becuse of their tendency of binding with different imed biomolecules, the pres-
ences of mny elements together dd up gin [12] in the heterogeneous ctlytic rection. This
lso improves distinct physicochemicl properties rther thn individul components. The prop-
erties include esy dispersibility, toughness, excellent brrier performnces, improved solvent,
good therml resistnce, inmmbility, excellent phototherml conversion, excellent electro-
mgnetic shielding, nd stores chrge cpcity in comprison with other nnocomposites [13].
The extrordinry properties of these composites mke them titled s wonder mterils for future
genertions. The mterils hve excellent potentil to be used in lmost ll mteril pplictions
in life. In this chpter, we discussed, in brief, the future spects nd pplictions of MXene poly-
mer nnocomposites.

16.2 MXene-BASED POLYMER NANOCOMPOSITES

APPLICATIONS: AN OUTLINE
MXene shows  rre combintion of high conduction nd is put to work on ctive surfces [14]. One
of the most importnt dvntges of MXene-lled polymer is improvements in frcture toughness.
As the surfce morphology hs drsticlly modied, with  functionl bonding of MXene with
polymers, the composites exhibit excellent mechnicl properties [15]. In ddition to surfce-mod-
iction reinforcement,  hybrid ller onto the surfce of  2D mteril to obtin hybrid-reinforced
polymers is lso reported. The lrge surfce re of MXene helps in developing strong interc-
tion between the Ti nd O toms in Ti2C nd Ti3C2 thn in the F- or OH-terminted MXene. The
O-terminted MXene is highly rigid, nd this highly rigid bonding is responsible for the bonding
between Ti–O, which is greter thn in the Ti–F, nd Ti–OH cses in terms of providing strength
[16]. In composites, this results in excellent mechnicl strength nd good therml stbility.
Thermodynmics clcultions predicted high stiffness for Ti4C3Ti2C, Ti3C2 MXenes [5]. Due to its
high mechnicl strength, MXene-lled polymers re emerging good cndidtes for supercpcitor
ppliction. MXenes give metllic to semiconducting behvior, this cn be found out by the elec-
tronic structures of MXenes [17]. The OH nd F groups in MXene impct the electronic structure
of  pristine MXene system. Ech F or OH group cn only receive one electron from the surfces.
Future Perspectives of MXene-Filled Polymer Nanocomposites 297

However, the O group differs from the F nd OH groups becuse it demnds two electrons from
the surfces to be stble [18]. Mn+1Xn-lled polymer gives controlled conductivity with n effective
enhncement [19].
The nonmgnetic ground sttes of the mjority of MXene result in  strong covlent bond
between the trnsition metl nd the X element. However, some MXenes lso exhibit mgnetic
nture due to unpired electrons in the spin split d-orbitls. Intrinsic point defects cn be used
to improve the mgnetic properties of MXenes. It hs lso been reported tht bre TiC smples
exhibit prmgnetic behvior, similr to the smples with F- or S-bsed termintions, but if the
smple contined two kinds of termintions, then its behvior ws shifted to ferromgnetic/pr-
mgnetic. Therefore, the mgnetic properties of Ti3C2Tx cn be ltered vi modultion of the sur-
fce termintions [20]. Polymer nnocomposite with controlled mgnetic properties hs  lot of
pplictions.
MXene-lled polymer nnocomposites exhibit extrordinry opticl properties mesured
through clcultion of the imginry prt of the dielectric function tensor [21]. These properties
include opticl trnsprency, plsmtic behvior, nd efcient phototherml conversion. The bility
of MXenes to interct with light in different wys hs drwn the ttention of the resercher [22].
The property of sturble bsorption of MXenes mkes it pproprite in the ppliction of
ultrfst lser. It ws lso found tht Ti3C2Tx cn rech similr performnce nd brodbnd
wvelengths rnging from 1550nm to 1620nm cn be produced. This property indictes its
potentil pplictions in the signl nd communiction re [23]. The studies of nonliner opti-
cl properties of MXene-lled polymers re in their initil stge nd re emerging s multiple
nd outstnding pplictions of the mteril. More interction cn be done on the interction of
MXene with light.
MXene-polymer nnocomposites hve their pplictions in the industry due to outstnding nd
different properties. It hs potentil in storge nd trnsfer of energy, biomedicl pplictions, nd
sensor pplictions. Mny pplictions hve been developed; still,  lot of work is going on with
vrious modictions concerning improvement in functionliztion, the inclusion of  new vriety
of MXene nd polymers. The future of vrious devices bsed on MXene-lled polymer is full of
pplictions nd innovtions.

16.3 EXISTING APPLICATIONS AND FUTURE PERSPECTIVES

OF MXene–POLYMER NANOCOMPOSITES
Becuse of surfce termintions, numerous compositions, nd high hydrophobicity, MXene-lled
polymers exhibit high therml, electricl, nd mechnicl properties. Due to excellent mechnicl,
electricl, mgnetic, nd opticl properties nd effective control over tht in polymer composites,
it hs been termed wonder mterils for future pplictions. MXenes nd their vrious lms show
excellent conduction with metls nd gret exibility, due to which they re importnt for exible
electrochemicl devices [24–28]. There re numerous pplictions of MXene lled Composites tht
hve lredy been strted nd hve lrge scope for future improvements.

