66 Nanoscience and Nanotechnology

Chapter 3

Synthesis Routes

Learning objectives
• Different routes for the synthesis of nanoparticles and nanocrystalline materials
• Different routes for the consolidation of nanoparticles and nanocrystalline materials

T here are different ways of classifying the synthesis routes for nanostructured materials.
One of them is based on the starting state of material, namely, gas, liquid and solid.
Techniques such as vapour condensation [physical vapour deposition (PVD) and chemical
vapour deposition (CVD) and variants of these techniques] use the gaseous state of matter
as the starting material for synthesizing nanoparticles. Techniques such as sol–gel, chemical
and electrochemical (electrolytic) deposition and rapid solidification processing use liquids as
the starting material. Severe plastic deformation processes such as high-energy ball milling,
equichannel angular extrusion, etc., and nano-lithography, start with solids for synthesizing
nanocrystalline materials.
However, the most popular way of classifying the synthesis routes is based on how the
nanostructures are built, and such an approach leads to two routes, namely, the ‘bottom-up’
and the ‘top-down’ approaches. In the bottom-up approach, individual atoms and molecules
are brought together or self-assembled to form nanostructured materials in at least one
dimension. All the techniques that start with liquid and gas as the starting material fall
into this category. In the second approach (top-down approach), a microcrystalline material
is fragmented to yield a nanocrystalline material. All the solid state routes fall into this
category.
Usually, the bottom-up techniques can give very fine nanostructures of individual
nanoparticles, nanoshells, etc., with narrow size distributions, if the process parameters
are effectively controlled. The top-down techniques do not usually lead to individual
nanoparticles; however, they can produce bulk nanostructured materials. Many of the
bottom-up approaches have difficulties in scale up, while the top-down approaches can
be easily scaled up. Thus, one can see that both these approaches are complementary to
each other, depending on the requirement of a particular application. The most prominent
techniques to synthesize nanostructured materials are described.

B. S. Murty et al., Textbook of Nanoscience and Nanotechnology,

DOI 10.1007/978-3-642-28030-6_3, © Universities Press (India) Private Limited 2013
 Chapter 3: Synthesis Routes 67

3.1 BOTTOM-UP APPROACHES

3.1.1 Physical vapour deposition (PVD)

PVD is a versatile synthesis method and is capable of preparing thin film materials with control
at the nanometre scale by careful monitoring of the processing conditions. PVD involves the
generation of vapour phase either via evaporation, sputtering, laser ablation or by using an
ion beam. In evaporation, atoms are removed from the source, usually by heating it above its
melting point. On the other hand, in sputtering, atoms are ejected from the target surface by the
impact of energetic ions. Thermal evaporation has a limitation in multicomponent materials
since one of the metallic elements typically evaporates before the other, due to the differences
in boiling point and vapour pressure of the evaporating species. On the contrary, sputtering
is capable of depositing high melting point materials such as refractory metals and ceramics,
which are difficult to convert to nanomaterials by evaporation. Sputtering can result in better
stoichiometric control of the film compared to evaporation techniques. Sputter-grown films
usually have higher density than those obtained by evaporation as the sputtered atoms have
more energy than the evaporated atoms. Sputtered films are more prone to contamination
than evaporated films due to the lower purity of the sputtering target materials.
Inert gas condensation
(IGC) combined with thermal evaporation is commonly used to synthesise metallic and
metal oxide nanopowders with a well-defined and narrow size distribution. This technique
was originally introduced by Ganqvist and Buhrman in 1976 and later developed by Gleiter
in 1981. In this process, a metal is evaporated inside an ultra-high vacuum (UHV) chamber
filled with inert gas, typically helium (Fig. 3.1). The vapourised species then loses energy

Fig. 3.1 Schematic inert gas condensation unit for the synthesis of nanocrystalline particles.
68 Nanoscience and Nanotechnology

via collisions with helium molecules. As collisions limit the mean free path, supersaturation
can be achieved above the vapour source. At high supersaturation, the vapours rapidly form
large numbers of clusters that grow via coalescence and agglomeration. The clusters in the
condensing gas are transported by convective flow to a vertical cold finger surface filled
with liquid nitrogen. The removal of particles from the cold finger is carried out by a scraper
assembly. They are collected via a funnel and transported to an in situ compaction device
or coated with a surfactant agent that prevents them from agglomeration. The scraping and
consolidation of particles are carried out under UHV conditions to prevent oxidation of the
metallic nanoparticles. The size, morphology and yield of the clusters in gas condensation are
dependent on three fundamental parameters:
• Rate of supply of atoms to the region of supersaturation where condensation occurs
• Rate of energy removal from the hot atoms via the condensing gas medium
• Rate of removal of clusters once nucleated from the supersaturated region
Particle nucleation, coalescence and growth during condensation also play key roles in
forming small particles in large numbers.
As the yield of inert gas deposition is rather low, Bigot and co-workers developed a process
wherein the metallic vapours condensed into a cryogenic medium to produce metallic
nanocrystals. The main advantage of this technique is that it exhibits a higher production
rate of about 60 g/h and a yield of 75%. Rapid overheating of the metal via radio frequency
(RF) induction technique produces a high vapour pressure and substantial evaporation rate.
The reactor is supplied continuously with cryogenic liquid, and nanoparticles are formed
by rapid condensation of the supersaturated metal vapour. The condensation region, where
the particles are formed by the nucleation, growth and coalescence processes, features a
high temperature gradient—typically from 2200 K at the metallic surface to 77 K in the
cryogenic medium. The low temperature of the surrounding medium produces a high rate
of nucleation and rapid cooling of the as-formed particles limits crystal growth. Liquid
argon is used for the synthesis of Al nanoparticles to prevent the formation of aluminium
nitrides. Liquid nitrogen has been used for making Cu and Fe nanopowders. This technique
yields Cu nanoparticles of spherical shape with their size distribution following a log-normal
function peaking at 25 nm. The aluminium nanoparticles produced are also spherical, with
size less than 70 nm.
IGC using a direct current (DC) or RF magnetron sputtering source has been used
to prepare refractory metal and ceramic nanoparticles. The gas pressure, sputter power
and source substrate distance are crucial process parameters during sputtering and gas
condensation. A careful selection of these parameters will lead to the successful formation
of nanoparticles rather than the formation of a granular film. The reported particle size
is strongly dependent on argon pressure and for Mo, it decreases from 12 nm at 0.4 mbar
to 5 nm at 0.8 mbar. Figure 3.2a shows nanocrystalline Ag–Cu deposit obtained by the
IGC technique. The nanocrystalline nature of the Ag–Cu particles is clearly evident from
the diffraction rings observed in the selected area electron diffraction pattern of Fig. 3.2b.
Figures 3.2c–3.2f show the TEM micrographs of the deposit heated in situ to 200, 300, 400
and 600°C, respectively, in the TEM for understanding the grain growth behaviour of the
 Chapter 3: Synthesis Routes 69

a b c

d
pv
Cu

np
Ag

d
pv
Cu
200 nm
200 nm

d e f

200 nm 200 nm 200 nm

Fig. 3.2 Ag–Cu nanoparticles—(a) and (b)—synthesised by IGC and subjected to heating to (c) 200, (d) 300,
(e) 400 and (f) 600°C. (Source: BS Murty, IIT Madras).

nanocrystalline deposit. The figure clearly indicates that nanocrystalline nature is retained
in the deposit even after heating it to 600°C, due to the solute drag effect from the Cu present
in Ag.
Laser ablation
It is generally known that laser ablation can provide better control of the evaporation process
by congruent evaporation of constituent elements of multicomponent materials in a very short
period of time. In this technique, an intense pulsed laser beam irradiates the target of interest,
thereby vaporising atoms and clusters from the target. The total mass ablated from the target
per laser pulse is usually referred to as the ablation rate. Laser ablation in combination with
IGC is an attractive route to synthesize larger amounts of the multicomponent nanocrystalline
materials. A typical laser ablation set up is shown in Fig. 3.3. In the process, atoms ablated by
laser pulse tend to collide with helium gas, losing their kinetic energy rapidly. They eventually
condense to form a cloud consisting of fine nanocrystalline clusters. The production rate of
nanoparticles in this technique varies with helium gas pressure and laser pulse energy. Several
workers have employed laser ablation and gas condensation to produce nanoparticles of
metals, metal oxides and metal carbides.
70 Nanoscience and Nanotechnology

50 nm

Fig. 3.4 Nanoparticles of Al synthesized

Fig. 3.3 Schematic of a laser ablation chamber equipped with a by wire explosion technique.
rotating target holder. (Source: R Sarathi, IIT Madras)

Wire explosion
Wire explosion technique is similar to physical vapour deposition. A fine wire of a metal is
exploded by applying a very high voltage. The gas of atoms generated by this explosion is
allowed to condense in the chamber to yield nanoparticles. This technique can lead to the
formation of not only metallic nanoparticles but also a variety of oxides, nitrides, etc. by using
different environments in the chamber. A typical example of nanoparticles generated by this
technique is shown in Fig. 3.4.

3.1.2 Chemical vapour deposition

Chemical vapour deposition (CVD) is a process where one or more gaseous adsorption species
react or decompose on a hot surface to form stable solid products. The main steps that occur
in the CVD process can be summarized as follows:
1. Transport of reacting gaseous species to the surface
2. Adsorption of the species on the surface
3. Heterogeneous surface reaction catalysed by the surface
4. Surface diffusion of the species to growth sites
5. Nucleation and growth of the film
6. Desorption of gaseous reaction products and transportation of reaction products away
from the surface
CVD is a more complicated method than PVD for the formation of thin films and coatings.
It exhibits several distinct advantages, such as the capability to produce highly pure and
dense films or fine particles at reasonably high deposition rates, and the capability of coating
complex-shaped components uniformly due to its non–line-of-sight nature. A variety of
 Chapter 3: Synthesis Routes 71

