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NANOPOWDERS AND
N A N O M AT E R I A L S

There are six widely known methods to produce nanomaterials other than by
direct atom manipulation. These are plasma arcing, chemical vapour deposi-
tion, electrodeposition, sol-gel synthesis, ball milling, and the use of natural
nanoparticles. In this chapter you will find out about different types of nano-
materials and how they are formed, what methods are used for different
materials and how the new materials can be used.

3.1 WHAT ARE NANOMATERIALS?

All materials are composed of grains, which in turn comprise many
atoms. These grains can be visible or invisible to the naked eye,
depending on their size. Conventional materials have grains varying in
size anywhere from hundreds of microns to centimetres.
Nanomaterials, sometimes called nanopowders when not compressed,
have grain sizes in the order of 1–100 nm in at least one coordinate and
normally in three. Typical nanomaterials (zinc oxide and cerium oxide)
are shown in Figure 3.1 under transmission electron microscopy.
Under normal conditions these oxides form crystals that can be as large
as a cubic millimetre in size, but these photographs show that as
nanoparticles they are less than 100 nm in length. They are not amor-
phous, because the atoms are still arranged in discrete crystals.
Nanomaterials are not new. However the understanding that cer-
tain preparations of oxides, metals, ceramics (a ceramic is defined as an
inorganic substance that can be heated into a useful hard structure) and
other substances are nanomaterials is relatively recent. Carbon black is
a nanomaterial that is used in car tyres to increase the life of the tyre
and provide the black colour. This material was first discovered in the

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early 1900s. Fumed silica, a component of silicon rubber, coatings,

sealants and adhesives, is also a nanomaterial. It became commercially
available in the 1940s. With the advent of the advanced microscopic
analysis techniques described in the last chapter, new nanomaterials
have been developed much more systematically and with a greater
understanding.
Figure 3.1
Nanocr ystals of
a) cerium oxide, CeO 2 and
b) zinc oxide, ZnO. By permission of Advanced Powder Technologies, Per th, Australia.

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58 • N A N OT E C H N O L O G Y

Interest in nanomaterials was already evident before Feynman’s

speech [1] or Drexler’s book [2] defined the new age of nanotechnol-
ogy. However, it was realised only at about this time that the particle
size of carbon black and fumed silica is of nanometre dimensions. In
typical nanomaterials, the majority of the atoms are located on the sur-
face of the particles, whereas they are located in the bulk of conven-
tional materials. Thus the intrinsic properties of nanomaterials are
different from conventional materials, since the majority of atoms are
in a different environment. Nanomaterials represent almost the ulti-
mate in increasing surface area.
Substances with high surface areas have enhanced chemical,
mechanical, optical and magnetic properties, and this can be exploited
for a variety of structural and non-structural applications. In aerospace
and automotive applications, for example, materials made from metal
and oxides of silicon and germanium exhibit superplastic behaviour,
undergoing elongations from 100 to 1000 per cent before failure. This
is because the individual nanosized particles can expand relative to each
other. Some nanomaterials are exceptionally strong, hard and ductile at
high temperatures. However, they are chemically very active because
the number of surface molecules or atoms is very large compared with
the molecules or atoms in the bulk of the material. Sometimes, to
retain the desired properties of the nanomaterial, a stabiliser must be
used to prevent further reaction. This enables them to be wear-resis-
tant, erosion-resistant and corrosion-resistant, but this resistance is
usually imparted by some sort of protection mechanism.

3.2 PREPARATION
There are six widely known methods to produce nanomaterials. These
are plasma arcing, chemical vapour deposition, electrodeposition, sol-
gel synthesis, ball milling, and the use of natural nanoparticles. In the
first two methods, molecules and atoms are separated by vaporisation
and then allowed to deposit in a carefully controlled and orderly man-
ner to form nanoparticles. The third method, electrodeposition,
involves a similar process, since individual species are deposited from
solution. The fourth process, sol-gel synthesis, involves some prior
ordering before deposition. In ball milling, known macrocrystalline
structures are broken down into nanocrystalline structures, but the
original integrity of the material is retained. However, the nanoparti-
cles can reform into new materials, which involve breaking the original
crystallite bonds. It might be construed that materials such as layered
phyllosilicate clays are not nanomaterials since they are natural sub-
stances. However nothing could be further from the truth. Layered
phyllosilicates are natural nanostructures, although they are normally
aligned in such a way that their nanostructure cannot be exploited. The
surface area to bulk atom ratio is huge and when dispersed they form

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nanocrystallites. Thus chemical treatment can generate nanomaterials

with different properties.
We will deal briefly with each of the methods of preparing nano-
materials in turn.

3.3 PLASMA ARCING [3]

Plasma is an ionised gas. A plasma is achieved by making a gas conduct
electricity by providing a potential difference across the two electrodes
so that the gas yields up its electrons and thus ionises. In a vacuum or
in an inert gas the electrodes can be made volatile. Heat is produced
and the electrodes or even other materials can be volatilised and ionised
using this heat. Plasma arcing has been important in forming carbon
nanotubes (Chapter 4). A typical plasma arcing device consists of two
electrodes. An arc passes from one electrode to the other. The first
electrode (anode) vaporises as electrons are taken from it by the poten-
tial difference. To make carbon nanotubes, carbon electrodes are used.
Atomic carbon cations are produced. These positively charged ions
pass to the other electrode, pick up electrons and are deposited to form
nanotubes.
The electrodes can be made of other materials but they must be
able to conduct electricity. An interesting variation is to make the elec-
trodes from a mixture of conducting and non-conducting materials.
During heating, the non-conducting material is vaporised and ionised
so that it also becomes part of the plasma arc and is transported and
deposited on the cathode.
Plasma arcing can be used to make deposits on surfaces rather than
new structures. In this way it resembles chemical vapour deposition (see
below) except that the species involved are ionised. As a surface deposit,
the nanomaterial can be as little as a few atoms in depth. It is not a nano-
material unless at least one dimension of the bulk particle of the surface
deposit is of nanometre scale. If this is not true, it is a thin film and not
a nanomaterial. Each particle must be nanosized and independent, other
than interacting by hydrogen bonding or van der Waals forces.
A variation on plasma arcing is flame ionisation. If a material is
sprayed into a flame ions are produced, and these can also be collected
and deposited in nanocrystallite form.