16.4 FUTURE SCOPE OF CONDUCTIVE APPLICATIONS

The drstic chnge in the electricl conductivity of MXene-bsed polymers mkes them suitble
for mny conductive pplictions [29–30]. An increse in the porosity of hybrid fom with high
electromgnetic wve ttenution is lso useful for modern pplictions like conducting fbrics. In
the future, MXene, cellulose nnocrystl cn be woven into fbrics mterils. Three-dimensionl
printing of MXene frmes with tunble electromgnetic interference lso hs excellent potentil s
3D printing tht might be very useful in industril, s well s medicl orgn, printing pplictions
[14, 30]. MXene-lled polymer ptterns with  thermochromic polymer like polydimethylsiloxne
298 MXene-Filled Polymer Nanocomposites

cn be used for tunbility in colors from blue to red under the tretment with high-intensity electro-
mgnetic rditions [31].
MXene-lled polymers hve lso shown excellent results in EMI shielding tht use to protect
ginst incoming or outgoing electromgnetic frequencies (EMF). EMI shield helps in protecting
electronic devices from EMI. It my replce trditionlly fbricted shields from metl sheets.
Although metl shields re effective in terms of shielding but hve the disdvntges of being
hevy nd bulky to design nd high susceptibility to corrosion. Its high density restricts its use
in broder pplictions in smll nd smrt electronic products [32–33]. Recently, MXene-bsed
polymers received vst ttention to using EMI shielding eld becuse of their exceptionl electricl
conductivity, hydrophilicity, nd chemicl ctivity.
In the recent future with fth-genertion (5G) mobile networks, the use of electronic devices
will be rised exponentilly, so it will be necessry to tke mesures for utmost cre bout people’s
physicl helth. For this, EMI nd rdition need to be controlled [34]. MXene-lled polymers give
hope to develop EMI shields with lightweight nd corrosion-resistnt mterils. With the continuous
increse in the use of portble nd werble devices, exibility nd excellent mechnicl stbil-
ity re new essentil development directions for EMI shielding mterils [35–37]. MXene-lled
polymers re the future mterils to cope with new development trends of electronic components
[38–40]. The cost of the MAX phse, MXenes re reltively high t this stge, nd it is vitlly
importnt to relize  low-cost industril production of MXenes.

16.5 FUTURE SCOPE OF TRIBOLOGICAL APPLICATIONS

The efciency of ny mchinery nd its lifetime re lwys  mtter of concern. As in modern
society, friction, wer of mterils, nd lubriction hve become incresingly crucil [41]. Industry
concern is lwys bout the minimiztion of friction, less use of nonrenewble energy in trnsport-
tion nd industril sectors. Reserch on the development of excellent lubricnt mterils to combt
friction nd wer of mterils is of gret importnce.
MXene-bsed polymers hve shown outstnding tribologicl properties s  promising lubricnt
nd s n excellent dditive to compositions for friction reduction, wer of the mterils, nd ther-
ml stbility. MXene lrgely improved the ntifriction properties of bse oil [42]. In  similr study
published by Zhng et l. 1.0 wt% of 10–20 nm, Ti3C2 nnosheets effectively improved the friction
nd ntiwer properties of bse oil [43]. Liu et l. reported low friction with 0.8wt% of highly exfoli-
ted Ti3C2 dded to bse oil [44].
Titnium crbide (Ti3C2) MXene-lled polymer is lso  promising mteril for solid lubric-
tion. Zhng et l. reported on the synthesis of Ti3C2/ultr-high moleculr weight polyethylene
composites tht reduced the friction wer due to dhesive behvior [45]. Ti3C2 nnosheets/copper
composites with  very low wer rte nd bout hlf the reduction in the coefcient of friction
were reported by Mi et l.[46]. Hu et l. reported Ti3C2Tx /Al composites with  coefcient of
friction 0.2 in dry sliding test, which is twice lower thn tht of bre Al [47]. Recently, Yin et l.
lso developed Ti3C2/nnodimond polymer composites tht exhibited ultr-wer resistnce t
room temperture on rubbing ginst  polytetruoroethylene (PTFE) bll in the ir. The com-
bintion of the rolling ction of nnodimond with the slipping nd intercltion of MXene pro-
vides n effective reduction in wer [48]. Zhng et l. predicted n increse in the friction with
Ti nd O vcncies, through the increse in surfce roughness. The –O-terminted Ti3C2 nd
the –OH termintions of Ti3C2 further reduced its interlyer friction [49]. Both surfce termin-
tions nd interclted wter in Ti3C2Tx MXene reduced the bond strength, resulting in  lower
friction force under dry on stinless steel surfces [49]. Ti3C2 MXene-lled polymers cn lso
ct s  solid lubricnt on different substrtes t the nnoscle [50]. All these studies hve shown
the gret potentil of MXene-lled polymers s solid lubricnts; however, no or very few studies
reported superlubricity n using MXene-lled combintion. MXenes re quite rective towrd
Future Perspectives of MXene-Filled Polymer Nanocomposites 299

the environment prticulrly in wter [51–52], therefore conducting mesurements should be per-
formed in n inert tmosphere.
In the future, superlubricity with MXene-lled polymers will be developed with n dditionl
benet of reduced wer. MXene/grphene composite coting reduces the brsion of MXene while
its superlubricity behvior remins unchnged.

16.6 FUTURE SCOPE FOR SENSING APPLICATIONS

MXene-lled polymers exhibit high metllic conductivity, tunble bndgp, excellent detection,
nd sensing pplicbility. MXene-lled polymers cn be developed s  vriety of sensors spe-
ciclly electrochemicl, gs, nd photoluminescence sensors. MXene-lled polymers lso show
 good response under low humidity nd high humidity conditions. Polycrylmide (PAM) nd
MXene were lminted to form  double-lyer sensor, nd with this, the wide-rnge liner sensitive
humidity sensing could be well nlyzed [53]. The development of exible nd werble sensors
cn lso be developed using MXene/polymer composite sensors. It hs been reported tht  degrd-
ble PLA nd Ti3C2Tx were blended to form  werble pressure sensor [54]. It ws found tht the
sensor hd excellent cycle stbility nd fter 10,000 compression cycles. The response nd recovery
were reported 11ms nd 25ms, respectively. Hu et l. reported Ti3C2 Nnosheet composite erogels
s werble pressure sensors [55]. MXene-lled polymers cn be developed s excellent stress sen-
sors in the future becuse they hve very good bending strength nd becuse of their electronic
properties. It cn lso be used to detect long-term stress nd strin in the civil construction of the
rodwys, bridges, nd buildings. In the future, MXene-lled polymers come up with mjor ppli-
ctions s physicl sensors.