metallic, ceramic and semiconducting thin films are being deposited by CVD. Depending on
the activation sources for the chemical reactions, the deposition process can be categorized
into thermally activated, laser-assisted and plasma-assisted CVD.
Thermally activated CVD
This is the conventional CVD technique where the resistive heating of hot wall reactors
gives sufficiently high temperatures for the dissociation of gaseous species. This leads to the
heating of the entire substrate to a high temperature before the desired reaction is achieved. It
precludes the use of substrates with melting points much lower than the reaction temperature.
Hot tungsten filament is also used to heat the reacting gases in the vicinity of the substrate.
Recently, hot filament CVD was used to grow one-dimensional SiC nanorods. Due to high
hardness, high thermal stability, wide band gap and high electron mobility, SiC nanorods are
potential materials for structural and electronic applications. Further, the Young’s modulus
of the nanorod can reach ∼ 600 GPa, which is close to the theoretically predicted value for
[111]-oriented SiC. In this CVD process, a silicon wafer was initially immersed in aqueous
Fe(NO3)3 solution to remove the contaminants before transferring it into the reactor chamber.
Carbon, silicon and silicon dioxide powders, compacted in the form of a plate, are used as
the silicon and carbon sources. The chamber was filled with hydrogen gas and a tungsten
filament was used to activate the hydrogen gas. The filament and substrate temperatures used
are 2570 and 1373 K, respectively. The hot filament causes dissociation of molecular hydrogen
to atomic hydrogen. The Fe(NO3)3 particles on the Si wafer surface were reduced by high
concentration of atomic hydrogen to iron nanoparticles, which acted as a catalyst. In order to
form hydrocarbon and silicon monoxide radicals, the silicon and carbon sources are thermally
activated by hot filaments. The rods are straight with diameters of 20–70 nm and lengths of
about 1 mm. Iron catalyst particles can be seen at the tips of the nanorods. HRTEM images
revealed that the nanorods grew along the [100] direction. An electron bright field image of
gold nanorods is shown in Fig. 3.5.
Plasma-enhanced CVD
This has a distinct advantage over thermal CVD due to its lower deposition temperature. The
plasma is generated by various energy resources such as DC, RF, microwave and electron
cyclotron resonance microwave (ECR-MW) radiation. In DC plasma, the reacting gases are
ionised and dissociated by an electrical discharge, generating plasma consisting of electrons
and ions. Microwave plasma is attractive because the excitation microwave frequency
(2.45 GHz) can oscillate electrons. Thus, high ionization fractions are generated as electrons
collide with gas atoms and molecules. SiC films have been deposited on silicon substrates
by RF plasma-enhanced CVD using a gaseous mixture of SiCl4, CH4, H2 and Ar. Recently,
microwave plasma-enhanced CVD (MW-CVD) has been used to grow one-dimensional
carbon nanotubes at a low temperature range of 600–800°C. Cold cathodes in field emission
displays need well-aligned carbon nanotube arrays. The MW-CVD method has the advantage
of achieving good alignment and selective growth on various substrates.
Conventional CVD of hydrocarbons over metal catalyst has been a typical method to
produce various forms of carbon fibres, filaments and multiwalled nanotubes. In this process,
72 Nanoscience and Nanotechnology

on c–Si

on a–SiO2

Fig. 3.5 Transmission electron micrograph of gold

nanorods, along with a small fraction of impurities. Fig. 3.6 GaN nanowires deposited by
(Source: http://commons.wikimedia.org/wiki/File: CVD on crystalline Si and amorphous silica.
Au_nr_mhore.jpg.). (Source: P Shankar, Saveetha University).

hydrocarbon molecules are absorbed and decomposed on transition metal (Fe, Ni, Co)
particles. The carbon atoms diffuse into the interior of the catalyst to form a metal–carbon
solid-state reaction. The precipitation of carbon from the supersaturated catalyst particle
gives rise to carbon tube structure. Figure 3.6 shows GaN nanowires deposited by CVD on
crystalline Si and amorphous silica.
Laser CVD is associated with the deposition of chemical vapours using a laser beam generated
from sources like CO2, Nd:YAG and Excimer. This process yields good quality films at lower
temperatures with better control on composition. For example, a silicon nitride film could be
deposited at 200°C using laser CVD, whereas it is deposited at 850°C and 450°C by thermally
activated CVD and plasma-enhanced CVD, respectively. In the case of nanoparticles, tungsten
powder of 54 nm could be synthesised from WF6/H2/M (M = Ar, Kr, Ne, Xe) gas mixtures
irradiated with an ArF Excimer laser. Moreover, ceramic Si–C–N nanometric powders can be
obtained from laser-induced gas phase reactions of SiH4, amines and NH3. The incorporation
of Si–C–N powders with sizes of 25–30 nm into aluminum improves its tensile and creep
properties considerably. The box below describes a technique (molecular beam epitaxy) for
precise formation of nanostructured thin films. There have also been attempts by people to
 Chapter 3: Synthesis Routes 73

MOLECULAR BEAM EPITAXY (MBE)

MBE is a special case of evaporation for single crystal film growth, with highly con-
trolled evaporation of a variety of sources in ultrahigh vacuum of about 10–10 torr.
Besides the ultrahigh vacuum system, the MBE system usually consists of real-time
structural and chemical characterisation capability, including reflection high energy
electron diffraction (RHEED), x-ray photoelectric spectroscopy (XPS) and Auger
electron spectroscopy (AES). Other analytic instruments may also be attached to the
deposition chamber or to a separate analytic chamber, from which the grown films
can be transferred to and from the growth chamber without exposure to the ambient
atmosphere.
In MBE, the evaporated atoms or molecules from one or more sources do
not interact with each other in the vapour phase under such low pressure.
Although some gaseous sources are used in MBE, most molecular beams are gener-
ated by heating solid materials placed in source cells, which are referred to as effusion
cells or Knudsen cells. The source materials are most commonly raised to the desired
temperatures by resistive heating. The mean free path of atoms or molecules (100 m)
far exceeds the distance between the source and the substrate (typically 30 cm) inside
the deposition chamber. The atoms or molecules striking the single crystal substrate
result in the formation of the desired epitaxial film. The extremely clean environment,
the slow growth rate and independent control of the evaporation of individual sources
enable the precise fabrication of nanostructures and nanomaterials as a single atomic
layer. The ultrahigh vacuum environment ensures the absence of impurity or con-
tamination, and thus a highly pure film can be readily obtained. Individually control-
led evaporation of sources permits the precise control of chemical composition of the
deposit at any given time. The slow growth rate ensures sufficient surface diffusion
and relaxation so that the formation of any crystal defect is kept minimal.

ATOM MANIPULATION
In addition to imaging surface topography at atomic resolution, scanning tunnelling
microscopy (STM) has the ability to carry out precise and controlled manipulation of
atoms, molecules and nanostructures. The usual technique to manipulate atoms is to
increase the current above a certain atom, which reduces the tip–atom distance, move
the tip with the atom to a desired position, and finally to reduce the current again
in order to decouple the atom and tip. The first demonstration of this technique was
performed by Eigler and Schweizer (1990), who used Xe atoms on an Ni (110) surface
to write the three letters ‘IBM’ on the atomic scale. Currently, many laboratories are
able to move different kinds of atoms and molecules on different surfaces with high
74 Nanoscience and Nanotechnology

precision. Controlled motion, pushing, pulling and sliding of the molecules depends
on the tunnelling current, the distance and the particular combination of molecule
and substrate. It is believed that the electric field between tip and molecule is the
strongest force moving the molecules, but other mechanisms such as electromigration
caused by the high current density or modifications of the surface potential due to the
presence of the tip may also play an important role.

manipulate atoms and arrange them ‘the way we want’ as has been dreamt by Feynman. These
efforts are described in the box above (atom manipulation).

3.1.3 Spray conversion processing

This route involves the atomization of chemical precursors into aerosol droplets that are
dispersed throughout a gas medium. The aerosols are then transported into a heated
reactor where the solution is evaporated to form ultrafine particles or thin films. This is an
inexpensive technique as various low cost chemical solutions are available. Various aerosol
generators—including pressure, electrostatic and ultrasonic atomisers—have been used
for atomization purposes. These atomizers affect the droplet size, rate of atomization and
droplet velocity. The most commonly used aerosol processing method is spray pyrolysis. In
the process, aqueous solution is atomized in a series of reactors where the aerosol droplets
undergo evaporation and solute condensation within the droplet; drying and thermolysis is
followed by sintering. Nanoparticles can be prepared directly, synthesized from droplets or
by liberating individual crystallites comprising the spray pyrolysis-derived particles from the
thermolysis stage. Spray pyrolysis can be used to prepare several metal oxide nanoparticles
such as ZnO, ZrO2 and Al2O3.
Combustion flame spraying
Another type of gas condensation technique that uses liquid chemical precursors as the
starting material is combustion flame spraying. The advantages of this process are low cost
and high production rates. In the combustion flame spraying process, burning a fuel–oxygen
mixture with a spray torch or flat-flame burner generates a flame. Chemical precursors
are vapourised in the hot zone of the flame and pyrolysis occurs in the thin hot zone. The
interaction between the flame and droplets yields nanoparticles. The use of a low-pressure
chamber for the flat-flame burner precludes contamination and ensures the temperature
profile across the entire burner surface is uniform. Low-pressure combustion flame spraying
is often referred to as combustion flame chemical vapour condensation (CF-CVC). Solid,
liquid and gaseous precursors can be used in this technique. CVC is an alternative to the
inert gas phase condensation approach in which the evaporator in the IGC system is replaced
by other sources such as burning flame, hot wall furnace and microwave plasma. The major
advantage of plasma-assisted pyrolysis in contrast to thermal activation is the low reaction
 Chapter 3: Synthesis Routes 75

temperature which reduces the tendency for agglomeration of nanoparticles. Combustion

flame spraying has been used to produce a variety of high purity and non-agglomerated
metal oxide nanoparticles such as TiO2, Al2O3, ZrO2, V2O5 and Y2O3–ZrO2.

3.1.4 Sol–gel process

The sol–gel processing method has been in use for many years for producing metal oxide
and ceramic powders with high purity and high homogeneity. The sol–gel route offers a
degree of control of composition and structure at the molecular level. The process involves the
generation of a colloidal suspension (‘sol’), which is subsequently converted to viscous gel and
solid material. Ebelman produced the first silica gel in 1846, and Cossa synthesized alumina
gel in 1870. Since then, aerogels of zirconia, silazane, borate and other ceramics have been
synthesized using the sol–gel technique.
In the process, reactive metal precursors were initially hydrolysed, followed by
condensation and polymerization reactions. Metal alkoxides are metalorganic compounds
with an organic ligand attached to a metal or metallic atom. They are the result of direct or
indirect reactions between a metal M and an alcohol ROH. Typical examples are methoxide
(OMe; MOCH3) and ethoxide (OEt; MOC2H5). During hydrolysis, the alkoxy group OR is
replaced by hydroxo ligands (OH), i.e.,