3.4 CHEMIC AL VAPOUR DEPOSITION [4]

This method involves depositing nanoparticulate material from the gas
phase. Material is heated to form a gas and then allowed to deposit as
a solid on a surface, usually under vacuum. There may be direct depo-
sition or deposition by chemical reaction to form a new product which
differs from the material volatilised. This process readily forms
nanopowders of oxides and carbides of metals if vapours of carbon or
oxygen are present with the metal.

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60 • N A N OT E C H N O L O G Y

Production of pure metal powders presents a greater challenge, but

it has been achieved using microwaves. In this method, microwaves
tuned to metal excitation frequencies are used to melt and vaporise the
reactants to produce a plasma at temperatures up to 1500˚C. Then the
plasma enters a reaction column cooled by water, which facilitates the
formation of nanometre size particles. The residence time of reactants
in the plasma can be controlled to ensure complete conversion. Metal
concentration in the gas phase (proportional to partial pressures — see
chemistry texts), flow rate of metal vapour, and temperature, alter the
particle grain sizes and their distribution. After cooling to 700˚C or
another appropriate temperature these nanoparticles are filtered from
the exhaust gas flow at high temperature, where they fall into a con-
tainer or bottle below. Depending on the material, slow introduction
of a stabiliser helps reduce their reactivity by forming a thin protective
coating.
Chemical vapour deposition can also be used to grow surfaces. An
object to be coated is allowed to stand in the presence of the chemical
vapour. The first layer of molecules or atoms deposited may or may not
react with the surface. However, these first formed depositional species
can act as a template on which material can grow. The structures of
these materials are often aligned, because the way in which atoms and
molecules are deposited is influenced by their neighbours. This works
best if the host surface is extremely flat. During deposition, a site for
crystallisation may form in the depositional axis, so that aligned struc-
tures grow vertically. This is diagrammatically shown in Figure 3.2a,
with a real structure formed from carbon nanotubes in Figure 3.2b.
This is therefore an example of self assembly (Chapter 2.12). It can be
seen from Figures 3.2a and 3.2b that the properties of the surface will
be different in the z axis than the x, y plane. This gives the surface
unique characteristics.

Figure 3.2
Aligned cylindrical molecules formed by chemical vapour deposition.
a) Model.
b) Aligned carbon nanotubes. Reproduced with permission from NASA Ames, the
Center for Nanotechnology.
a b

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Chemical vapour deposition is particularly useful when nanosites

have first been engineered on a surface and the material is subsequent-
ly placed on the sites. This is normally done by electron lithography
(Chapter 8) or etching (Chapter 2.11). A material is coated on a sur-
face and then parts of the coating are evaporated using a strong elec-
tron beam or chemicals. In particular variants, the electron beam can
be used to polymerise certain compounds — such as compounds with
triple bonds — thereby creating heterogeneous areas. Chemical vapour
deposition can be used to build structures on these surfaces (Figure
3.3a), so there is structure in both the micro- and the nano- domain
(Figure 3.3b). A variation on this is masking. In masking, a layer is
placed on a surface over the structures that we do not want to remove.
This protects the structure and the mask is removed after treatment.
Alternatively, dip pen nanolithography (see Chapter 2.12) can be
used to write on the surface. The main advantage of chemical vapour
deposition over dip pen nanolithography is that it can build nanos-
tructures rapidly by self assembly. The disadvantage is that the mole-
cules cannot be directed. In dip pen nanolithography, the molecules
can be precisely placed.

Figure 3.3 Coating

a) Diagram to
illustrate method-
ology for forming
nanopillars by
chemical vapour
deposition. Electron
b) Example with Burning
carbon forests. Chemical
Reproduced with vapour
permission from
NASA Ames, the deposition
Center for
Nanotechnology.

100 µm

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62 • N A N OT E C H N O L O G Y

3.5 SOL-GELS [5]

Sol-gel is a useful self assembly process for nanomaterial formation. A
characteristic of a solution is that it is clear. That is, you can see
through it. Solutions are clear because molecules of nanometre size are
dispersed and move around randomly. In colloids the molecules are
much larger and range from 20 m to 100 m in diameter. Colloids
are suspensions of these sized molecules in a solvent. Colloid particles
are thus much larger than normal sized molecules or nanoparticles, but
they still cannot be seen with a light microscope. However, when
mixed with a liquid, colloids can often look cloudy or even milky,
whereas nanosized molecules in solution always look clear. A colloid
that is suspended in a liquid is called a sol. A suspension that keeps its
shape is called a gel. Thus sol-gels are suspensions of colloids in liquids
that keep their shape.
The sol-gel process, as the name implies, involves the evolution of
networks through the formation of a colloidal suspension (sol) and
gelation of the sol to form a network in a continuous liquid phase (gel).
The precursors for synthesising these colloids normally consist of ions
of a metal but sometimes other elements surrounded by various reac-
tive species, which are called ligands. Metal alkoxides and alkoxysilanes
are most popular because they react readily with water. The most wide-
ly used alkoxysilanes are tetramethoxysilane (TMOS) and
tetraethoxysilane (TEOS), which form silica gels. However, alkoxides
such as aluminates, titanates, and borates are also commonly used in
the sol-gel process, often mixed with TMOS or TEOS. Additionally,
because water and alkoxides are immiscible, a mutual solvent such as
an alcohol is used. The miscibility of the alkoxide and water is facilitat-
ed by the presence of this homogenising agent.
Sol-gel formation occurs in four stages:

1 hydrolysis;
2 condensation and polymerisation of monomers to form particles;
3 growth of particles;
4 agglomeration of particles followed by the formation of networks that
extend throughout the liquid medium resulting in thickening, which
forms a gel.

SILICA GELS
All four of the above processes are affected by the initial reaction con-
ditions. Thus the characteristics and properties of a particular sol-gel
network are related to a number of factors that affect the rate of
hydrolysis and condensation reactions, such as:

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• pH
• temperature and time of reaction
• reagent concentrations
• nature and concentration of catalyst
• H2O/Si molar ratio [H2O/Si]
• aging temperature and time
• drying.