16.7 FUTURE SCOPE FOR ENERGY STORAGE APPLICATIONS

It hs been found tht the electricl properties of MXenes re like those of metls nd semiconduc-
tors, which is due to their composition of elements nd groups on the surfce terminl [56]. Idelly,
pure MXenes re metllic. But they cn be turned into semiconductors. Similr to other 2D mte-
rils, both orgnic/inorgnic molecules nd vrious ions cn spontneously perform intercltion
between MXene lyers, which provides  lrger surfce re for chrge storge nd gives  wy to
increse the conductivity of lyered mterils by incresing the crrier concentrtion. MXenes hs
 wide ppliction in electronics becuse of the like exibility nd metl-like electric conductivity
[57–58]. MXene lyers with  lrge interlyer spcing nd intercltion of different-sized ctions
in the MXene-bsed polymers mke them the best cndidte for the energy storge device. In the
future, in spite of using lithium, there re  vriety of ctions vilble, for exmple, sodium, pots-
sium, mgnesium, nd others, tht cn be interclted between the MXene lyers for the develop-
ment of hybrid devices. In the future, conducting polymers shll lso be explored to develop exible
devices. The provision of n dditionl route for electron conduction by keeping suitble interlyer
seprtions my lso be useful to trnsprent nd exible energy sources. Hence, contributing to the
improvement of electrochemicl performnce. The effect of interlyer distnce in energy storge
devices nd MXene hybrids would led to  useful pth for further investigtions towrds energy
storge pplictions.

16.8 FUTURE SCOPE OF MXene-POLYMER NANOCOMPOSITES

IN BIOMEDICAL STORAGE APPLICATIONS
MXene hs different end groups on its surfce, which helps it rect differently on the surfce,
excellent hydrophilicity, mzing biocomptibility, nd remrkble electricl nd opticl proper-
ties. Thus, MXene hs  gret source for biomedicl purposes [59].
300 MXene-Filled Polymer Nanocomposites

MXenes might be used in mny biomedicl pplictions, like ntimicrobil ctivities, drug
delivery, dignostic, sensing, nd 3D printing of orgns [60–62]. MXene hs found its ppliction
in mny biomedicl elds but is still in its growing stge in this eld. However, the performnce of
MXenes minly focuses on the electricl nd opticl properties so fr. In the future, more biomedi-
cl pplictions shll be developed on mgnetic properties besides mgnetic resonnce imging
(MRI). A better understnding of the mechnism, improving their properties, nd using them more
ppropritely. More pplictions of MXenes shll be explored in biomedicl elds, such s cous-
tic dynmics therpy. MXene/polymer nnocomposites need to be further explored nd developed
becuse they re rrely used in this eld. MXene-bsed polymers hve gret potentil for surfce
modiction nd functionliztion, so in the future they cn nd their ppliction in phototherml
nd chemo-phototherml therpy [63–64]. Due to low toxicity, MXene does not ffect the envi-
ronment much. MXene cn lso nd its ppliction in trgeted nticncer drug delivery [65–66].
MXene cn nd its mjor ppliction in cncer dignosis.

16.9 FUTURE SCOPE FOR WEARABLE SMART

DEVICES STORAGE APPLICATIONS
The rst genertion of werble nd smrt devices lredy begins in the form of smrt wer-
ble displys, smrt grments, nd wtches with helth monitoring systems., this pves  pth for
future werble electronics. However, there re mny chllenges like durbility, performnce in
comprison to existing conventionl devices, nd  truly exible nture [67–69]. The extrordi-
nry cpcitnce, metllic conductivity, superior hydrophily, nd rich surfce functionlity mke
MXene–polymer nnocomposites the best cndidte for promising exible electrodes. The interc-
ltion of polymers into MXene lyers will promote the moleculr-level coupling between MXene
nd polymer molecules. This condensed combintion is supposed to effectively improve the strength
nd exibility of MXene polymers. Mny polymers hve been reported, however, PVA demon-
strtes enormous potentil s the cndidte reinforcement to prepre MXene-bsed lm electrodes
becuse of the high solubility in wter nd the fuent hydroxyl groups long the moleculr chin,
which cn be used to form hydrogen bonds between PVA nd MXene, with rich electronegtive
oxygen nd uorine groups. Reserch on high-qulity exible energy devices hs now become the
core re of reserch nd product development. Supercpcitors, s energy storge devices, ttrct
ttention due to their high power densities nd long cycle life spn. devices, especilly in exible
supercpcitors. The outstnding conductivity of MXenes polymers results in higher power density
thn semiconductor-type metl oxides, mking them suitble for rpid-chrge function from the
current consumer electronics [70–72]. Promising ctive sites in MXene support  lot for excellent
photoctlytic nd hydrogen evolution rections.
Nowdys foldble phones re lredy vilble in the mrket. MXene-lled polymer s  mte-
ril hs high exibility, so it cn nd its future ppliction in the exible nd trnsprent electronic
devices, such s mobile phone, smrtwtches, nd the like, cn be cost-effective lso [75].