M(OR)z + H2O M(OH)(OR)z–1 + ROH

where R is an alkyl group, CnH2n+1. The mechanism of this reaction involves the addition of a
negatively charged HOδ– group to the positively charged metal centre (Mδ+) followed by the
removal of ROH.
The factors that influence the hydrolysis reaction are:
• Nature of the alkyl group
• Nature of the solvent
• Concentration of each species in the solvent
• Temperature
• Water to alkoxide molar ratio
• Presence of acid or base catalysts
Subsequent condensation eliminates either water or alcohol to produce metal oxide or
hydroxide linkages. In this process, two mononuclear complexes of M, each comprising only
one metal M, can react with one another to form a polynuclear complex consisting of two
metal atoms. Condensation occurs only when at least one hydroxo ligand is bonded to the
cation M, and is designated as M-OH for simplicity. Olation and oxolation reactions lead to
condensation. Olation is a reaction by which the hydroxo or ‘ol’ bridge (M–OH–M) is formed
between two cations, while oxolation involves the formation of oxo bridges (M–O–M) between
two metal cations:

olation: M – OH + M – OH2 M – OH – M + H2O

76 Nanoscience and Nanotechnology

oxolation: M – OH + H – OM M – O – M + H2O
M – OH + ROM M – O – M + ROH

The ‘ol’ or ‘oxo’ bridges between two metal atoms lead to the formation of condensed oxide or
hydroxide species. Under acid conditions, three-dimensional solid phase networks consisting
of extended linear M–O–M chain polymers are developed. Inorganic polymerization is
believed to occur in three stages during acid-catalysed condensation:
1. Polymerization of monomer units to form particles
2. Growth of particles
3. Linking of particles into chains, then solid networks that extend throughout the liquid
medium, thickening it to a gel
In acid solution, the sol-to-gel transition allows the solid phase to be shaped into films,
fibres and monoliths. For preparing coating films and fibres, the sol must exhibit spinnability.
It appears that only solutions containing long-chained polymers are spinnable. Films are
generally coated on the surface of the substrate via spin coating and dipping processes. Gel fibres
are made by fibre drawing from the viscous alkoxide solution at or near room temperature. In
contrast, on basic hydrolysis of metal alkoxides, a colloidal sol is generated. The gel is colloidal
when the solid network is made of round sol particles.
Removal of the solvents and appropriate drying are important steps to achieve gel
densification. When a solvent is evaporated from the gel under atmospheric conditions, capillary
pressure due to the interfacial tension of the solvent places a high stress on the gel network.
This leads to considerable shrinkage and fracture of the gel during drying. The resultant hard,
glassy and porous product is called a xerogel. When the liquid within the gel is removed above
its critical temperature and pressure (hypercritical) in an autoclave, the capillary pressure can
be eliminated. The product thus obtained is referred to as an aerogel. An aerogel is generally
amorphous and exhibits several unique properties such as high surface areas and porosities,
and low densities and conductivities.
The most commonly studied metal alkoxide is silicon tetraethyl orthosilicate [TEOS;
Si(OC2H5)4]. The TEOS precursor can react readily with water via the following reaction:

Si(OR)4 + H2O Si(OR)3(OH) + ROH

As the hydrolysis of silicon alkoxides is very slow, the conversion of metal precursor
molecules into trialkoxy silanol, Si(OR)3(OH) proceeds more rapidly by adding acid or base
catalysts. Depending on the amount of water and catalyst present, hydrolysis may proceed
partially, in which the metal alkoxides convert into Si(OR)4n(OH)n, or may go to completion
in which all OR groups of alkoxides are replaced by OH:

Si(OR)4 + 4H2O Si(OH)4 + 4ROH

Subsequent condensation reaction sequences produce cluster species with Si–O–Si

(siloxane) bonds and water or alcohol as the by-products:
 Chapter 3: Synthesis Routes 77

(OR)3Si – OH + HO – Si(OR)3 (OR)3 Si – O – Si(OR)3 + H2O

(OR)3 Si – OR + HO – Si (OR)3 (OR)3 Si – O – Si(OR)3 + ROH

In silica aerogels, particles of 1–100 nm are arranged in a highly cross-linked silica solid
network. In a recent study, colloidal silica particles were synthesized from hydrolysed TEOS,
ethanol (C2H5OH) and de-ionised water using ammonium hydroxide (NH4OH) as a catalyst.
Silica nanoparticles can also be prepared simply via thermal decomposition, e.g., oxidation
of TEOS or rice husk in a reactor, and the CF-CVC route as mentioned previously. Thermal
decomposition of rice husk appears to be more cost effective due to global availability of cheap
rice husk. Another process involves the precipitation of silica particles from the silicate solution
and buffering with sulphuric acid.
Alkoxides of transition metals (e.g., titanium, zirconium) are highly reactive towards water.
This implies that the rate of hydrolysis and condensation is very high, and thus it is difficult
to form a stable sol of titania (TiO2). Titania exists in three main crystallographic structures,
namely, rutile, anatase and brookite. Among these, rutile is the only stable phase. Many acid
catalysts such as nitric acid, hydrochloric acid and acetic acid have been added to lower the
reaction rates. Apart from these acids, acetylacetone (C5H8O2) can also moderate the reaction
rate. It is added as a chelating agent to decrease the reactivity of titanium alkoxides and to
form stable colloidal sols of ∼ 5 nm. Under more controllable hydrolysis and condensation
reactions, smaller particle sizes with more unique properties can be achieved. For example,
TiO2 aerogel nanocrystals can be obtained by supercritical evacuation of solvent from gels
prepared through HCl-controlled hydrolysis condensation reactions of titanium isopropoxide
in isopropanol. HCl catalyst favours the synthesis of titania powders with smaller grain size
compared to acetylacetone catalyst under the same heat treatment conditions. Further, anatase
crystallites are more stable if HCl is used as catalyst, while the pure rutile phase can be more
easily obtained if acetylacetone is used as a catalyst. Figures 3.7a and 3.7b show the TEM
micrographs of nanocrystalline titania prepared by the sol–gel route with a precursor to water
ratio of 1 and 4, respectively. Figures 3.7c and 3.7d indicate that the nanocrystallite titania does
not significantly grow on calcination up to about 500°C. According to the literature, various
metal oxide nanocrystalline powders, e.g., SnO2, Ba2Ti2O5, PbTiO3, (Pb, La)(Zr, Sn, Ti)O3,
nanocomposite powders containing elemental particulates, e.g., nano-Ni/SiO2, Fe–Al2O3 and
oxide nanocomposites, e.g., Fe2O3–SiO2, NiO–SiO2, and 3Al2O3–2SiO2, have been synthesized
using the sol–gel process.
The sol–gel process has been useful for synthesizing only metal oxides as a result of the
presence of metal–oxygen bonds in the alkoxide precursor, and the resulting gels are essentially
metal hydroxides or oxides. This process has distinct advantages over other techniques for
preparing metal oxide nanoparticles. These include the formation of high purity powders as
a result of homogeneous mixing of the raw materials on the molecular level, and the large-
scale industrial production of nanopowders. The disadvantage of the process is the high cost
of alkoxide precursors. In some cases, the sol–gel route can also be used to prepare non-oxide
ceramic powders such as β-SiC and ferroelectrics like (Pb, La)(Zr, Sn, Ti)O3 (PLZST). In the
78 Nanoscience and Nanotechnology

(a) (b)

(c) (d)

Fig. 3.7 TEM micrographs of nano titania (a) as-prepared (bright field image) with precursor to water ratio of 1,
(b) as-prepared (dark field image) with precursor to water ratio of 4, (c) after calcination at 400°C for 2 h (bright
field image) with precursor to water ratio of 4 and (d) Variation of the crystallite size of the anatase and rutile
phases with calcination temperature with precursor to water ratio of 4. (Source: BS Murty, IIT Madras).

former case, heat treatment of the gel product at 1500°C in argon atmosphere resulted in
0.6 mm spherical agglomerates consisting primarily of particles of 40 nm in diameter. Recently,
β-SiC nanopowders of 13–30 nm were synthesized by the chemical vapour reaction of the
SiH4–C2H4–H2 system in the temperature range of 1423 K and 1673 K; the products were free
from agglomeration. β-SiC powders can be made available at relatively low cost by the process
of pyrolising rice husks at 1200–1500°C. The disadvantage is the larger size of β-SiC powders
produced by this process, i.e., within micrometre range. It is worth noting that transition metal
 Chapter 3: Synthesis Routes 79

nanorods can be made by reacting carbon nanotubes with volatile metal oxides or halides.
Thus, β-SiC nanorods can be produced from reactions of carbon nanotubes with SiO or Si–I
reactants. The preferred growth direction of these nanorods is [111], though rods with [100]
growth are also observed at low reaction temperatures.
The anti-ferroelectric ceramics are promising candidates for new ceramic actuators because
of their unique characteristics of big and isotropic strain changes under applied electric field, as
well as shape memory effects. Nano-sized ceramics prepared by the sol–gel method are usually
more homogeneous and reactive than those fabricated by conventional solid-state reactions
since the mixing of the reagents occurs on a finer scale. The lower processing temperature is also
helpful in minimising the PbO loss. One of the problems in lead-based complex perovskites is
the evaporation of PbO at high temperatures, leading to undesirable phases. Sol–gel derived
powders of single perovskite phase can be used to produce bulk ceramic samples after sintering
at various temperatures.

3.1.5 Wet chemical synthesis

Solution-based processing routes used for the synthesis of nanoparticles include precipitation
of solids from a supersaturated solution, homogeneous liquid phase chemical reduction and
ultrasonic decomposition of chemical precursors. These processes are attractive due to their
simplicity, versatility and availability of low cost precursors. Inorganic salt compounds used in
the wet chemical synthesis routes are more versatile and economical than alkoxides employed
in the sol–gel process. A typical example is the formation of nanocrystalline titania powders
via hydrolysis of TiCl4 at lower temperatures:

TiCl4 + 2H2O TiO2 + 4HCl

Once the solution becomes saturated, crystallization of titania takes place either through
homogeneous or heterogeneous nucleation. In the latter case, crystal seeds are added to the
solutions to promote the crystallization of titania nanoparticles.
Salt reduction is one of the most commonly adopted methods to generate the metal colloid
particles. The process involves the dissolution of metal salts in aqueous or non-aqueous
environments followed by the reduction of metal cations to the zero-valent state. The nature
of the metal salts determines the kind of reducing agent to be applied. To produce transition
metal nanoparticles, group 6 metal chlorides such as CrCl3, MoCl3 and WCl4 are reduced with
NaBEt3 in toluene solution at room temperature to form metal colloids of high yield. A typical
reaction for forming metal powders is given as:
1 x
MClx + xNaBEt3 M + xNaCl + xBEt3 + —
2 ( )
H2

where x = 3 for M = Cr and Mo; x = 4 for M = W. However, the reduction of the chromium,
molybdenum and tungsten halides with either LiBEt3H or NaBEt3 in tetrahydrofuran (THF)
solution generates the corresponding metal carbides (M2C) rather than the metals. In another
80 Nanoscience and Nanotechnology

experiment, nanostructured Fe50Ni50 alloy has been synthesized by ultra-rapid autocatalytic

chemical reduction of the corresponding transition metal ions in alkaline aqueous solution
with hydrazine hydrate (N2H4·H2O) at 353 K. The alloy powder is composed of spherical
particles with 96 nm mean size diameter.
Metal nanoparticles can also be generated via ultrasonic and thermal decomposition
of metal salts or chemical precursors. Recently, ultrasonic waves were employed to
stimulate the chemical reactions of inorganic salts. Sonication of argon-saturated
aqueous solutions of NaAuCl and PdCl2 results in the formation of noble metal AuPd
alloy nanoparticles. Power ultrasonic waves can stimulate certain novel chemical
processes due to the formation of localised hot spots in the liquid of extremely high
temperatures (∼ 3000 K) and high pressures (∼ 1000 atm). The main event in the
process is the nucleation, growth and collapse of cavitation bubbles formed in the liquid.
The cooling achieved during the cavitation collapse is estimated to be greater than
2 × 109 K. This process is commonly referred to as the sonochemical method. Transition
metal nanoparticles can be produced via sonication of their respective chemical precursors.
For example, Ni(CO)4 has been sonicated under argon atmosphere to obtain amorphous
nickel. Nanostructured α-Fe is usually synthesized either via sonication or thermal
decomposition of Fe(CO)5 solution. One disadvantage of the sonication process is the
difficulty in controlling the resulting particle size and distribution due to the agglomeration
of particles into a porous coral-like microstructure.
A number of traditional and herbal methods of materials processing could also possibly
lead to nanostructure formation. The box overleaf gives the highlights of these routes.