Of the factors listed above, pH, nature and concentration of cata-

lyst, H2O/Si molar ratio [H2O/Si], and temperature have been iden-
tified as most important. By controlling these factors, it is possible to
vary the structure and properties of the sol-gel-derived inorganic net-
work over wide ranges. As the number of siloxane bonds increases, the
individual molecules are bridged and jointly aggregate in the sol. When
the sol particles aggregate, or inter-knit to form a network, a gel is
formed. Upon drying, trapped volatiles (such as water or alcohol) are
driven off and the network shrinks as further condensation can occur.
With hydrolysis under basic conditions (pH greater than 7) and
[H2O/Si] values ranging from seven to twenty-five, dispersed spheri-
cal nanoparticles are produced.
HYDROLYSIS
In hydrolysis the reaction occurs through the addition of water, which
results in the replacement of alkoxide groups (OR) with hydroxyl
groups (OH). Subsequent condensation reactions involving the silanol
groups (Si-OH) produce siloxane bonds (Si-O-Si) plus the by-prod-
ucts water or alcohol. Under most conditions, condensation com-
mences before hydrolysis is complete. However, conditions such as
pH, H2O/Si molar ratio, and catalyst can force completion of hydrol-
ysis before condensation begins. Nevertheless, regardless of pH,
hydrolysis occurs by the attack of the oxygen contained in water on the
silicon atom. This is evidenced by the reaction of isotopically labelled
water (water with oxygen of atomic weight 18 instead of 16) with
TEOS, which produces only unlabelled alcohol in both acid- and base-
catalysed systems:

H218O + ROSi(OR)3 R OH + H18OSi(OR)3

where R = alkyl groups of various types.

Although hydrolysis can occur without the addition of external cat-
alysts, it is most rapid and complete when they are employed. Mineral
acids (HCl) and ammonia (NH3) are most generally used, however,
other catalysts are acetic acid (CH3COOH), potassium hydroxide

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64 • N A N OT E C H N O L O G Y

(KOH), amines, and hydrofluoric acid (HF). It has been observed that
the rate and extent of the hydrolysis reaction is most influenced by the
strength and concentration of the acid or base catalyst.
Under acidic conditions, it is likely that an alkoxide group is pro-
tonated in a rapid first step. Electron density is withdrawn from the sil-
icon atom, thus making it more susceptible to attack from water. The
water displaces a protonated alkoxy group:

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

It has been proposed that H2O displaces ROH with simultaneous

attack on the opposite side from which the ROH leaves.
Under basic conditions, it is likely that water dissociates to produce
hydroxyl anions in the first step and the hydroxyl anion then attacks the
silicon atom. It has been proposed that -OH displaces -OR by attack
from the opposite side, similar to acid catalysis:

HO- + ROSi(OR)3 RO- + HOSi(OR)3

Hydrolysis occurs until all -OR (alkoxy) groups are replaced by

-OH (hydroxyl). However, as noted, condensation to form siloxane
bonds (Si-O-Si) often begins before all groups are exchanged and
therefore the reaction is quite complex.
CONDENSATION AND POLYMERISATION OF MONOMERS TO FORM
PARTICLES
Polymerisation to form siloxane bonds occurs by either an alcohol-pro-
ducing or a water-producing condensation reaction. The monomer
HOSi (OR)3 reacts:

2 HOSi (OR)3 (OR)3 SiOSi(OR)3 + H2O

2HOSi(OR)3 (OR)2OH SiOSi(OR)3 + HOR

Like hydrolysis, it is generally believed that the acid-catalysed con-

densation mechanism involves a protonated silanol species.
Protonation of the silanol makes the silicon more susceptible to attack.
Subsequently the trimer (three silicon) and tetramer (four silicon)
species are formed. The reaction is not simple and there is a wide range
of silicon species in solution, some of which produce cyclic structures.
Cyclisation occurs because of the proximity of the chain ends and the
substantial depletion of the monomer population. It should therefore
be favoured by dilute solution. Rings, like linear species, may open and
accept more monomers. A typical sequence of condensation products
is monomer, dimer, linear trimer, cyclic trimer, cyclic tetramer, and

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higher order rings. This sequence of condensation requires both

depolymerisation (ring opening) and the availability of monomers that
are in solution equilibrium and/or are generated by depolymerisation.
The most basic silanol species (silanols contained in monomers and at
the end of chains) are the most likely to be protonated. Therefore, con-
densation reactions may occur preferentially between neutral species
and protonated silanols situated on monomers, and the end groups of
chains.
Silica solubility is also important when the pH is changed. In poly-
merisations below pH 2, the condensation rates are proportional to the
[H+] concentration, but because the solubility of silica is quite low
below pH 2, precipitation occurs. Formation of primary silica particles
results and it is not possible for a network to grow. Thus, developing
gel networks consist of extremely small primary particles, not exceed-
ing 2 nm in diameter.
Between pH 2 and pH 6, condensation preferentially occurs
between more highly condensed species and those less highly con-
densed. This suggests that the rate of dimerisation is low, however,
once dimers form, they react preferentially with monomers to form
trimers, which in turn react with monomers to form tetrameters.
Further growth occurs by addition of lower molecular weight species
to more highly condensed species and aggregation of the condensed
species to form chains and networks. The solubility of silica in this pH
range is again low and particle growth stops when the particles reach
2–4 nm in diameter.
Above pH 7, polymerisation occurs in the same way as in the pH 2
to pH 6 range. However, in this pH range, the condensed species are
ionised and therefore they are mutually repulsive so reaction is slower.
Due to the greater solubility of silica and the greater size dependence
of solubility above pH 7, particles grow in size and decrease in num-
ber as highly soluble small particles dissolve and re-precipitate on larg-
er, less soluble particles. Growth stops when the difference in solubility
between the smallest and largest particles becomes indistinguishable.
This process is referred to as Ostwald ripening. Particle size is mainly
temperature dependent, because solubility of larger particles is higher
at higher temperatures, so that at higher temperatures larger particles
are formed before they drop out of solution.
Particle size can also be affected by adding surfactants (often
organic quaternary ammonium salts). These have polar structures,
which can interfere with particle growth by binding to small particle
surfaces.
ZIRCONIA AND YTTRIUM GELS
Similar processes can be developed with zirconia. A slurry of the
hydroxide is dissolved in acid. Yttrium nitrate is added to form a sol,

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66 • N A N OT E C H N O L O G Y

which gels and forms powders. Surfactants are used to control the size
of the spheres and particles:

Zr(OH)4 + HNO3 sol Yttria sol spheres gel powder

ALUMINOSILICATE GELS
Aluminosilicate gels are special because they form tubular structures.
The overall pathway proposed is shown in Scheme 1. Tetraethoxysilane
or other alkoxy species hydrolyse sequentially, as shown below, to give
rise to species containing alkoxy groups, for example (CH3CH2 O):