16.10 FUTURE SCOPE FOR MEMBRANE SEPARATION

Deslintion of wter is one of the most potentil res of reserch, due to the scrcity of potble
wter. In vrious methods of deslintion, membrne deslintion is gining  lot of interest, in
which minerls nd slts re removed from wter by pssing through  semipermeble membrne.
The idel deslintion nd wter tretment membrnes should hve high ux, high selectivity,
stbility, nd resistnce ginst fouling nd chlorine-like chemicl [76]. In the eld of the mem-
brne, the seprtion of MXene hs drwn ttention. MXene-bsed membrnes hve shown vri-
ous potentil in seprtion pplictions, such s wter tretment, osmotic energy conversion, gs
seprtion, nd the like [77]. MXenes re considered skeleton mterils for prepring lmellr-
structure membrnes. different types of nnomterils such s re dded to fbricte mixed-mtrix
Future Perspectives of MXene-Filled Polymer Nanocomposites 301

membrnes with MXenes nd MXenes re used s coting mterils on membrne supports con-
sisting of vrious mterils such s nodic luminum oxide, polyvinylidene uoride, nd polycr-
bonte [78]. The membrne’s rejection of inorgnic slts is below 23% with ux bove 432 L m−2 h−1
t 0.1 MP, which indictes tht the membrne cn be used with extremely high efciency in dye
deslintion nd wstewter tretment [79].
Recent reports show tht MXenes hve emerged s one of the mzing mterils with potentil
pplictions in deslintion; however, more still my need to be ddressed to exploit their remrk-
ble properties [80–81]. It is still  need for n effective long time storing technique for MXene
solution without oxidtion. Low yield, control in ggregtion, low-cost methods need to be devel-
oped. The bottom-up design of n efcient, nd environment-friendly system for the production of
MXene polymers will be helpful in opening  new door for possible pplictions [82–83]. Surfce
modiction in polymer-bsed composites will help to improve their stbility, biocomptibility, nd
recyclbility. MXene–polymer-bsed composites s  solution emerging nd hve been considered
s future deslintion technology. Despite chllenges, MXene–polymer composites hve ssured
n er of the next-genertion 2D nnomterils wter puriction nd environmentl remedition.

16.11 CHALLENGES IN THE DEVELOPMENT OF APPLICATIONS

MXene–polymer nnocomposites hve found their ppliction in industries but re still in their
primry stge. The results tht hve been reported re commendble, but the problem relted to
the production is not resolved. The current studies do not focus on the ppliction in industries
[84–86]. Mteril property improvements cnnot be relized without the use of colloidl MXene-
lled polymers t scle. Their doption by industries hs chllenged the fce of the sme brriers
found in the eld of grphene [87]. Figure 16.1 shows  summry of properties, pplictions, nd
future scope.
In ddition to the chllenges tken into considertion from  commercil or industril point of
view, the other issues might be, cost, sfety, nd end of life. Production costs nd then dispersing re
quite expensive. Stbility during storge nd trnsport must lso be considered; the dispersion must
be stble for  sufciently long period, during trnsport nd for storge. Toxic nd highly mmble
solvents would be voided. Finlly, the end of life nd disposl must lso be considered [88–89].

16.12 CONCLUSION
MXene-lled polymers hve extrordinry conducting, mechnicl, opticl, nd tribologicl prop-
erties. The rre combintion of these properties nd superior control over these using vrious rtios,
constituents, nd functionliztion mke them suitble for vrious pplictions in energy devices,
sensing devices, electronic devices, low-friction mterils, nd medicl nd environmentl pplic-
tions. Recent reserch nd the future scope of MXene-lled polymers in conducting pplictions
like conducting fbrics, 3D printing, medicl orgn printing, 5G mobile networks pplictions, EMI
shielding, nd tribologicl pplictions like super-lubricnt mterils. Sensing pplictions, like
exible nd werble sensors, efcient gs sensors, storge devices, nd seprtion membrnes,
hve been envisioned in this chpter. Although MXene-lled polymers re emerging s n excellent
cndidte for mny pplictions, still, chllenges like lrge-scle production, nontoxic, bottom-up
production; effective control on gglomertion; nd oxidtion re still to be ddressed so tht more
efcient devices cn be developed in lrge-scle environmentlly friendly wys. A lot of hope exists
in the future of trnsprent, exible MXene-lled polymers tht shll serve society in lmost ll
domins of dy-to-dy life.

ACKNOWLEDGMENT
Authors re thnkful to ITM University Gwlior, for providing librry nd lb fcilities.
 302

FIGURE 16.1 Properties, pplictions, nd future scope of MXene-lled nnocomposites.

MXene-Filled Polymer Nanocomposites
Future Perspectives of MXene-Filled Polymer Nanocomposites 303