3.1.6 Self-assembly
Self-assembly is a nanofabrication technique that involves aggregation of colloidal
nanoparticles into the final desired structure. This aggregation can be either spontaneous
(entropic) and due to the thermodynamic minima (energy minimization) energy minimization
constraints, or chemical and due to the complementary binding of organic molecules and
supramolecules (molecular self-assembly). Molecular self-assembly is one of the most
important techniques used in biology for the development of complex functional structures.
Since these techniques require that the target structures be thermodynamically stable, they
tend to produce structures that are relatively defect-free and self-healing. Self-assembly is by
no means limited to molecules or the nano-domain and can be carried out on just about
any scale, making it a powerful bottom-up assembly and manufacturing method (multi-scale
ordering). Another attractive feature of this technique relates to the possibility of combining
the self-assembly properties of organic molecules with the electronic, magnetic and photonic
properties of inorganic components.
The central theme behind the self-assembly process is spontaneous (physical) or chemical
aggregation of colloidal nano-particles. Spontaneous self-assembly exploits the tendency
of mono-dispersed nano- or submicro-colloidal spheres to organise into a face-centred
cubic (FCC) lattice. The force driving this process is the desire of the system to achieve a
 Chapter 3: Synthesis Routes 81

INDIAN TRADITIONAL METHODS OF NANOSTRUCTURE SYNTHESIS

Science and technology had significantly advanced in India in ancient times. Grant
Duff, British Historian of India, observed “Many of the advances in the sciences that
we consider today to have been made in Europe were in fact made in India centuries
ago.” One such Indian heritage in materials science is the rustless wonder, the Delhi
Iron pillar, which has been standing for 1600 years without getting corroded. Another
example of Indian excellence is Wootz steel, which is an extremely strong steel
developed in India around 300 bc. This steel has been extensively used for making
swords as it could cut a metal helmet into two pieces (popularly known as Damascus
steel). Recently (Nature, 2006) Paufler’s group from Technical University Dresden,
Germany, reported the presence of carbon nanotubes and nanowires in Damascus
steel. Similarly, it is also possible to produce carbon nanotubes and nanoparticles from

Carbon nanotubes and nanoparticles by the herbal route

200 nm 200 nm

Copper nanoparticles by the herbal route

100 nm

Energy (keV)

(Source: BS Murty, IIT Madras)

82 Nanoscience and Nanotechnology

various vegetable oils, as shown in the images below. Such nanostructures appear to
have been traditionally prepared in India.
Recently a Sanskrit scholar, Dr ABS Sastry, demonstrated the formation of copper
nanoparticles by a simple chemical displacement reaction, where traditional herbs have
been successfully used to cap the nanoparticles and prevent them from agglomeration.
The transmission electron bright field image confirms the nanocrystalline nature of
these copper particles. The energy dispersive x-ray spectrum from these individual
nanoparticles confirms that they are pure copper.

thermodynamically stable state (minimum free energy). In addition to spontaneous thermal

self-assembly, gravitational, convective and electro-hydrodynamic forces can also be used
to induce aggregation into complex 3D structures. Chemical self-assembly requires the
attachment of a single molecular organic layer (self-assembled monolayer, or SAM) to the
colloidal particles (organic or inorganic) and subsequent self-assembly of these components
into a complex structure using molecular recognition and binding.
Physical self-assembly
This method is driven by entropy that relies on the spontaneous organisation of colloidal
particles into a relatively stable structure through non-covalent interactions. For example,
Fig. 3.8 shows quinacridone molecules adsorbed on a graphite surface. The organic
semiconductor molecules self-assemble into nanochains via hydrogen bonds. Natural assembly
of on-chip silicon photonic band gap crystals, which are capable of reflecting the light arriving
from any direction in a certain wavelength range, are also examples of this process. In this
method, a thin layer of silica colloidal spheres is assembled on a silicon substrate. This is

Fig. 3.8 Scanning tunnelling microscope image of quinacridone molecules adsorbed on a graphite surface.
The organic semiconductor molecules self-assembled into nanochains via hydrogen bonds.
(Source: http://commons.wikimedia.org/wiki/File:Selfassembly_Organic_Semiconductor_Trixler_LMU.jpg.).
 Chapter 3: Synthesis Routes 83

achieved by placing a silicon wafer vertically in a vial containing an ethanolic suspension of

silica spheres. A temperature gradient across the vial aids the flow of silica spheres. Once such
a template is prepared, LPCVD can be used to fill the interstitial spaces with Si, so that the high
refractive index of silicon provides the necessary band gap.
One can also deposit colloidal particles in a patterned substrate (template-assisted self-
assembly, TASA). This method is based on the principle that when an aqueous dispersion
of colloidal particles is allowed to de-wet from a solid surface that is already patterned, the
colloidal particles are trapped by the recessed regions and assemble into aggregates of shapes
and sizes determined by the geometric confinement provided by the template. The patterned
arrays of templates can be fabricated using conventional contact mode photolithography,
which gives control over the shape and dimensions of the templates, thereby allowing the
assembly of complex structures from colloidal particles. This method can be used to fabricate
a variety of polygonal and polyhedral aggregates that are difficult to generate.
Chemical self-assembly
Organic and supramolecular (SAM) molecules play a critical role in colloidal particle self-
assembly. SAMs are robust organic molecules that are chemically adsorbed onto solid substrates.
Most often, they have a hydrophilic (polar) head that can be bonded to various solid surfaces and
a long, hydrophobic (non-polar) tail that extends outward. SAMs are formed by the immersion
of a substrate in a dilute solution of the molecule in an organic solvent. The resulting film is a
dense organization of molecules arranged to expose the end group. The durability of a SAM is
highly dependent on the effectiveness of the anchoring to the surface of the substrate. SAMs have
been widely studied, because the end group can be functionalised to form precisely arranged
molecular arrays for various applications ranging from simple, ultra-thin insulators and
lubricants to complex biological sensors. Chemical self-assembly uses organic or supramolecular
SAMs as the binding and recognition sites for fabricating complex 3D structures from colloidal
nanoparticles. Most commonly used organic monolayers include:
• Organosilicon compounds on glass and native surface oxide layer of silicon
• Alkanethiols, dialkyl disulfides and dialkyl sulfides on gold
• Fatty acids on alumina and other metal oxides
• DNA
Octadecyltrichlorosilane (OTS) is the most common organosilane used in the formation
of SAMs, mainly because it is simple, readily available and forms good, dense layers.
Alkyltrichlorosilane monolayers can be prepared on clean silicon wafers with a surface of
SiO2 (with almost 5 × 1014 SiOH groups/cm2). Since the silicon chloride bond is susceptible
to hydrolysis, a limited amount of water has to be present in the system in order to obtain
good quality monolayers. Monolayers made of methyl- and vinyl-terminated alkylsilanes are
autophobic to the hydrocarbon solution and hence emerge uniformly dry from the solution,
whereas monolayers made of ester-terminated alkylsilanes emerge wet from the solution used
in their formation. The disadvantage of this method is that if the alkyltrichlorosilane in the
solvent adhering to the substrate is exposed to water, a cloudy film is deposited on the surface
due to the formation of a gel of polymeric siloxane.
84 Nanoscience and Nanotechnology

Another important organic SAM system is the alkanethiols X(CH2)nSH, where X is the
end group) on gold. A major advantage of using gold as the substrate material is that it does
not have a stable oxide, and can thus be handled in ambient conditions. When a fresh, clean,
hydrophilic gold substrate is immersed (several minutes to several hours) in a dilute solution
(10−3 M) of the organic sulphur compound (alkanethiols) in an inorganic solvent, a close-
packed, oriented monolayer can be obtained. Sulphur is used as the head group, because
of its strong interaction with gold substrate (44 kcal/mol), resulting in the formation of a
close-packed, ordered monolayer. The end group of alkanethiol can be modified to render
hydrophobic or hydrophilic properties to the adsorbed layer.
Another method for depositing alkanethiol SAM is soft lithography. This technique is based
on inking a PDMS stamp with alkanethiol and its subsequent transfer to planar and non-
planar substrates. Alkanethiol functionalised surfaces (planar, non-planar, spherical) can also
be used to self-assemble a variety of intricate 3D structures.
Carboxylic acid derivatives self-assemble on surfaces (e.g., glass, Al2O3 and Ag2O)
through an acid–base reaction, giving rise to monolayers of fatty acids. The time required
for the formation of a complete monolayer increases with decreased concentration. A higher
concentration of carboxylic acid is required to form a monolayer on gold compared to Al2O3.
This is due to differences in the affinity of the COOH groups (more affinity to Al2O3 and glass
than gold) and also the surface concentration of the salt forming oxides in the two substrates.
In the case of amorphous metal oxide surfaces, the chemisorption of alkanoic acids is not
unique. For example, on Ag2O the oxygen atoms bind to the substrate in a nearly symmetrical
manner, resulting in ordered monolayers with a chain tilt angle from the surface normally of
15 to 25°. But on CuO and Al2O3, the oxygen atoms bind themselves symmetrically and the
chain tilt angle is close to 0°. The structure of the monolayers is thus a balance of the various
interactions taking place in the polymer chains.
Deoxyribonucleic acid (DNA), the framework on which all life is built, can be used to self-
assemble nanomaterials into useful macroscopic aggregates that display a number of desired
physical properties. DNA has a double-helix structure with two strands coiled around each
other. When the two strands are uncoiled, singular strands of nucleotides are left. These
nucleotides consist of a sugar (pentose ring), a phosphate (PO4) and a nitrogenous base.
The order and architecture of these components are essential for the proper structure of a
nucleotide.
There are typically four nucleotides found in DNA: adenine (A), guanine (G), cytosine
(C) and thymine (T). A key property of the DNA structure is that the described nucleotides
bind specifically to another nucleotide when arranged in the two-strand double helix (A to
T and C to G). This specific bonding capability can be used to assemble nanophase materials
and nanostructures. For example, nucleotide functionalised nano-gold particles have been
assembled into complex 3D structures by attaching DNA strands to the gold via an enabler
or linker. In a separate work, DNA was used to assemble nanoparticles into macroscopic
materials. This method uses alkane dithiol as the linker molecule to connect the DNA template
to the nanoparticle. The thiol groups covalently attach themselves to the colloidal particles,
leading to aggregate structures.
 Chapter 3: Synthesis Routes 85