H2O + (CH3CH2O)4Si (CH3CH2O)3SiOH + CH3CH2OH

H2O + (CH3CH2O)3SiOH (CH3CH2O)2Si(OH)2 + CH3CH2OH

Normally aluminium is introduced as aluminium chloride. In this

form aluminium has an octahedral structure since it is surrounded by
six molecules of water (scheme 1). This will react rapidly with various
ethoxy-substituted silica tetrahedra (Scheme 1, Step 1) but some will
rapidly transform into tetrahedral aluminium (Scheme 1, Step 2).
These species would rapidly lose OEt (ethoxy) groups and polymerise,
possibly with silicon or alumina groups (the latter is shown in scheme
1, step 3). In this step we have written:

Si(OEt)3OAl(OH) 3- Si(OEt)3OAl(OH)2OAl(OH)3

It is probably more complex than this since a range of molecules

may be present and in some of them, many of the ethoxy groups are
substituted by silicon tetrahedra. Evidence suggests that any tetrahe-
dral aluminium must then rehydrate (Scheme 1, step 4) and lose any
remaining ethoxy groups (step 5). The final stages of the process
involve the conversion of the structure shown on the right side of line
6, Scheme 1 into a polymer of that form, called protoimogolite. This
structure naturally curves due to the binding of oxygen across two alu-
minium atoms, and can then form an aluminosilicate tube called
imogolite (Figure 3.4). This last step appears to be a crystallisation
process.

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Scheme 1
Possible reaction paths in imogolite formation. Et is an ethoxy group (CH3CH20).

1 Si(OEt)3OH + Al(H2O)6+3 Si(OEt)3OAl(H2O)52+ + H3O+

2 Si(OEt)3OAl(H2O)52+ Si(OEt)3OAl(OH)3 - + 2H2O + 3H+

3 Si(OEt)3OAl(OH)3 - + Al(H2O)6+3 2H+ + 4H2O +

Si(OEt)3OAl(OH)2Al(OH)3

4 Si(OEt)3OAl(OH)2Al(OH)3 Si(OEt)3OAl(OH)2 (H2O)2Al(OH)3

(H2O)2

5 Si(OEt)3OAl(OH)2 (H2O)2 Al (OH)3 (H2O)2

Si(OH)3OAl(OH)2(H2O)2Al(OH)3 (H2O)2

OH2 OH2 OH2 OH2

H2O OH OH H2O OH OH
Al Al Al Al
HO HO OH
OH OH OH
OH2 O
O

Si
Si
OH OH
OH OH OH
OH

Protoimogolite

Figure 3.4
Cross section of an
imogolite nanotube.

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68 • N A N OT E C H N O L O G Y

The external tube diameter of imogolite has been shown to be

approximately 2.5 nm by TEM and the tubes are several micrometres
long. Electron micrographs have shown that the tubes exist in a high
degree of order as self-aligned bundles.
Adsorption has been used to measure the internal diameter of the
intra-tube pore. Nitrogen studies of the pore volume indicate that the
intra tube pore diameter is 1.5 nm.
Imogolite pore measurements have been calculated with the aim of
exploiting charge and intra-tube pores in nanotechnology as useful
voids for adsorbing and storing things. Imogolites have also been
shown to be adsorbents for anions such as chloride, chlorate, sulfate
and phosphates. Because the structure can be dissolved away with
hydrofluoric acid, if the tube is filled with a few atoms and then dis-
solved away, rows of atoms can be formed. This is an alternative to dip
pen nanotechnology or chemical vapour deposition (Chapter 2.12).
FORMING NANOSTRUCTURED SURFACES USING THE SOL-GEL
PROCESS
The sol-gel process discussed so far is summarised in steps one to three
of Figure 3.5, that is, to the gel stage. While the spheres can be col-
lected as gelled spheres or collapsed gels (xerogels), a better means of
exploiting their surface area is to capture the gel on a surface. This way
a greater surface to bulk area ratio is obtained. Another possibility is
aerogels. Aerogels are composed of three-dimensional, continuous net-
works of particles with air (or any other gas) trapped at their interstices.
Aerogels are porous and extremely light, yet they can withstand 100
times their own weight.
Another very clever way of maximising the surface area is colloidal
crystallisation on surfaces. In this process, water is very carefully
removed so that the sol gel structure is not lost in the precipitate.
Nanostructured silica with controlled pore size, shape and ordering can
be obtained this way. When surfactants are mixed with water, long
range spatially periodic architectures are created in a nanofoam, with
lattice parameters in the range of 2 nm to 15 nm. The hydrolysis and
polycondensation of silica precursors confined to the aqueous domains
of these phases affords a simple and versatile method of producing
monolithic nanostructured silica whose architecture is effectively the
cast of the structure of the liquid crystalline phase used in the synthe-
sis [6]. For example, hexagonal patterns of silica with cylindrical pores
2.0–3.0 nm in diameter (Figure 3.6) are obtained on a surface by con-
ducting the reaction in a hexagonal liquid crystalline phase and subse-
quently removing the surfactant by heating (called calcination). In this
material, the silica walls are approximately 1.2 nm thick. The hydroly-
sis and condensation reactions, which at room temperature proceed
over a period of approximately six hours, are confirmed by analysis

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Figure 3.5
Summar y of sol-gel process

[7–10]. These studies demonstrate the continuity of the nanostructure

from the fluid liquid crystalline reaction mixture, through the gelled
system to the calcined material. Similarly, by conducting the reactions
in a cubic liquid crystal phase, it is possible to obtain silicas with the
corresponding nanostructures of this phase. These silicas have specific
surface areas of around 1500 m2g-1. The combination of high surface
area, large pores and uniform pore diameter makes these materials of
considerable interest for applications in catalysis and chemical separa-
tions, especially if catalysts such as transition metals (such as V, Co etc)
are incorporated as framework species and appropriate salts are includ-
ed in the reaction mixtures.
Another significant advantage of the liquid crystal method is to
produce nanostructured metals. This development involves dissolving
the metals and again retaining the liquid crystal structure pattern [9].
This development is significant because it creates metallic catalysts that
have surface areas greater than those of conventional or even colloidal
metals. This gives them a greater potential as catalysts. Metals of par-
ticular interest are platinum, Pt, and palladium, Pd. There are also big
cost benefits. Almost every platinum atom takes part in the reaction
and not just the surface atoms as in a conventional solid.