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Index
A C
acetone sensors, 229, 230 cancer
acryl amide (AA), 175 photothermal therapy for, 11, 44, 56
aerogels theranostics, 252, 252–253
in electromagnetic shielding, 57, 199–201 capacitive strain sensor, 174
in microsupercapacitors, 183 carbon dioxide sensors, 226–227, 227
in sensing applications, 55 carbon nanotube (CNT), 14, 38, 72, 76, 81, 83, 97, 112–113,
in strain sensors, 264 133, 141, 173, 183, 193–194, 239, 262–263, 265, 284
template method in fabrication of, 121 chemical exfoliation, 1–2
AFM, see atomic force microscopy (AFM) chemical intercalation, 3, 4
agricultural ammonia, 221–222 chemical properties, 5–6
ammonia sensors, 218–223, 220–221, 225–226, 228 chemical vapor deposition (CVD), 5, 157
ANF, see aramid nanober (ANF) CNT, see carbon nanotube (CNT)
antennas, wearable, 272 conductivity
antibacterial applications, 44, 56, 92, 100, 179, 253, 254 of green polymer MXene nanocomposites, 91, 95–96
applications of MXene elastomer nanocomposites, 76, 76–77
exible and wearable, 262–274 of MXene polymer nanocomposites, 297–298
of green polymer MXene nanocomposites, 92, 98–102, of thermal properties, of MXene elastomer
99, 101 nanocomposites, 110
of MXene elastomer nanocomposites, 80–83, 81, 82, 82 contrast agents, in medical imaging, 248, 251, 251, 252
of MXene polymer nanocomposites, 37, 38, 261–274, crystallization
296–297 cold, 135, 141, 146–148
of MXenes, 10–15, 14–15 effect of MXene in, of polymer nanocomposites,
of self-healing materials, 185, 185 148–149, 149
of thermoplastic MXene polymer nanocomposites, 55–58 MAX phases and, 141–142
of thermoset/MXene nanocomposites, 126–127 of MXene polymer nanocomposites, 133–149, 136,
see also biomedical applications 138–139, 143–144, 145, 149
aramid nanober (ANF), 10, 113, 200, 270 orientation and, 143
atomic force microscopy (AFM), 156, 156, 156–157 of polymer nanocomposites, 142–143, 143
atomistic friction, 154–158, 155–156, 157–158 thermodynamics of, 141–142
CVD, see chemical vapor deposition (CVD)
B
D
barrier properties, of MXene elastomer nanocomposites,
79, 79–80 Danusso–Tieghi (D-T) Model, 283
battery DEA, see dielectric analysis (DEA)
lithium-sulfur, 13 DIC, see differential interference contrast (DIC)
MXene polymer nanocomposites in, 240, 240–241, 241 dielectric analysis (DEA), 134
sodium-ion, 13 dielectric properties
zinc-ion, 183 of MXene elastomer nanocomposites, 77
see also energy storage applications of MXene polymer nanocomposites, 41
bioimaging, 11, 56 of polyvinylidene uoride, 202
contrast agents in, 248, 251, 251, 252 of thermoset epoxy, 111, 202
MXene polymer nanocomposites in, 44, 250, 251 differential interference contrast (DIC), 135
biomedical applications differential scanning calorimetry (DSC), 134–135
antibacterial, 254 Drager nitrogen tube method (DTM), 222
biosensing, 253–254, 255, 273–274 drug delivery, 11, 56, 250, 251, 273
in drug delivery, 11, 56, 250, 251, 273 DSC, see differential scanning calorimetry (DSC)
future of, 299–300 DTM, see Drager nitrogen tube method (DTM)
glucose sensor, 12, 56 dynamic mechanical analysis (DMA), 134
of green polymer MXene nanocomposites, 100
of MXene polymer nanocomposites, 247–256,
E
248–249, 251–252, 254–255, 273–274
of MXenes, 11–12 electrical properties
of thermoplastic MXene polymer nanocomposites, 56 of MXene elastomer nanocomposites, 76, 76–77
tissue regeneration, 273 of thermoplastic MXene polymer nanocomposites, 54,
wound healing materials, 92, 100, 180, 253, 254, 273 54–55
biosensing, 253–254, 255, 273–274 see also dielectric properties

309
310 Index

electrochemical applications, 12–15, 14–15 G

electrodes, 13, 98–99, 183–184, 184, 236–240, 237–238
electrolytes, non-aqueous, 14, 14 gas sensors, 10–11, 212–213, 216–217, 267–268
electromagnetic interference (EMI) shielding see also sensing applications
absorption lossn, 195 generators, nano-, 58, 102, 114, 214, 223–224, 271–272
aerogels in, 199–201 glass transition temperature, 143–146, 144, 145
efciency, 195 glucose sensor, 12, 56
exible and wearable, 269–271 green polymer MXene nanocomposites
foams in, 199–201, 201 applications of, 92, 98–102, 99, 101
hierarchical architectures in, 199–201 biomedical applications of, 100
material design, 196–197, 197 characterization of, 91–97, 92, 93–94
measurement techniques with, 196 conductivity of, 91, 95–96
mechanism of, 194–196 in electrodes, 98–99
multiple reections in, 196 ame retardancy of, 95
with MXene elastomer nanocomposites, 83, 83, 84, 204 in fuel cells, 101–102
with MXene polymer nanocomposites, 198–204, mechanical properties of, 97–98, 98
200–201, 269–271 overview of, 89
reection loss in, 195–196 processing of, 92
stimuli-responsive, 198, 198–199 in supercapacitors, 100–101
with thermoplastic MXene polymer nanocomposites, synthesis of, 89–91, 91
57, 201–203 tensile properties of, 98
with thermoset/MXene nanocomposites, 126–127, 203 viscosity of, 91
electronic applications, 10–11
electronic properties, of MXenes, 2–3, 6, 7 H
EMI, see electromagnetic interference (EMI) shielding
emulsion method, with MXene elastomer heater, wearable, 271
nanocomposites, 76 hierarchical architectures
energy conversion systems, 235–243, 237–238, 240, in electromagnetic shielding, 199–201
241–243, 242 HMC, see Hoffman modulation contrast (HMC)
energy storage applications Hoffman modulation contrast (HMC), 135
future of, 299 hot press/injection molding
of MXene-based nanocomposites, 235–243, 237–238, with thermoset/MXene nanocomposites, 118
240, 241–243, 242 humidity sensors, 55, 266, 267
of MXenes, 12–15, 14–15 hydrogels
of thermoplastic MXene polymer nanocomposites, in drug delivery, 250, 251
44, 56–57 in electrodes, 13
see also battery in electronic applications, 10
epidermal sensors, 177, 179, 268–269 properties of, 5–6
ethanol sensors, 228–229, 229–230 as self-healing, 183, 184
self-healing characteristics in, 173–177, 175–176, 178
in skins sensors, 38
F in strain sensors, 55, 265–266
fabrication
of thermoset/MXene nanocomposites, 115–123, I
116–117, 119–120, 122, 127
see also synthesis ICPs, see intrinsically conducting polymers (ICPs)
fabrics, 272–273 imaging, medical, see bioimaging
fast scanning chip calorimetry (FSC), 135–136 in situ polymerization
FEM, see nite element modeling (FEM) with MXene polymer nanocomposites, 33, 216–217
ltration applications, with thermoplastic MXene polymer with thermoplastic MXene polymer nanocomposites,
nanocomposites, 58 47, 48
nite element modeling (FEM), 285–286 with thermoset/MXene nanocomposites, 115–116, 116
ame retardancy, 79, 92, 95 intrinsically conducting polymers (ICPs), 197, 204
exible and wearable applications ionic intercalation and sonication-assisted method
future of, 300 with thermoset/MXene nanocomposites, 121–123
of MXene polymer nanocomposites, 262–274
foams L
conductivity in, 77
in electromagnetic shielding, 10, 199–201, 201 latex compounding
in pressure sensors, 55 with MXene elastomer nanocomposites, 72, 72
freeze-drying methods, with MXene elastomer with MXene polymer nanocomposites, 31, 32, 36
nanocomposites, 72–73, 73 layer-by-layer deposition method, with MXene elastomer
FSC, see fast scanning chip calorimetry (FSC) nanocomposites, 73–74, 74
fuel cells, 12, 58, 101–102, 114, 199, 236, 242, 243 light, absorption of, 8–9, 9
Index 311