3.2 TOP-DOWN APPROACHES

3.2.1 Mechanical alloying

The mechanical alloying (MA)/milling process was originally developed by Benjamin of the
International Nickel Company for the production of oxide dispersion strengthened (ODS)
superalloys. It is now a widely used process for the fabrication of nanocrystalline powders.
The possible spectrum of the uses of MA are shown schematically in Fig. 3.9. Recently,
nanocrystalline high-entropy solid solutions with high hardness have been synthesized in
multicomponent equiatomic alloys by MA.
Mechanical alloying or milling is usually carried out in high-energy mills such as vibratory
mills (Spex 8000 mixer/mill), planetary mills (Fritsch and Retsch) and attritor mills (Szegvari
attritor and Simoloyer). The vibratory mill has one vial, containing the sample and grinding
balls and vibrates in all three directions. Because of the amplitude (about 50 mm) and speed
(about 1200 rpm), the ball velocities are high (in the order of 5 m/s) and consequently the force
of the ball’s impact is unusually high. Another popular mill for conducting MA experiments is
the planetary ball mill. In this mill, the vials rotate around their own axes and at the same time
around the axis of a disc on which they are mounted. The centrifugal force produced by the vials
rotating around their own axes and that produced by the rotating support disk together act on
the vial contents, consisting of material to be ground and the grinding balls. Since the vials and
the supporting disc rotate in opposite directions, the centrifugal forces alternately act in opposite
directions. Due to this, the balls run down the inside wall of the vial. This is followed by the
material being ground and grinding balls being lifted off and travelling freely through the inner
chamber of the vial and colliding against the opposing inside wall. Grinding vials and balls are
available in eight different materials—agate, silicon nitride, sintered corundum, zirconia, chrome
steel, Cr–Ni steel, tungsten carbide and plastic polyamide.
An attritor ball mill consists of a stationary vertical drum in which a vertical shaft rotates
with a series of horizontal impellers attached to it. Set progressively at right angles to each other,
the impellers, through their rotation, energise the ball charge, causing powder size reduction

Fig. 3.9 Attributes of mechanical alloying or high-energy ball milling.

86 Nanoscience and Nanotechnology

due to the impact between balls, between balls and the container wall, and between balls,
the agitator shaft and impellers. Particle size reduction also occurs partially by interparticle
collisions and by ball sliding on the walls of the vials. Attritors are the mills in which large
quantities of powder (from about 0.5 to 40 kg) can be milled at a time. The most recent of
the ball mills is the horizontal attritor (Simoloyer) that can be operated in dry processing at
high relative velocity of the grinding media (up to 14 m/s) under controlled condition like
vacuum or inert gas and in closed circuits. In these mills, the grinding media is accelerated
by a horizontally arranged rotor inside the grinding vessel. These mills have the advantage
of highest relative velocity of grinding media, which leads to high level of kinetic energy
transfer, an intensive grinding effect and short processing times. The short processing times
and collision-based grinding process results in low contamination levels. The simoloyers are
available with 0.5- to 990-litre grinding chamber capacity, which makes it very convenient to
scale-up the laboratory experiments to commercial production plants.
The mechanism of nanocrystallization during high-energy ball milling was first proposed
by H.J. Fecht in 1983. He summarised the phenomenon of the development of nanocrystalline
microstructure into three stages;
Stage 1: Localization of deformation into shear bands with high dislocation density.
Stage 2: Dislocation, annihilation and recombination to form nanometre-scale subgrains,
which extend throughout the sample with further milling.
Stage 3: Transformation of subgrain boundary structure to randomly oriented high-
angle grain boundaries. Superplastic deformation processes such as grain boundary sliding
causes self-organisation into a random nanocrystalline state.
During high-energy milling, the powder particles are repeatedly flattened, cold welded,
fractured and re-welded. Whenever balls collide, some amount of powder is trapped in between
them. The impact from the balls causes plastic deformation of the powder particles, causing
work hardening and fracture. The new surfaces formed by the fracture of the particles weld
together. The composite particles at this stage have a characteristic layered structure consisting

2 μm
(a) (b)

Fig. 3.10 (a) Secondary electron image and (b) backscattered electron image of layered structure observed
during initial stages of high-energy ball milling of Ti and Al powder particles (Source: BS Murty, IIT Madras).
 Chapter 3: Synthesis Routes 87

of various combinations of the starting constituents and are shown in Figs. 3.10a and 3.10b
for the Ti–Al system. As deformation continues, the particles become work hardened and
fracture. When fracture predominates over cold welding, the particle size is refined.
The minimum grain size achievable by high-energy ball milling has been related to
several physical properties of elemental metals. It is reported that the minimum grain size,
dmin, is inversely proportional to the melting temperature for low melting FCC metals.
However, for HCP and BCC systems as well as FCC elements with melting temperature
above that of Pd (1555°C), dmin appears to be insensitive to the melting point. For FCC
metals, an inverse relationship was also found between dmin and bulk modulus, and a direct
relationship between dmin and critical equilibrium distance between two edge dislocations.
The majority of nanocryztalline metals have been synthesised to understand the mechanism
of nanocrystallization and minimum grain size obtained by high-energy ball milling. Research
has also been focussed on the validity of the Hall–Petch relation, and mechanical and physical
properties of nanocrystalline metals. Fe, Cu, Ni, Pd, Cr, Nb, W, Hf, Ru, Zr, Co, Ag, Al, Si and
graphite are among the few mentioned. Fecht et al, presented the first systematic report on
the synthesis of nanocrystalline metals (Fe, Cr, Nb, W, Zr, Hf, Co and Ru) by high-energy
ball milling. It is postulated that the grain boundary energy of the ball-milled nanocrystalline
materials is higher than that of fully equilibrated grain boundaries.
An allotropic and polymorphic transformation induced by high-energy ball milling has
been widely studied. High-energy ball milling of elemental Nb to a crystallite size of below
10 nm resulted in an allotropic transformation of BCC-Nb to FCC-Nb. Similar allotropic
transformations such as HCP-Zr to FCC-Zr and HCP-Ti to FCC-Ti have been observed
during high-energy ball milling by Manna and his group at IIT, Kharagpur. FCC to HCP
transformation in Ni during high-energy ball milling was found to be aided by the addition of
small amounts of Si and Al, which when dissolved in Ni can make it harder. A harder material
can become nanocrystalline much more easily during high-energy ball milling due to extensive
fracture when compared to a ductile material. Thus, the critical grain size of about 10 nm for
the FCC to HCP transition in Ni could be achieved early during milling. It has been argued
that the structural instability due to plastic strain, increasing lattice expansion and negative
hydrostatic pressure was responsible for such transformations. Polymorphic transformations
were also observed during high-energy ball milling of the Ti50Zr50 binary alloy. Transformation
of quasicrystalline phase to crystalline BCC phase has also been observed in the Al–Cu–Fe
and Al–Cu–Co systems. It was even observed in a number of systems such as Ti–Al, Ti–Ni,
Ti–Cu, Fe—Si, etc., that nanocrystalline alloys below a certain critical size of about 10 nm (and
above a critical lattice strain) can get structurally destabilised and become amorphous due to
the large defect concentration.
Nanocrystallization by high-energy ball milling has also been demonstrated to help in
extending the solid solubility of different solute elements into various solvent elements, as
discussed in the previous chapter. This is basically due to the large fraction of grain boundaries
in these nanocrystalline materials, which can accommodate large solute fractions.
Many ordered intermetallic compounds show high yield strength up to high temperatures
and have the advantage of lower density compared to commercial superalloys. However,
88 Nanoscience and Nanotechnology

these advantages are hampered due to their brittleness at low temperatures. It has been
shown that the nanocrystalline intermetallics have improved formability. This finding
has created an interest in the synthesis of several nanocrystalline aluminides, silicides
and other intermetallics through MA. Interestingly, it has been observed that the phase
fields of intermetallics can be significantly enhanced in the nanocrystalline state. In case of
nanocrystalline NiAl synthesized by MA, the phase field NiAl has been extended from 45–
55 at.%Ni in the conventional microcrystalline state to 25–65 at.%Ni in the nanocrystalline
state. Similarly, studies on the Ni–Si, Fe–Si, Ni–Al, Al–Cu systems have indicated that only
congruent melting compounds (which are expected to have lower surface energies) are
expected to be stable in the nanocrystalline state.
It has also been observed that polymorphic transitions can be induced in intermetallics in the
nanocrystalline state. Nayak and Murty synthesized the nanocrystalline L12–Al3Ti intermetallic
compound with the crystallite size less than 15 nm by MA of Al67M8Ti25 (M = Cr, Mn, Fe, Co,
Ni and Cu), while Al3Ti usually has a DO23 structure. Among all the elements studied, Cu
appears to be the best to stabilize L12–Al3Ti. Another interesting observation was that the L12–
Al3Ti phase formed at an Al crystallite size of 15 nm. Similarly, L12–Al3(Ti, Zr) compounds
have formed at an Al crystallite size of about 20 nm, irrespective of the composition, as shown
in Fig. 3.11. These observations clearly indicate that nanocrystallization is a prerequisite for
the formation of intermetallic compounds. Figures 3.12a and 3.12b show the TEM dark field
image and corresponding SAD pattern, respectively, obtained from nanocrystalline Al3Zr.

Fig. 3.11 Crystallite size of Al and intermetallic as a function of composition. Nanocrystalline intermetallic
compound formation was observed when the crystallite size of Al was below 24 nm. The dotted line demarcates
the phase field of mixture of elements and intermetallic compound. (Source: BS Murty, IIT Madras).
 Chapter 3: Synthesis Routes 89

In situ nanocomposite formation by MA has found significant interest due to their potential
application. It has been shown by Naser and his co-workers that no grain growth occurs in
the matrix close to its melting point when Cu and Mg are reinforced with nanocrystalline
Al2O3 by MA. In another interesting study, nanocomposites in the Al–Fe system have been
synthesized by MA, which have shown exceptionally high hardness of about 13 GPa with
densities very close to theoretical density. The very high hardness in these nanocomposites
has been attributed to the presence of nanocrystalline/quasicrystalline intermetallic phases.
Figure 3.13a shows the bright field image of nanocomposites in the Al–20Fe alloy. Detailed

100 nm

Fig. 3.12 TEM dark field image and corresponding diffraction pattern of Li12–Al3Ti intermetallic.
(Source: BS Murty, IIT Madras).