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70 • N A N OT E C H N O L O G Y

Figure 3.6
Hexagonal patterns of silica with 2–3 nm pores prepared by sol-gel.

TRAPPING BY SOL-GELS
In another useful development, organic, inorganic and bio-organic
molecules are doped (entrapped) in silica glass using sol-gel proce-
dures. Most existing organic and bio-organic molecules cannot be
doped in glass, because glass is prepared at elevated temperatures
(about 1000˚C). However, due to the relatively low temperature need-
ed for the preparation of sol-gel matrices (in some cases room temper-
ature), these molecules can now be entrapped in sol-gel glass.
Sol-gel technology offers the following advantages:
• The glasses are inert.
• The glasses are much more stable to heat than plastics.
• The glasses are much more stable to decomposition by sunlight.
• The stability of the encased molecules or enzymes is higher in the sol-gel
glasses than in plastics. (This is due to the high rigidity of the glass cage
within which the molecule is doped, in comparison to plastic cages).

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• The sol-gel glasses are highly transparent, rendering this technology suit-
able for all optical requirements. This transparency includes the ultra-vio-
let range, which is far beyond the transparency of most commercial
plastics.
• Compared to using the surface of porous glasses for the attachment of
molecules, this technology offers much better protection of organic mol-
ecules. Molecules that are adsorbed on porous glass surfaces are easily
leached out; molecules that are anchored on the surface can be dislodged
when the anchor decomposes; and there is no protective cage as there is
with sol-gel glasses.
In addition to the unique advantages of the sol-gel technology, it
also shares the common advantages of the plastics technology:
• It is a low temperature process.
• The product can be obtained in any form (plates, discs, powders, thin
films, etc.).
• It can be attached to most other materials (plastics, paper, metal, etc.).
• It can be polished to optical quality.
Sol-gel technologies can also produce encapsulated active ingredi-
ents for sunscreens. With the increasing awareness that ultraviolet
(UV) sunlight is the primary cause of skin aging, wrinkles, blotchy pig-
mentation and skin cancer, people are using sunscreens more often.
These preparations contain concentrations of up to 40% active ingredi-
ents. A direct and undesired consequence of the increasing use of sun-
screen is that an increased amount of the active ingredients penetrate
through the epidermis into the body. Sunscreens function by absorb-
ing, reflecting or scattering UV light, and while they are performing
this task, photodegradation products and free radicals are formed. It is
safer to isolate this photochemistry from body tissues by confining it
within the glass particles. The active ingredients of many sunscreens are
therefore encapsulated as nanoparticles in smooth, cosmetically accept-
able microparticles (1000 nm). The particle loading (content of active
ingredient) is around 80 per cent. The product is presented in the form
of an aqueous suspension containing about 40 per cent microparticles.
When added to a sunscreen lotion formulation the product has a pleas-
ant feel and leaves no white residue.

3.6 ELECTRODEPOSITION [11]

Electodeposition has been used for a long time to make electroplated
materials. By carefully controlling the number of electrons transferred,
the weight of material transferred can be determined in accordance with
Faraday’s law of electrolysis. This states that the number of moles of
product formed by an electric current is directly proportional to the
number of moles of electrons supplied. Since the quantity of electricity

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72 • N A N OT E C H N O L O G Y

passed (measured in coulombs) is current (amps) x time (sec) and

Faraday’s constant F (96 485 coulombs is currently the most accurate
estimate) is the charge per mole of electrons (1 mole of electrons =
96 485 coulombs), then the number of moles of electrons is charge sup-
plied /F. Thus if we wished to copper plate an object with 5 g of cop-
per, we would need 5 / 63.546 (atomic weight of copper) = 0.07868
moles of copper or 2 x 0.07868 moles of electrons if we were reducing
Cu2+ ions. This is 1.52 x 104 coulombs or 4.2 amps for one hour. If
the surface of the object to be coated is 2 m2, each m2 would have 2.5 g
of copper or 0.03934 x 6.022 x 1023 (Avogadro’s number) atoms =
0.237 x 1023 atoms. Each nm2 would therefore have 0.237x 1023/ 1018
= 23 700 Cu atoms.
If the surface was perfectly flat, then knowing the diameter
(Chapter 1, Figure 1.6) of a copper atom it should be possible to cal-
culate the height and number of atoms in the copper layer. In practice
the surface is rocky (Chapter 2, Figure 2.15) so a coverage factor needs
to be included which is related to root-mean-squared roughness or
average roughness (Chapter 2.5).
In nanotechnology the aim is to place only a single layer or more
of coverage on a surface by electrodeposition in a very controlled way.
Thus, hypothetically if an atom of 10 nm diameter, which packs cubi-
cally (that is, at the corners of a square), is to be deposited as a mono-
layer at 50% coverage of a 1 cm2 surface, then 0.5 x 1012 atoms are
needed. If it is prepared from a divalent cation this requires 1x 1012
electrons or 0.166 x 10-11 moles (=16 016 x 10-11 coulombs) or
160.16 milliamps per microsecond. The current and time must be
carefully measured and any other factors involved in consuming cur-
rent, such as impurities, must be known in great detail. Hence the
necessity for super clean rooms.
Nevertheless, nanostructured films of platinum can be produced by
electrodeposition from liquid crystalline mixtures. The films obtained
are mechanically robust, remarkably flat, uniform, and shiny in appear-
ance. They also have surface areas comparable with those of the plat-
inum blacks deposited from conventional electroplating baths, and
exhibit quite different and favourable electrical properties than conven-
tional platinum deposits. The concept of electroplating from liquid crys-
talline mixtures can be used for other metals including Pd, Ni, and Au,
organic polymers (for example, polyaniline), oxides and semiconduc-
tors. The unique nature of nanostructured films from liquid crystals
makes them of considerable interest for a very wide range of applica-
tions. These include batteries, fuel cells, solar cells, windows that can
disperse heat and change properties depending on the environment
(electrochromic windows), sensors, field emitters, and photonic devices.
An electrochromic device consists of materials in which an optical
absorption band can be introduced, or an existing band can be altered