lithium-sulfur battery, 13 layer-by-layer deposition method with, 73–74, 74

lubricant additives, 158–164, 159, 161–162, 163 mechanical properties of, 77–78, 78
melt blending method with, 73
preparation methods with, 72–75, 72–76
M
properties of, 76, 76–80, 78, 79
magnetic properties, 6, 7 in sensors, 80–82, 81, 82, 82
mechanical properties solution casting method with, 74
of green polymer MXene nanocomposites, 97–98, 98 solvent mixing-melt blending method with, 73
of MXene elastomer nanocomposites, 77–78, 78 spin-coating method with, 74
of MXenes, 5–6 suction ltration method with, 75, 75
of thermoplastic MXene polymer nanocomposites, thermal properties of, 76, 76–77
51–54, 52–53 thermal stability of, 78–79
of thermoset/MXene nanocomposites, 110–111, vacuum-assisted ltration method with, 75, 75
124–126, 125 MXene nanocomposite organohydrogel (MNOH),
medical applications, see biomedical applications 174–175
melt, non-isothermal MXene polymer nanocomposites
of MXene-based polymer composites, 146–148 in ammonia sensors, 218–223, 220–221
melt blending, 33 in antennas, 272
with MXene elastomer nanocomposites, 73 in antibacterial applications, 253, 254
with MXene polymer nanocomposites, 33 applications of, 37, 38, 261–274, 296–297
with thermoplastic MXene polymer nanocomposites, atomistic friction in, 154–158, 155–156, 157–158
48, 49 in batteries, 240, 240–241, 241
melting in bioimaging, 250, 251
thermodynamics of, 141–142 in biomedical applications, 247–256, 248–249,
membrane separation, 300–301 251–252, 254–255, 273–274
methanol sensors, 229, 230 biomedical properties of, 249, 249–250
micro/nanoscale local thermal analysis (MNLTA), 134 in biosensing, 253–254, 255, 273–274
micro-supercapacitors (MSCs), 13–14, 14, 181–183, 185, in cancer theranostics, 252, 252–253
201, 238, 271 classication of, 261
microwave absorption, 198–204, 200–201 cold crystallization of, 146–148
MILD, see minimally intensive layer delamination (MILD) conductivity of, 250, 261, 297–298
minimally intensive layer delamination (MILD), 3–4, 4 in drug delivery, 273
MNLTA, see micro/nanoscale local thermal analysis drug delivery with, 250, 251
(MNLTA) in electrodes, 236–240, 237–238
MNOH, see MXene nanocomposite organohydrogel (MNOH) in electromagnetic shielding, 198–204, 200–201,
modeling and simulation (M&S) 269–271
base model in, 279 in energy storage and conversion applications,
experimental frame in, 279 236–242, 237–238, 240, 241–243, 242
nite element modeling in, 285–286 evaluation of thermal behavior of, methods for,
lumped model in, 279 134–136, 136
merits and demerits of, 291–292 fabrication of sensors with, 216–217
of MXene polymer nanocomposites, 285–291, 286–291 exible and wearable applications of, 262–274
object in, 279 in fuel cells, 242, 243
reduced-order model in, 282 future of, 295–301, 302
representative volume elements in, 286–290, 287–289 in gas sensors, 212–213, 267
rule of mixture in, 281 glass transition temperature and, 143–146, 144, 145
system in, 279 in heaters, 271
theoretical, 280, 280–285 in humidity sensors, 266, 267
variables in, 279 hydrogels, 265–266
verication in, 279 hydrophilicity of, 249–250
M&S, see modeling and simulation (M&S) latex compounding in, 31, 32
MSCs, see micro-supercapacitors (MSCs) as lubricant additives, 158–164, 159, 161–162, 163
MXene elastomer nanocomposites M2X-based, 223–226
applications of, 80–83, 81, 82, 82 melt blending with, 33
barrier properties of, 79, 79–80 microwave absorption of, 198–204, 200–201
conductivity of, 76, 76–77 modeling of, 284–291, 286–291
dielectric properties of, 77 non-isothermal melt of, 146–148
electrical properties of, 76, 76–77 photothermal conversion in, 250
electromagnetic interference shielding with, 83, 83, in piezoresistive sensors, 262–263
84, 204 in pressure sensors, 262–263
emulsion method with, 76 properties of, 33–36, 35–36, 37
ame retardancy of, 79 sensing applications of, 262–269, 267
freeze-drying methods with, 72–73, 73 sensing characteristics in, 213–215, 214
latex compounding with, 72, 72 sensing measurements with, 217
312 Index