50 nm

(a) (b)

Fig. 3.13 (a) TEM bright field image of images of nanocomposites in Al–20Fe alloy after MA and subsequent
annealing at 673 K for 2 h and (b) high resolution image, showing lattice fringes from nano-quasicrystalline particles
in the Al matrix. (Source: BS Murty, IIT Madras).
90 Nanoscience and Nanotechnology

high-resolution electron microscopy of these nanocrystalline intermetallics in this alloy

indicated the possible presence of nano-quasicrystalline phase in these alloys, as shown in
Fig. 3.13b.
Cu is a good electrical conductor; however, it has low strength due to which the life
of Cu conductors as electrodes and as electrical contacts is quite short. Increasing the
strength of Cu by using it in nanocrystalline form can improve the life of these conductors.
However, nanocrystalline pure Cu can have significant grain growth at high temperatures.
Cu-based nanocomposites such as Cu–W and Cu–Ta would be the answer to this problem.
Figure 3.14a shows TEM evidence of the nanocrystalline nature of these Cu–20wt.%Ta
nanocomposites. The AFM analysis of nanocomposites after sintering clearly showed that
W and Ta can restrict the grain growth in Cu and retain the nanocrystalline grains. Figure
3.14b represents a typical AFM image of Cu–20wt.%W after sintering at 500°C. This indicates
that even after sintering at about half the melting point of Cu, the nanocrystalline nature
is retained in these nanocomposites. Interestingly, the nanocomposites could be sintered
close to their theoretical densities at 500°C, while the micro-composies had to be sintered
at temperatures close to the melting point of Cu for achieving similar densities as shown
in Figs. 3.15a and 3.15b. These metal–metal nanocomposites synthesized by high-energy
ball milling showed superior hardness and compressive strength without much reduction
in conductivity. The Cu–W nanocomposites showed ~ 2.6 times higher hardness than
microcomposites of similar composition. A similar observation is also made with Cu–Ta
nanocomposites. Figure 3.16a shows the compressive strength of the Cu–Ta nanocomposites
and microcomposites. The figure also shows the strength contribution (according to
Hall–Petch equation) of the nanocrystalline grains. The Cu–Ta nanocomposites exhibited
3.6 to 5 times higher compressive strength than the microcrystalline composites of similar
composition. The compressive strength of Cu–Ta nanocomposite is 4.5 to 7 times higher

300

200

100

80 nm 0
0 100 200 300
(a) (b)

Fig. 3.14 (a) TEM image of Cu-20wt.%W ball-milled powders after 20 h of ball milling; (b) AFM analysis revealed
nanograins in Cu-20wt.%W nanocomposites after sintering at 500°C for 2 h. (Source: BS Murty, IIT Madras).
 Chapter 3: Synthesis Routes 91

(a) (b)

Fig. 3.15 Variation of density of Cu–Ta (a) nanocomposites and (b) microcomposites as a function of sintering
temperature. (Source: BS Murty, IIT Madras).

than that of microcrystalline Cu, as shown in Table 3.3. The resistivity values of Cu–Ta
nanocomposites (Fig. 3.16b) indicate that the major contribution of resistivity is due to
Ta rather than fine grain size. Figure 3.17 shows the hardness to resistivity ratio of Cu–Ta
nanocomposites normalized with that of the oxygen-free high conductivity (OFHC) Cu,
which clearly indicates that the hardness on nanocomposites is three times higher than that
of OFHC Cu for similar resistivity.

Fig. 3.16 (a) Compressive strength and (b) electrical resistivity of Cu–Ta nanocomposites synthesized by
high-energy ball milling. (Source: BS Murty, IIT Madras).
92 Nanoscience and Nanotechnology

Table 3.3 Compressive strength of Cu matrix nanocomposites

Vol. % / wt. % Nanocomposite Microcomposite Increase Increase wrt
of dispersoids (MPa) (MPa) wrt microcrystalline
microcomposite Cu (130 MPa)
Cu–Al2O3
5.0/2.3 501 182 2.8 3.9
10.0/4.7 633 221 2.9 4.9
20.0/10.0 853 275 3.1 6.6
Cu–W
2.4/5.0 536 168 3.2 4.1
11.6/20.0 770 229 3.4 5.9
16.5/30.0 853 284 3.0 6.6
Cu–Ta
2.7/5.0 586 164 3.6 4.5
11.8/20.0 870 174 5.0 6.7
18.7/30.0 930 185 5.0 7.1

Fig. 3.17 Hardness to resistivity ratio of Cu–Ta nanocomposites normalized with oxygen-free high conductivity
(OFHC) Cu. (Source: BS Murty, IIT Madras).

3.2.2 Equal channel angular pressing (ECAP)

The principle of ECAP [or equal channel angular extrusion (ECAE)] is illustrated schematically
in Fig. 3.18. For the die shown in the illustration, the internal channel is bent through an
 Chapter 3: Synthesis Routes 93

abrupt angle, φ, equal to 90°, and there is an

additional angle, ψ, equal to 0° in Fig. 3.19, which
represents the outer arc of curvature where the
two channels intersect. In this process, a rod-like
sample is pressed through the die using a plunger.
Shear deformation occurs as the sample passes
through the die. Despite the introduction of an
intense strain as the sample passes through the
shear plane, the sample ultimately emerges from
the die without experiencing any change in the
cross-sectional dimensions.
Researchers all over the world are now studying
the ECAE process as it is easy to install and does
not require special equipment in the laboratories,
except for the dies and a press machine. The ECAE
process has been applied to various kinds of metals
Fig. 3.18 Schematic illustration of ECAP
and alloys and has succeeded in producing ultrafine
facility.
grain (UFG) microstructures (Fig. 3.19). However,
the major materials used are light metals like Al- and Mg-alloys and the trials for steels are
limited. This is presumably because large force is required to put the materials through the
channel die, overcoming large flow stress and frictional stress. The hydrostatic compressive
stress field in the ECAE process is an advantageous point to prevent fracture of the materials.
However, cracking due to shear localization has been reported in less workable materials such
as Ti–Al–V alloy.
Though the ECAE can fabricate bulk materials, the typical size of the samples is small.
Further, the ECAE is principally not a continuous process but a batch process. A few
experiments to make the ECAE continuous have been attempted (Fig. 3.20). Saito and

10 μm 1 μm

(a) (b)

Fig. 3.19 Microstructure of (a) annealed CP aluminum and (b) after ECAP.
(Source: Uday Chekkingal, IIT Madras).
94 Nanoscience and Nanotechnology

his co-workers developed the conshearing process for continuous ECAE of sheet metals
(Fig. 3.20a). They equipped the ECAE die at the end of the satellite mill they previously invented.
The satellite mill is the special rolling mill which can maintain the rotating speed of all the
satellite rolls constant. As a result, compression force along the rolling direction (RD) appears
in the materials between adjacent satellite rolls. Folding of the materials is prevented by the
guide shoe equipped between the satellite rolls. The compression force in the satellite mill was
used to put the sheet into the ECAE die. The conshearing was applied to obtain aluminium
of commercial purity up to four cycles and succeeded in fabricating sound sheets, but UFG
microstructures have not been obtained. Because they used sheet material, it was probably not
effective to impose ideal shear strain owing to the bending and bending-back deformation and
friction. Further, it is difficult to make the channel angle 90° in this configuration (they used
125°). On the other hand, the processed materials showed unique textures.
Lee and co-workers developed another continuous ECAE process, named the dissimilar
channel angular pressing (DCAP) process, which is principally the same as conshearing
(Fig. 3.20b). They used a conventional two-high mill, but the surface of the lower roll was
mechanically roughened in order to feed the material into the ECAE die. As a result, the surface
quality of the specimens would be worse than the conventionally rolled materials. Strips of
1.55 × 20 × 1000 mm were processed by the continuous confined strip shearing process and
the UFGs similar to those obtained in the conventional ECAE have been reported in 1050-Al,
though the difficulties and the disadvantages are not obvious from the limited publications
currently available. The channel angle was varied from 100° to 140°, and it was found that the
critical strain to form the UFGs increases by increasing the angle.

3.2.3 High-pressure torsion (HPT)

A method for fabrication of disc-type bulk nanostructured samples using high-pressure torsion
is shown in Fig. 3.21. In HPT, the sample disk is strained in torsion under the applied pressure
(P) of several GPa between two anvils. A lower holder rotates and surface friction forces the
ingot to deform by shear. Due to the specific geometric shape of the sample, the main volume
of the material is strained in conditions of quasihydrostatic compression under the applied

Fig. 3.20 Principle of (a) conshearing and (b) dissimilar channel angular pressing process.
 Chapter 3: Synthesis Routes 95

pressure and the pressure of sample outer layers. As a result, in spite of large strain values, the
deformed sample is not destroyed. Various strains can be achieved by rotating the lower anvil
through a defined angle. The shear strain γ may be simply estimated as,

2πRN
γ=
d

where R is the distance from the sample centre, N is the number of anvil rotations and d is the
thickness of the sample. In this method of microstructure refinement, the simple shear stress
conditions are realised at relatively low temperatures under high applied pressure (5–15 GPa).
The samples fabricated by severe torsion straining are usually disc-shaped, with a diameter
of 10 to 20 mm and thickness 0.2±0.5 mm. A significant change in the microstructure is
observed already after deformation by 1/2 rotation, but for formation of the homogeneous
nanostructure, as a rule, several rotations are required.
Using high-pressure torsion, the first nanocrystalline structures were developed in single
crystals of Ni and Cu. It was found that the mean grain size had gradually decreased with
increasing shear strain and had finally stabilized at the level of ~ 100 nm. Further experiments
with initially coarse grained Cu, Ni, Fe, Cr and Ti revealed that strong grain refinement can
be achieved in all these metals after 3–5 revolutions, whereupon the mean grain size usually
reaches the steady state value of 100–200 nm, depending on the material (Table 3.4). Slightly
smaller grain size has been reported for single phase matrix Fe and Al alloys and significantly
smaller grain size, down to 10 nm, can be obtained for some
multiphase alloys and intermetallic compounds.
Recent investigations also showed that severe torsion
straining can be used successfully not only for the
refinement of a microstructure but also for the consolidation
of powders. It was revealed that during torsion straining
at room temperature, high pressures equal to several
GPa can provide a rather high density close to 100% in
the processed disc-type nanostructured samples. For
fabrication of such samples via severe torsion straining

Table 3.4 Grain size of various kinds of HPT processed metals

Metal Details of HPT processing Grain size (nm)
Ni P = 6 GPA, γ = 300, RT 170
Cu P = 5 GPA, γ = 300, RT 200
Cu P = 8 GPA, γ = 250, RT 200
Fe P = 5 GPA, γ = 600, RT 100
Fe P = 5 GPA, γ = 420, RT 127
Cr P = 7.8 GPA, γ = 120, T = 623 K 500
Mo P = 6 GPA, γ = 300, T = 623 K 190 Fig. 3.21 Principle of high
Ti P = 5 GPA, γ = 600, RT 120 pressure torsion.
96 Nanoscience and Nanotechnology

consolidation, not only conventional powders but also powders subjected to ball milling
can be used. The HPT consolidation of nanostructured Ni powder prepared by ball milling
can be given as an example. The conducted investigations showed that the density of the
fabricated powders is close to 95% of the theoretical density of the bulk coarse-grained
Ni. TEM examinations showed the absence of porosity with a mean grain size of about
20 nm. It is also very interesting that the value of microhardness of the Ni samples fabricated
by HPT consolidation is as high as 8.6 GPa.