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by passing a current through the materials, or by the application of an

electric field. Nanocrystalline materials, such as tungstic oxide
(WO3.xH2O) gel, are used in very large electrochromic display devices.
The reaction governing electrochromism (a reversible colouration
process under the influence of an electric field) is the double-injection
of ions (or protons, H+) and electrons, which combine with the
nanocrystalline tungstic acid to form a tungsten bronze. These devices
are mostly used in public billboards and ticker boards to convey infor-
mation. Electrochromic devices are similar to the liquid-crystal displays
(LCDs) commonly used in calculators and watches. However, elec-
trochromic devices display information by changing colour when a
voltage is applied. When the polarity is reversed, the colour is bleached.
The resolution, brightness, and contrast of these devices greatly
depend on the grain size of the tungstic acid gels. Hence, nanomateri-
als are being explored for this purpose. More optical uses of nanoma-
terials are described in Chapter 7.
Electrodeposition can be used to fill holes to make dispersed nano-
materials. Nanoholes have been strategically placed in membranes.
These materials start with the bombardment of a polymer sheet by
energetic heavy ions accelerated by a cyclotron. The heavy ions pass
through the sheet and leave minuscule damage tracks. Chemical etch-
ing is used to turn these tracks into holes (nanoholes) with diameters
in the 10 to 100 nanometre range. Filling nanosized holes in polymer
membranes with various combinations of metals (Figure 3.7) produces
nanocomposites, which have different uses. For example, if some holes
are filled with a conducting metal like gold, then they can be charged
and this can influence the nature of ions that will go through the
unfilled holes. If there is a device at the other end that responds to
charge then the device becomes a specific ion detector. Other
nanocomposite materials can be produced with designer optical, elec-
trical, magnetic or chemical properties. Such materials can be used as
screening materials for heat, light or radiation, for example as thermo
liners in ovens and utensils, and in mobile phones. However, if they are
compound-specific they can be used as the active sensing material in
so-called intelligent materials for ‘artificial noses’ or sensors of biolog-
ical material. The most important development is the manufacture of
multipurpose chips, which will be able to sense a host of substances at
once and thus provide very specific and effective diagnoses.
Certain non-carbon types of nanotubes (Chapter 4) can be made
by electrodeposition and also by sol-gel processes.

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74 • N A N OT E C H N O L O G Y

Figure 3.7
Metal plastic nanocomposites
for selective ion separations

3.7 BALL MILLING [12, 13]

In the introduction to this chapter, we mentioned that we have known
for one hundred years that the structure of very finely divided powders
is quite different to their macrocrystalline counterparts, but it is only
lately that we have realised why. These early nanomaterials were made
by a simple method called ball milling, which is better described as
mechanical crushing. In this process, small balls are allowed to rotate
around the inside of a drum and drop with gravity force on to a solid
enclosed in the drum. Ball milling breaks down the structure into
nanocrystallites. The significant advantage of this method is that it can
be readily implemented commercially. Ball milling can be used to make
a variety of new carbon types, including carbon nanotubes [12, 13].
This is dealt with in Chapter 4. It is useful for preparing other types of
nanotubes, such as boron nitride nanotubes [14] and a wide range of
elemental and oxide powders. For example, iron with grain sizes of
13–30 nm can be formed. Other crystallites, such as iron nitrides, can
be made using ammonia gas. A variety of intermetallic compounds
based on nickel and aluminium can be formed with the empirical for-
mulae NixAl100-x, where 47 < x < 61.
Ball milling is the preferred method for preparing metal oxides
(Table 3.1). Their uses range from pigments to capacitors to coatings

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Table 3.1
Uses for nanometal oxides
Market Par ticles required Nanotechnology advantages
Polishing slurries Aluminium Oxide Faster rate of surface removal
reduces operating costs
Cerium Oxide Less material required due to
small size of par ticles
Tin Oxide Better finishing due to finer
par ticles
Capacitors Barium Titanate Less material required for a
given level of capacitance
Tantalum Higher capacitance due to
reduction in layer thickness and
increased surface area resulting
from smaller par ticle size
Alumina Thinner layers possible, thus
significant potential for device
miniaturisation
Pigments Iron Oxide Lower material costs, as
opacity is obtained with
smaller par ticles
Zirconium Silicate Better physical-optical proper-
Titanium Dioxide ties due to enhanced control
over par ticles
Dopants Wide variety of Improved compositional
materials required uniformity
depending on
application
Reduction in processing
temperature reduces operating
and capital costs
Structural ceramics Aluminium Oxide Improved mechanical proper ties
Aluminium Titanate Reduced production costs due
to lower sintering temperatures
Zirconium Oxide
Catalysts Titanium Dioxide Increased activity due to smaller
par ticle size
Cerium Oxide Increased wear resistance
Alumina
Hard coatings Tungsten Carbide Thin coatings reduce the
amount of material required
Alumina
Conductive inks Silver Increased conductivity reduces
consumption of valuable metals
Tungsten Lower processing temperatures
Nickel Allows electron lithography

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76 • N A N OT E C H N O L O G Y

to inks. All of these applications rely on the increased surface to bulk

ratio, which alters the chemical properties of the metal oxide.
To successfully prepare metal oxides, it is important to keep the
crystallites from reacting, and to have an understanding of the kinetic
energy transferred during crushing. Much of the commercial know-
how is in the nature of the additive. However, a by-product can some-
times be useful. In the production of nanocrystalline Zirconia (ZrO2)
zirconium chloride is treated with magnesium oxide during milling to
form zirconia and magnesium chloride:

ZrCl4 + 2MgO ZrO2 + 2MgCl2

The by-product, magnesium chloride, acts to prevent the individual

nanocrystallites of zirconia agglomerating. It is washed out at the end
of the process.
Ball milling techniques could be improved by applying a greater
knowledge of the energetics involved in the process. The exact energy
of delivery to each crystal needs to be determined and methods devel-
oped to ensure that each crystal receives the same energy, rather than
relying on ‘cook and look’ processes.