shape and morphology in, 249 polyvinylidene uoride (PVDF), 10, 31, 38, 45–46, 50, 50,
simulation of, 278–285 55–58, 148, 202
in situ polymerization with, 33, 216–217 polyvinyl pyrrolidine (PVP), 11, 46, 56, 176, 252, 263
solution blending with, 30–31, 31 pressure sensors, 31, 36, 38, 38, 55, 77, 80–81, 82, 172,
in strain sensors, 263–266 185, 262–263
in supercapacitors, 236–240, 237–238 properties
surface-to-volume ratio in, 249 of MXene elastomer nanocomposites, 76, 76–80, 78, 79
synthesis of, 29–33, 30, 31, 32 of MXene polymer nanocomposites, 33–36, 35–36, 37
in textiles, 272–273 of MXenes, 5–10, 7–9
thermal and crystallization behavior of, 133–149, 136, of thermoplastic MXene polymer nanocomposites,
138–139, 143–144, 145, 149 51–55, 52–54
thermal behavior of, 138–141, 139 PTT, see photothermal therapy (PTT)
thermoplastic, 45–58, 47–54 PVDF, see polyvinylidene uoride (PVDF)
in tissue regeneration, 273 PVP, see polyvinyl pyrrolidine (PVP)
tribological performance of, 153–166, 155–156, 157,
158, 159, 161–162, 163, 165, 298–299
R
in vapor sensors, 212–213
in wound healing materials, 273 reduced-order model (ROM), 282
MXenes representative volume elements (RVEs), 286–290,
applications of, 10–15, 14–15 287–289
properties of, 2–3, 5–10, 7–9 resin transfer molding
synthesis of, 3–5, 4 with thermoset/MXene nanocomposites, 118–119, 120
rheological properties, 9–10
N ROM, see reduced-order model (ROM); rule of
mixture (ROM)
nanogenerators, triboelectric, 58, 102, 114, 214, 223–224, rubbery state, 144
271–272 rule of mixture (ROM), 281
NBR, see nitrile butadiene rubber (NBR)
nitrile butadiene rubber (NBR), 31, 36, 37, 77, 83, 83
S
N-N model, 284
SAAM, see sulfuric acid absorption method (SAAM)
O SAs, see saturable absorbers (SAs)
saturable absorbers (SAs), 8–9, 9
OFETs, see organic eld-effect transistors (OFETs) SB, see Schottky barrier (SB)-free metal contacts
optical properties, 8, 8, 8–9, 9 Schottky barrier (SB)-free metal contacts, 10
organic eld-effect transistors (OFETs), 10 self-healing, 5–6
organic thin-lm transistors (OTFTs), 10 applications, 185, 185
OTFTs, see organic thin-lm transistors (OTFTs) characteristics in hydrogels, 173–177, 175–176, 178
characteristics of MXene-based nanocomposites/
nanosheets, 178–180, 179–180
P
characteristics of MXene-based supramolecules,
PAA, see polyacrylic acid (PAA) 180–181
PANIF, see polyaniline ber (PANIF) efciency, 184
PDMS, see polydimethylsiloxanes (PDMS) in electrodes, 183–184, 184
PDT, See photodynamic therapy (PDT) in lms, 183–184, 184
photodetector, 10–11 history of, 172–173
photodynamic therapy (PDT), 247, 250, 252 in MXene polymer nanocomposites, 171–186185,
photoluminescence, 8, 11, 252, 261, 299 172–173, 175–176, 178–182, 184
photonic applications, 11 sensor applications and, 37, 80
photothermal therapy (PTT), 8, 11, 44, 56, 126, 250, 251, in supercapacitors, 181–183, 182
252, 300 time, 184
piezoresistive sensors, 11, 38, 80–81, 82, 199, 262–263 sensing applications
PLM, see polarized light microscopy (PLM) acetone sensors, 229, 230
polarized light microscopy (PLM), 135, 136 ammonia sensors, 218–223, 220–221, 225–226, 228
polyacrylic acid (PAA), 46, 89–92, 92, 93, 100, 175, biosensing, 253–254, 255
176, 177 carbon dioxide, 226–227, 227
polyaniline ber (PANIF), 264 epidermal sensors, 177, 179, 268–269
polydimethylsiloxanes (PDMS), 31, 38, 47, 58, 74, 77–78, ethanol sensors, 228–229, 229–230
78, 80–81, 82–83, 92, 96, 102, 180, 193–194, 200, ex situ approaches in, 216
201, 204, 263, 272 exible and wearable, 262–269, 267
polyvinyl alcohol (PVA), 5, 27, 29–30, 30, 36, 45–48, future of, 299
53–57, 72, 90–92, 92, 93, 95, 97, 98, 100, 139–140, gas sensors, 10–11, 212–213, 216–217, 267–268
174–177, 183, 215, 228, 237, 252, 253, 255, 263, humidity and, 221
265, 267, 270, 273, 300 humidity sensors, 55, 266, 267
Index 313