3.2.4 Accumulative roll bonding (ARB)

Accumulative roll bonding is the only SPD process using rolling deformation itself
(Fig. 3.22). Rolling is the most advantageous metal working process for continuous
production of plates, sheets and bars. However, the total reduction applied to the materials
is substantially limited because of the decrease in the cross-sectional dimension of the
materials with increasing reduction. In the ARB process, a 50% rolled sheet is cut into two,
stacked to the initial thickness, and then rolled again. As is evident, the rolling in the ARB is
not only a deformation process but also a bonding process (roll bonding). To achieve good
bonding, the surface of the materials is degreased and wire brushed before stacking, and the
roll bonding is sometimes carried out at elevated temperatures below the recrystallization
temperature of the materials. Repeating this ARB process a number of times can lead to very
large plastic strain in the materials.
It has been observed that achieving good bonding is the critical step in the ARB process.
Surface treatment is indispensable for achieving good bonding. Furthermore, there is a
critical rolling reduction in one-pass roll bonding, below which it is difficult to achieve
sufficient bonding. Though the critical reduction depends on the materials and the processing
temperatures, more than 35% reduction by one pass is necessary in general, so that the

Fig. 3.22 Principle of accumulative roll bonding.

 Chapter 3: Synthesis Routes 97

rolling force is large in comparison with conventional rolling. Except for the necessity of
large enough capacity of the rolling mill which can realise one-pass heavy roll bonding,
there are no special requirement in the equipments for the ARB. A serious problem in
the ARB process is fracture of the materials. Since a large amount of total plastic strain is
accumulated in the materials, the rolling is not a hydrostatic process; edge-cracks sometimes
appear in the sheets, especially at higher cycles. In certain kinds of materials, such as Al–Mg
alloy, the edge cracks largely propagate into the centre of the sheets. In that case, it becomes
impossible to proceed to the subsequent cycles. With ductile materials, for example, pure
aluminum and iron, the UFG sheets with dimension 1 × 50 × 300 mm are fabricated without
cracking by the ARB process.
Irrespective of the kind of material studied, the average grain diameter of UFG materials
is around 500 nm. The UFGs are surrounded by clear but irregular-shaped boundaries; the
number of dislocations inside the grains seems small. These features are similar to those
observed in materials that have been heavily deformed by other SPD processes. The most
characteristic feature of the UFGs in the ARB-processed materials is the elongated morphology.
Measurements clearly confirm that the elongated UFGs are not subgrains, but are grains
surrounded by high-angle grain boundaries.
ARB-processed materials with elongated UFG structures exhibit very high strength.
The grain size and the tensile strength of the various UFG materials fabricated by ARB are
summarised in Table 3.5. In most cases, the mean grain thickness of the pancake-shaped
UFGs or the ultrafine lamellar structures are 100 ~ 200 nm. Materials with higher purity tend
to show larger grain size. ARB at lower temperature results in smaller grain size within the
similar materials. UFG materials exhibit tensile strength which is two to four times higher
than that of the starting materials with conventional grain sizes. On the other hand, ARB-
processed materials have limited tensile elongation owing to early plastic instability.

Table 3.5 Grain size and tensile strength of various ARB-processed metals and alloys
Materials ARB process Grain size Tensile strength
(wt.%) (nm) (MPa)
4N-Al 7 cycles RT 670 125
100-Al (99%Al) 8 cycles RT 210 310
5052-Al (Al–2.4Mg) 4 cycles RT 260 388
5083-Al (Al–4.5Mg-0.6Mn) 7 cycles at 100°C 80 530
6061-Al (Al–1.1Mg–0.6Si) 8 cycles RT 100 357
7075– l (Al–5.6Zn–2.6Mg–1.7Cu) 5 cycles at 250°C 300 376
OFHC-Cu 6 cycles RT 260 520
Cu–0.27Co–0.09P 8 cycles at 200°C 150 470
Ni 5 cycles RT 140 885
IF steel 7 cycles at 500°C 210 870
0.041P-IF 5 cycles at 400°C 180 820
SS400 steel (Fe–0.13C–0.37Mn) 5 cycles RT 110 1030
Fe–36 Ni 7 cycles at 500°C 87 780
98 Nanoscience and Nanotechnology

3.2.5 Nanolithography
STM-based nanolithography This has been exploited for local oxidation and passivation,
localized chemical vapour deposition, electrodeposition, mechanical contact of the
tip with the surface, and deformation of the surface by electrical pulses. Patterns
with a minimal size from 10–20 nm to 1 nm in ultrahigh vacuum (UHV) have been
demonstrated. Nanometre-sized holes can be formed using low energy electrons from
a scanning tunnelling microscope (STM) tip when a pulsed electric voltage is applied in
the presence of sufficient gas molecules between the substrate and the tip. For example,
holes that are 7 nm deep and 6 nm wide on highly ordered pyrolytic graphite (HOPG)
substrate were formed in nitrogen at a pressure of 25 bar by applying a 7 V pulse to the
tip for 130 mins, with the distance between the tip and the substrate being 0.6–1 nm.
A possible mechanism is that the electric field induces the ionisation of gas molecules
near the STM tip, and accelerates the ions towards the substrate. Ions bombard the
substrate and, consequently, nanometre-sized holes are created. A certain electric field
is required to generate field emitted electrons. The diameter of an electron beam ejected
from an STM tip is dependent on the applied bias voltage and the diameter of the tip.
At low bias (<12 V), the diameter of the ejected electron beam remains almost constant;
however, the beam diameter changes significantly with bias voltage and the diameter of
the tip.
Nanostructures can be created using field evaporation by applying bias pulses to the
STM tip–sample tunnelling junction. For example, nanodots, nanolines, and nanocorrals of
gold on a clean stepped Si (111) surface were fabricated by applying a series of bias pulses
(< 10 V and ∼30 μs) to an STM gold tip at UHV (a base pressure of 10-10 mbar). Nanodots with
diameter as small as a few nanometres can be realised. By decreasing the distance between
adjacent nanodots, it was possible to create continuous nanolines, a few nanometres wide
and over a few hundred nanometres long. A nanocoral of diameter about 40 nm, formed
by many Au nanodots, each with diameter of a few nanometres, was also created on the
Si (111) surface.
AFM-based nanolithography Direct contacting, writing or scratching is referred to as a
mechanical action of the AFM tip that is used as a sharply pointed tool in order to produce fine
grooves on sample surfaces. Although direct scratching creates grooves with high precision, low
quality results are often obtained due to tip wear during the process. An alternative approach
is to combine scratching on a soft resist polymer layer, such as PMMA or polycarbonate, as
a mask for the etching process and subsequent etching to transfer the pattern to the sample
surface. This method ensures reduced tip damage, but also precludes an accurate alignment to
the structures underneath. A two-layer mask has been investigated as a further improvement.
For example, a mask coating consisting of a thin layer of polycarbonate of 50–100 m and
a film of an easy-to-deform and fusible metal such as indium or tin was used to create
50 nm–wide structures. Figure 3.23 is a typical layout of the sample and process steps with
AFM lithography.
 Chapter 3: Synthesis Routes 99

Dip-pen nanolithography In dip-pen nanolithography (DPN), the tip of an AFM operated

in air is ‘inked’ with a chemical of interest and brought into contact with a surface. The ink
molecules flow from the tip onto the surface similar to a fountain pen. The water meniscus
that naturally forms between the tip and the surface enables the diffusion and transport of
the molecules, as shown in Fig. 3.24. Inking can be done by dipping the tip in a solution
containing a small concentration of the molecules, followed by a drying step (e.g., blowing dry
with compressed difluoroethane). Line widths down to 12 nm with spatial resolution of 5 nm
have been demonstrated with this technique. Species patterned with DPN include conducting
polymers, gold, dendrimers, DNA, organic dyes, antibodies and alkanethiols. Alkanethiols
have also been used as an organic monolayer mask to etch a gold layer, and subsequently etch
the exposed silicon substrate.

Fig. 3.23 Layout of the sample and the process steps with AFM lithography: (a) sample multilayer structure,
(b) thin mask patterning by AFM lithography, (c) polymer removal in plasma oxygen, (d) titanium stripe etching,
and (e) resulting electrodes after sacrificial layers removal.

Fig. 3.24 Schematic representation of the working principle of dip-pen nanolithography.

100 Nanoscience and Nanotechnology

3.3 CONSOLIDATION OF NANOPOWDERS

The commercial application of nanomaterials beyond the boundaries of materials science
laboratories is possible only on successful consolidation of these materials into bulk-sized
components preserving the nanostructures. Due to the long duration of sintering at high
temperature that is involved in conventional consolidation techniques, it is difficult to retain
the nanograin-size due to grain growth in such techniques.
The density of the green compact depends on the frictional forces of the powder particles
that originate from electrostatic, van der Waals and surface adsorption forces. These forces
are significantly high in nanoparticles, forming hard agglomerates and inter-agglomerates,
which are relatively large. Further, nanoparticles contain a large number of pores which
require not only higher temperature but also prolonged sintering times for their successful
elimination; consequently, it becomes difficult to retain the grain size in the nanometre
domain. Large pores undergo pore–boundary separation that restricts the attainment of full
density in the consolidated nanoparticles. During sintering of nanoparticles, pores smaller
than the critical size shrink, while larger pores undergo pore–boundary separation. The
fraction of grain boundaries in nanomaterials is large compared to that in coarse-grained
materials. The density of the grain boundary regions is less than the grain interior due mainly
to the relaxation of atoms in the grain boundaries; they also contain other lattice defects.
Therefore, consolidated nanoparticles with retained nanostructure are expected to exhibit a
density lower than the theoretical density of the bulk counterpart.
There are numerous conflicting views on the sintering behaviour of nanoparticles.
Nanoparticles show depressed onset of sintering temperature to the range of 0.2 Tm–0.3 Tm
compared to conventional powders that normally exhibit a range of 0.5 Tm–0.8 Tm, where
Tm is the melting point (in K). Cu–Ta nanocomposites have been consolidated to close to
theoretical densities at 500°C, while the microcomposites in the same system need a sintering
temperature of 1000°C (Fig. 3.15). Similarly, W, which is used in filaments, is usually sintered
at about 2800°C due to its high melting point. However, nanocrystalline W could be sintered
to close to its theoretical density at 1500°C itself leading to significant energy savings.
Figure. 3.25 shows the dilatometry results of microcrystalline W and nanocrystalline W
(50 mm) obtained by high-energy ball milling of W (50 mm) in Simoloyer for two hours.
Significant differences in sinterability are evident from the extent of consolidation observed
in the nanocrystalline W. Such results may possibly be attributed to significantly high
diffusivities due to large surface/grain boundary area and large defect densities.
Synthesis of nanoparticles of ceramic, metallic and their mixture has made substantial
progress in the last decade. However, retention of nanostructures in these materials after
consolidation into fully dense components is a challenge. A brief review of the various
consolidation processes is presented here.