3.8 USING NATURAL NANOPARTICLES [15]

As noted above, there has been considerable interest in producing
pores in materials that moderately sized small molecules of 10 nm or
so can fit into and react on the surface. Bombarding materials with
energetic heavy ions accelerated by a cyclotron is an expensive way of
doing things. Some of the most successful materials, called zeolites,
have been synthesised by conventional chemistry, and operate at
nanopore size. There is a wealth of data on these materials beyond the
scope of this book. Phyllosilicates, which consist of layers of silicate
tetrahedra and aluminium octahedra, have potential but consist of
many individual stacked plates. It is possible to pillar these platelets
using species such as the polycation [Al13O4 (OH)24]7+, which is about
1 nm in size, and other materials. These bricks open the platelets and
make large pores (Figure 3.8) and the pillars can be converted to oxide
by thermal treatment. However they are not very thermally stable at
high (500˚C) temperatures often needed for catalytic reactions. Other
complications can arise because the number of pillars per platelet can
differ and it is possible to make the pillars longer or shorter [15].

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Figure 3.8
The formation of nanostructured phyllosilicates. Cour tesy of Professor Max Lu,
University of Queensland, Australia

Na-CLAY PILLARING
SOLUTION

EXCHANGE
REACTION

OH H2O O

INTERCALATED CLAY

CALCINATION

PILLARED CLAY

There have been some interesting new developments in altering

pore spaces [16]. In a novel approach, quaternary ammonium salts
(surfactants) which form micelles are used as centres around which sil-
ica species condense. These templates are removed by heating to cre-
ate a continuous network of pores that mimic the size and shape of the
template. The advantage of this approach is that the pore volume is
controlled by the volume fraction of the template constituents, and the
pore size is controlled by the size of the surfactant micelles. This
approach has been used with pillared clays [16]. Interestingly, the
porosity of the products depends on the quantity rather than the size
of the surface of the surfactant molecules. These materials have been
called composite clay nanostructures [16]. The quaternary ammonium

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78 • N A N OT E C H N O L O G Y

salts form micelles in the interlayer regions and the pillaring agents
form pillar materials beside them because of the affinity of surfactant
molecules for the surface of the pillar precursors. The micelles act as
templates, preventing the intercalated framework from collapsing dur-
ing the dehydration process in which the framework hardens. The sur-
factants can be removed at temperatures between 150 and 250˚C
leaving a highly porous product. One interesting application is to fill
these new pores with organic materials, thereby forming nanosilicocar-
boalumina composites.
Different surfactants can be used. For example, a series of com-
pounds with (CH2CH2O)n with different values of n can be added to
assist in understanding the mechanism. It appears that the size of the
molecule is important, but in the reverse of what would naïvely be
expected, it is found that larger surfactant molecules produce smaller
pores. A surfactant with large n is expected to have a much stronger
interaction with the precursor surface compared to a surfactant with
small n. The strong interaction must influence the formation and con-
figuration of the micelles. The mean diameter of the framework pores
decreases with n because the stronger interaction results in micelles
with a smaller diameter.

3.9 APPLIC ATIONS OF NANOMATERIALS

The uses of materials are determined by their mechanical and chemical
properties. Young’s modulus, which describes elasticity, hardness, ease
of fracture, and conductivity, are all important properties. These stud-
ies are supported by an understanding of the chemical properties of the
material, such as elemental analysis and molecular or atomic structure.
Using the tools described in Chapter 2 it is now possible to describe
these properties by actually looking at the molecules. Figure 3.9 shows
TEM of a Si3N4 based ceramic material. Each atom can be seen in
rows. The different material in the middle is the early stages of a phase
transformation to a different arrangement of atoms, known as a
nanoscaled nucleation. These structures and dislocations determine the
strength of materials, their possible applications and their macroscopic
properties. Corrosion, chemical modification and other influences can
all be studied the same way.
It is fairly easy to understand why nanomaterials are more flexible.
Each of the nanocrystallites, (particles) can move past each other so
that stretching is easy. However, nanosize particles can also enhance
hardness. Crystallites can pack together along boundaries in macro-
crystallites and prevent the structure from unzipping. Super strength
materials can be produced using nanocomposites with, say, a nanocrys-
talline particle embedded in a non-crystalline matrix. For example, a
hardness in excess of 60 Gigapascals (GPa) has been reported for
nanocrystals of titanium nitride embedded in thin films of silicon

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Figure 3.9
TEM of a Si 3N 4 based ceramic material. The different material in the middle is the
beginnings of a phase transformation — a nanoscaled nucleation. Cour tesy of
Dr John Drennan, University of Queensland, Australia.

Phase
transition

Rows of atoms

nitride (we measure hardness by the pressure required to indent the

material). Superhardness is classed as > 40 GPa; and in some nanocom-
posite systems, measurements of > 80 GPa or ultra hardness, have been
reported. These materials are therefore almost as hard as diamond
(hardness > 100 GPa).
Future applications are discussed in more detail in Chapter 9 and
some special optical uses are described in Chapter 7. Current applica-
tions include, but are not limited to, the following:

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INSULATION MATERIALS
Nanocrystalline materials synthesised by the sol-gel technique result in
aerogels (Chapter 3.5). Since they are porous and air is trapped at the
interstices, aerogels are currently being used for insulation in offices,
homes, and so on. By using aerogels for insulation, heating and cool-
ing bills are drastically reduced, thereby saving power and reducing the
attendant environmental pollution. They are also being used as mate-
rials for ‘smart’ windows (Chapter 7), which darken when the sun is
too bright and lighten when the sun is not shining brightly.
MACHINE TOOLS
Some nanomaterials are harder than conventional materials. Cutting
tools and drills made of nanocrystalline materials, such as tungsten car-
bide, tantalum carbide, and titanium carbide, are much harder, much
more wear-resistant, erosion-resistant, and last longer than their con-
ventional (large-grained) counterparts. They also enable the manufac-
turer to machine various materials much faster, thereby increasing
productivity and significantly reducing manufacturing costs.
Nanocrystalline silicon nitride (Si3N4) (Figure 3.9) and silicon carbide
(SiC), have been used in automotive applications as high-strength
springs, ball bearings, and valve lifters, because they are readily
machineable and have excellent physical, chemical, and mechanical
properties. They are also used as components in high temperature
furnaces.
On the other hand, some nanomaterials are softer than conven-
tional materials. Conventional ceramics are very hard, brittle, and dif-
ficult to machine. Zirconia, ZrO2, a hard, brittle ceramic, has even
been rendered superplastic by nanocrystalline grains. It can be
deformed to great lengths (up to 300% of its original length).
Nanocrystalline ceramics can be pressed and sintered into various
shapes at significantly lower temperatures, whereas it would be very
difficult, if not impossible, to press and sinter conventional ceramics
even at high temperatures.
PHOSPHORS
The resolution of a television or a monitor depends greatly on the size
of the pixel. These pixels are essentially made of materials called phos-
phors, which glow when struck by a stream of electrons inside the cath-
ode ray tube (CRT). The resolution improves when the pixels, or the
phosphors, are smaller. Nanocrystalline zinc selenide, zinc sulfide, cad-
mium sulfide, and lead telluride synthesised by the sol-gel technique
improve the resolution of monitors. The use of nanophosphors would
reduce the cost of making high resolution televisions. Carbon nan-
otubes (Chapter 4) are also candidates. Similar arguments apply to low
cost flat panel displays.