M2X-based MXene polymer composites in, 223–226 textiles, 272–273

materials in, 215–216 TGA, see thermogravimetric analysis (TGA)
methanol sensors, 229, 230 thermal properties
monitoring of analytes in, 218 evaluation of, 134–136, 136
MXene elastomer nanocomposites in, 80–82, 81, 82, 82 of MXene, 136–138, 138
piezoresistive sensors, 11, 38, 80–81, 82, 199, 262–263 of MXene elastomer nanocomposites, 76, 76–77
pressure sensors, 31, 36, 38, 38, 55, 77, 80–81, 82, 172, of MXene polymer nanocomposites, 133–149, 136,
185, 262–263 138–139, 143–144, 145, 149
ranges of detection in, 214 thermal stability
repeatability in, 214 of MXene elastomer nanocomposites, 78–79
reproducibility in, 214 thermodynamics
response and recovery time in, 214 of crystallization and melting of polymers, 141–142
room temperature operation in, 214 thermogravimetric analysis (TGA), 134–135, 138–139
selectivity in, 213 thermomechanical analysis (TMA), 134
sensing measurements in, 217 thermoplastic MXene polymer nanocomposites, 45–58,
sensitivity in, 213 47–54
in situ approaches with, 216 applications of, 55–58
stability in, 213 biomedical applications of, 56
strain sensors, 31, 54–55, 80–81, 82, 174–176, 255, characterization of, 48–51, 49–52
263–266 electrical properties of, 54, 54–55
temperature and, 221 electromagnetic interference shielding with, 57,
of thermoplastic MXene polymer nanocomposites, 55–56 201–203
sensing characteristics, in MXene polymer energy storage applications of, 56–57
nanocomposites, 213–215, 214 ltration applications with, 58
SERS, see surface-enhanced Raman scattering (SERS) mechanical properties of, 51–54, 52–53
simulation, see modeling and simulation (M&S) melt blending with, 48, 49
sodium-ion batteries, 13 processing of, 46–48, 47–48
solar cells, 10 properties of, 51–55, 52–54
solution blending sensing applications of, 55–56
with MXene polymer nanocomposites, 30–31, 31 in situ polymerization method with, 47, 48
with thermoplastic MXene polymer nanocomposites, solution blending with, 46, 47
46, 47 thermoset/MXene nanocomposites
solution casting method, with MXene elastomer applications of, 126–127
nanocomposites, 74 carbon nanotubes and, 112–113
solution mixing/blending challenges with, 127
with thermoset/MXene nanocomposites, 116–117, 117 conductivity of, 110
solvent mixing/blending electromagnetic shielding with, 126–127, 203
with MXene elastomer nanocomposites, 73 fabrication of, 115–123, 116–117, 119–120, 122, 127
spin-coating method, with MXene elastomer hot press/injection molding with, 118
nanocomposites, 74 ionic intercalation and sonication-assisted method
strain sensors, 31, 54–55, 80–81, 82, 174–176, 255, 263–266 with, 121–123
suction ltration method, with MXene elastomer mechanical properties of, 110–111, 124–126, 125
nanocomposites, 75, 75 morphology of, 123–124, 124
sulfuric acid absorption method (SAAM), 222 overview of, 109–110
supercapacitors, 13–14, 14, 44, 100–101, 181–183, 182, resin transfer molding with, 118–119, 120
183, 185, 201, 236–240, 237, 238, 238, 271 restacking in, 127
supramolecules, MXene-based in situ polymerization blending with, 115–116, 116
self-healing in, 180–181 solution mixing/blending with, 116–117, 117
surface-enhanced Raman scattering (SERS), 8, 11 structure of, 123–124, 124
surface functionality, 5 synthesis of, 114, 114–115
synthesis template-assisted fabrication of, 119–121, 120, 122
of green polymer MXene nanocomposites, 89–91, 91 thermal stability of, 126
of MXene polymer nanocomposites, 29–33, 30, 31, 32 thermosets in, 110–113, 111
of MXenes, 3–5, 4 ultrasonic mixing with, 117
of thermoset/MXene nanocomposites, 114, 114–115 vacuum-assisted ltration with, 118, 119
see also fabrication Ti3C2Tx MXene, 237
in ammonia sensors, 218–220, 221
in antibacterial applications, 254
T
atomistic friction and, 156, 156, 157
template-assisted fabrication barrier properties of, 80
of thermoset/MXene nanocomposites, 119–121, 120, 122 in batteries, 240, 241
TENG, see triboelectric nanogenerators (TENG) in carbon dioxide sensors, 226
tensile properties, of green polymer MXene in drug delivery applications, 250, 251
nanocomposites, 98 in elastomer MXene/nanocomposites, 204
314 Index

electrical conductivity of, 2, 12, 54, 92, 200 triboelectric nanogenerators (TENG), 58, 102, 114, 214,
in electrodes, 237, 239 223–224, 271–272
in electromagnetic shielding, 38, 270 tribological performance
in electronic applications, 10 atomistic friction and, 154–158, 155–156, 157–158
in emulsion method, 76 lubricant additives and, 158–164, 159, 161–162, 163
in fuel cells, 242, 243 of MXene polymer nanocomposites, 153–166, 155–156,
in gas sensors, 38, 267 157, 158, 159, 161–162, 163, 165, 298–299
in green polymer nanocomposites, 90, 92, 92, 96, tribology, 153
98, 98
in lubricants, 160, 163, 164 U
in micro-supercapacitors, 14, 14
in microwave absorption, 198 ultrasonic mixing
minimally intensive layer delamination with, 4 with thermoset/MXene nanocomposites, 117
optical properties in, 8
polymer crystallization and, 148 V
in pressure sensors, 82
in in situ polymerization, 33, 35 vacuum-assisted ltration
in solution blending, 46 with MXene elastomer nanocomposites, 75, 75
in strain sensors, 265 with thermoset/MXene nanocomposites, 118, 119
thermal behavior of, 138, 140, 146 vapor sensors, 212–213, 216–217, 228
thermal conductivity of, 78, 136 see also sensing applications
thermal stability of, 126 viscosity, 9–10
in thermoplastic nanocomposites, 202
in thermoset/MXene-based nanocomposites, 124
W
in tribological applications, 298–299
vacuum-assisted ltration with, 118 wet chemical etching method, 3, 4
in vapor sensors, 228, 229–230 WFs, see work functions (WFs)
tissue regeneration, 273 work functions (WFs), 10
TMA, see thermomechanical analysis (TMA) wound healing materials, 92, 100, 180, 253, 254, 273