3.3.1 Shockwave consolidation

Shock wave consolidation, also termed dynamic consolidation, is used to densify powdered
materials without inducing thermal activated microstructural and compositional changes
 Chapter 3: Synthesis Routes 101

Fig. 3.25 Improved sinterability of nanocrystalline W in comparison to microcrystalline W.

(Source: BS Murty, IIT Madras).

that are normal in conventional thermomechanical processing. Such densification is

possible because of the interparticle bonding due to localized melting at the interfaces
between the particles. High pressure and rapid loading rates that create high plastic
deformation finally lead to high shock initiated chemical reactions completely different
from the conventional ones. Metallic or alloy powders are usually processed through this
route due to the fact that plastic deformation in metal is comparatively easier than for
ceramics.
In this process, particles are enclosed in a steel block that looks similar to a cold compaction
chamber that is covered using a plate, on top of which a driver plate usually bears the brunt
of explosions and drives the shock wave towards the sample (Fig. 3.26). The driver plate is
usually made of highly conductive and ductile material. Explosives are packed on top of
this plate carefully and the spillage, if any, has to be removed. The detonator is set on top of
the explosive and the set up is ready for processing to start. Ammonium nitrate is usually
used as the explosive. Shock compaction of powders is a dynamic consolidation technique
which provides a viable method for densification of amorphous as well as ultrafine powders.
Fe-, Ni- and Ti-based alloys have been studied more often using this technique. Pure metals
and alloys with retained nanostructures can be consolidated using this technique. Some of
the systems that have been investigated are: Fe73.5Cu1Nb3Si13.5B9, Fe, Fe–Al, diamond–Si, Al,
Pr2Fe14B/α-Fe, Ti5Si3 and NiAl.
102 Nanoscience and Nanotechnology

3.3.2 Hot isostatic pressing (HIP)

and cold isostatic pressing (CIP)
The process of using high hydrostatic
pressure and high temperature to
compress fine particles into coherent
parts is termed ‘hot isostatic pressing’
(HIPing). This process provides a
method for producing components
from diverse powdered materials,
including metals and ceramics. A
typical schematic of the HIPing
process is shown in Fig. 3.27. In this
process, the elemental blend is placed
in a container, usually a steel can.
The container is subjected to elevated
temperatures, and very high vacuum
to remove air and moisture from the
powder, after which it is sealed and
HIPed. The application of high inert gas
Fig. 3.26 Schematic of shock wave consolidation setup. pressures and elevated temperatures
results in the removal of internal voids
and creates a strong bond throughout the material. The result is a clean homogeneous material
with a uniformly fine grain size and near 100% density.
In cold isostatic pressing (CIPing), pressure is applied from multiple directions to get
better uniformity of compaction, compared to uniaxial pressing. There are two methods in
isostatic pressing. In wet bag isostatic pressing, the powder is encased in a rubber sheath that is
immersed in a liquid that transmits the pressure uniformly to the powder. In dry bag isostatic
pressing, instead of immersing the tooling in a fluid, the tooling itself is built with internal
channels into which high pressure fluid is pumped.
Some of the material systems that have experimented with the HIPing process are TiC,
TiCN, SiC, Si3N4–Y2O3–Al2O3, Si3N4, intermetallic TiAl, TiAlSi, MgAl2O4, Ni–Fe, Y2O3
dispersed steels, MgAl2O4 dispersed steels, Al and carbon nanotube reinforced Si3N4. There
have been instances where HIP is used as an add-on processing to CIP to increase the
densification and thereby mechanical properties, for example, consolidation of Fe. Using
CIP as a primary consolidation technique works well for a micron-sized particle whereas
a nanoparticle might need some kind of secondary consolidation process to form a bulk
part, as the nanoparticles are friable and can crumble even if crushed with a hand. The
only solution is to either use sintering after CIPing or to use HIPing. It has been found that
HIPing leads to better densification in less time compared to the time required for sintering
to achieve the same density.
 Chapter 3: Synthesis Routes 103

Fig. 3.27 Schematic of a hot isostatic pressing setup.

3.3.3 Spark plasma sintering

With the growing need for processing and consolidating nanopowders, retaining the initial
microstructure in the fabricated component remains a challenge. Though the manufacture of
novel materials is limited to laboratory scale, vigorous demand in the market persists and is
driving the demand for new consolidation techniques apart from hot pressing, high temperature
extrusion and hot isostatic pressing. Since longer processing times at high temperatures often
result in extraneous grain growth, the new nanopowder processing technique, namely spark
plasma sintering (SPS), which has evolved in the last decade, overcomes these obstacles by
applying rapid heating to sintering temperatures, leading to rapid sintering of nanocomposites.
The attractive properties of nanopowders are well conserved by the fabrication of bulk
material through SPS. Consolidation of metals, composites, ceramics, intermetallics, cermets,
nanocomposites and carbon nanotube reinforced ceramics has been accomplished by spark
plasma sintering.
The schematic of a typical SPS apparatus is shown in Fig. 3.28. It consists of a graphite
die where powder is loaded and heated by passing an electric current. Hold time, ramp rate,
pulse duration, and pulse current and voltage can be set for controlling the temperature of the
sintering cycle. Change in temperature, pulse power (voltage/current), sintering displacement
104 Nanoscience and Nanotechnology

Fig. 3.28 Schematic of SPS setup.

and sintering rate are recorded in situ during spark plasma sintering. Powder mixtures are
initially cold pressed (∼ 200 MPa) into a compact disc (with diameter around 2 cm and thickness
around 5 mm), followed by SPS processing to produce nano-consolidated nanocrystalline
composites. Typical SPS processing parameters include:
• Applied pressure between 50 and 100MPa
• Pulse duration of ∼ 10 ms with on–off cycle of 2–2.5 ms
• Maximum pulse parameter of 10,000 A and 10 V
After applying the given pressure, samples are heated to the preset temperature (for a few
minutes) and are ramped rapidly (∼150–500 K/min) to sintering temperatures with hold
time of 3–5 min to complete the sintering. Samples are usually cooled to below 100°C within
5 minutes of the completion of sintering.
Densification of the green compact occurs in four stages: vacuum creation, pressure
application, resistance heating and cooling down as shown schematically in Fig. 3.29. SPS is
carried out in vacuum to account for removal of gases, and results in a densely consolidated
composite. Heating is accomplished by spark discharge between particles, which activates the
surface by removing surface oxide. This helps in heat and mass transfer between the purified
particles to carry heat and sinter them to full density. Initially, samples show an increase in
volume due to thermal expansion, followed by shrinkage occurring primarily during resistance
heating when the green discs are held at high temperatures and pressure. Onset of sintering
is dependent on the initial particle size, which decides the onset of shrinkage. It is generally
difficult to determine when the sintering process is complete; however, shrinkage of the
specimen could help in deducing the completion of SPS sintering. Some of the nanopowder
material systems that have been consolidated with SPS process are amorphous Si–C–N, Ni–Ti
shape memory alloy, (Al–12.5Cu)3Zr intermetallic, TiCN cermet, SiC–ZrO2–Y2O3–Al2O3
 Chapter 3: Synthesis Routes 105

Fig. 3.29 Schematic of SPS sintering stages.

composites and CNT-Al2O3 composites. Figure 3.30 shows the TEM images of SPS consolidated
structural nanocomposites (NiAl–Al2O3 and FeAl–Al2O3), both of which demonstrate that
the nanocrystalline nature is retained after SPS.
Considering the rapid advancement in the field, it is a mammoth task to cover all the
techniques of synthesis and consolidation of nanoparticles and nanocrystalline materials that
are available, and the reader is encouraged to further explore this exciting world.

(a) (b) (c)

0.5 μm 1000 nm 50 nm

Fig. 3.30 TEM images of SPS consolidated samples of (a) NiAl–Al2O3 and (b) FeAl–Al2O3 nanocomposites;
(c) Higher magnification image of a region in (b). (Source: BS Murty, IIT Madras).
106 Nanoscience and Nanotechnology

SUMMARY

• Various techniques are available for the synthesis of nanoparticles and

nanostructured materials.
• The techniques available can be grouped broadly into the ‘top-down’ and ‘bottom-
up’ approaches.
• These techniques can also be classified, based on the state of the matter from
which the nanomaterials are synthesized.
• In bottom-up techniques, nanoparticles are prepared from the vapour or liquid
phase, while in top-down approaches, they are made from solids.
• The challenge in consolidation of nanoparticles is to retain the nanocrystallinity
after consolidation.
• Among the various techniques of consolidation, spark plasma sintering is popular.

EXERCISES
1. Define ‘top-down’ and ‘bottom-up’ approaches for the synthesis of nanomaterials.
2. Identify the category (top-down or bottom-up) to which the methods listed below
belong:
(a) Sol–gel
(b) MBE
(c) E-Beam lithography
(d) ECAP
(e) Wire explosion
(f) Laser ablation
3. Describe the principle involved with suitable figures in the following techniques:
(a) RF and DC sputtering
(b) Electron beam evaporation
(c) Microwave plasma based CVD
4. It is desired to synthesize yttria nanoparticles of about 2–3 nm in size. Discuss the suitability
of the following techniques for the purpose with reasoning.
(a) Mechanical milling, (b) Electron beam evaporation, (c) CVD, (d) Sol–gel
5. Identify a suitable technique for the synthesis of (a) Au nanoshells and (b) Silica nanoshells,
and list a few applications for each.
6. Describe the distinctive features of a self-assembled nanostructure.
7. Compare ion and electron beam nanolithography for nanofabrication.
8. List a few deformation-based techniques for the development of nanostructures.
9. Discuss briefly what we can learn from nature for the synthesis of nanostructures.
10. Identify techniques for the development of bulk nanostructured solids from
nanopowders.