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BATTERIES
Nanocrystalline materials synthesised by sol-gel techniques are used as
separator plates in new generation batteries because of their aerogel
structure, which can hold considerably more energy than convention-
al plates. Nickel metal hydride (Ni-MH) batteries made of nanocrys-
talline nickel and metal hydrides require far less frequent recharging
and last much longer.
HIGH POWER MAGNETS
The strength of a magnet increases with increased surface area per unit
volume. It has been shown that magnets made of nanocrystalline yttri-
um-samarium-cobalt nanoparticles possess very unusual magnetic
properties due to their extremely large surface area. Typical applica-
tions for these high power rare-earth magnets include quieter sub-
marines, automobile alternators, land-based power generators, motors
for ships, ultra-sensitive analytical instruments, and magnetic resonance
imaging (MRI) in medical diagnostics.
MOTOR VEHICLES AND AIRCRAFT
Motor cars waste significant amounts when thermal energy generated
by the engine is lost. This is especially true in the case of diesel engines.
To prevent this waste, the engine cylinders (liners) are currently coat-
ed with nanocrystalline ceramics, such as zirconia and alumina, so that
they retain heat much more efficiently and result in complete and effi-
cient combustion of the fuel.
In aircraft, fatigue strength is critical. The fatigue strength increas-
es with a reduction in the grain size of the material. Nanomaterials pro-
vide such a significant reduction in the grain size over conventional
materials that the fatigue life is increased by as much as 300 per cent.
Furthermore, components made of nanomaterials are stronger and can
operate at higher temperatures. This means that aircraft can fly faster
and more efficiently using the same amount of aviation fuel. In space-
craft, elevated-temperature strength is crucial for components such as
rocket engines and thrusters, and particularly for surface material that
will be in contact with the atmosphere on re-entry. Likewise, the
amount of fuel that can be carried on board is crucial so the ratio of
fuel to total weight is important. Nanomaterials, such as nanocrys-
talline tungsten-titanium diboride-copper composites, are potential
candidates for increasing combustion efficiencies and hence reducing
fuel use in these applications.
MEDICAL IMPLANTS
For an implant to effectively mimic a natural human bone, the sur-
rounding tissue must penetrate the implants to give the implant the
strength it needs. Since conventional materials are relatively impervious,

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82 • N A N OT E C H N O L O G Y

human tissue does not penetrate the implants, and they are not as effec-
tive. Furthermore, these metal alloys wear out quickly, necessitating fre-
quent, and often very expensive, surgery. However, nanocrystalline
zirconia ceramic is hard, wear-resistant, corrosion-resistant (biological
fluids are corrosive), and biocompatible. Nanoceramic aerogels can also
withstand up to 100 times their weight. The products last longer and
the patient needs less frequent implant replacements. This leads to a sig-
nificant reduction in surgical expenses. Nanoceramics can also be made
of apatite, a calcium phosphate material from which bone is derived,
thereby mimicking nature’s own process [17, 18]. The sol-gel prepared
nanotitania (TiO2) forms a chemical bond with the living bone in the
body, although the bond is not very strong. However, impregnating the
titania gel with hydroxyapatite is a promising way to increase its bioac-
tivity. Nanocrystalline silicon carbide (SiC) is a candidate material for
artificial heart valves primarily due to its low weight, high strength,
extreme hardness, wear resistance, inertness (SiC does not react with
biological fluids), and corrosion resistance.
OTHER MEDICAL USES
Gel technology has also been used in DNA separations. There has been
a quest for an artificial gel that would replace the organic gels used to
separate fragments of DNA for analysis. Traditionally this has been
done by a process called gel electrophoresis. Enzymes are used to chop
DNA strands into many short pieces of varying length. The sample is
placed at one end of a column of organic gel and an electric field is
applied to force the DNA to move through the gel. As they slowly pass
through the tiny pores of the material, DNA fragments of different
lengths move at different speeds and eventually collect in a series of
bands as a ladder-like structure that can be photographed using fluo-
rescent or radioactive tags. The resulting image is a list of the lengths
of the fragments, from which genetic information can be determined.
Silicon-based nanostructures with pores comparable to the size of a
large DNA molecule can also perform these separations. These meth-
ods could also be applied to the study of other large organic molecules,
including proteins, carbohydrates and lipids, for many of which elec-
trophoresis is useless.
As noted, nanoparticles of iron can be used to form strong mag-
nets. However, the size of the particle can be put to good use medically
in other ways. Nanoparticles of the iron oxide Fe3O4 have diameters in
the 5–100 nm range. These particles are magnetic and thus can be fol-
lowed by a magnet in the body using nuclear magnetic resonance
imaging (this is known as magnetic resonance imaging (MRI) so that
the use of the word ‘nuclear’ does not scare the patient). In MRI, pro-
tons are excited with short pulses of radio-frequency radiation. The
free induction decay as the protons relax is measured and deconvoluted

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by means of a mathematical process called a Fourier transform, which

provides an image of the tissue that corresponds to proton density.
Areas of high proton density, usually in the form of water or lipid mol-
ecules, have a strong signal and appear bright. Areas of bone or ten-
don, which have a low proton density because of the lack of water and
lipids, have a weak signal and appear dark.
Traditionally, a major limitation of MRI has been its inability to dis-
tinguish differences in soft tissue types (such as healthy parts of the
liver from diseased regions), as the relative proton densities can be very
similar. Other regions, such as the bowel, are hard to image because air
pockets and faecal matter make the proton density inconsistent.
Various contrast agents have been developed to circumvent these imag-
ing problems.
Contrast agents work by changing the strength of the MRI signal
at a desired location. For example, iron oxide contrast agents change
the rate at which protons decay from their excited state to the ground
state, allowing more effective decay through energy transfer to a neigh-
bouring nucleus. As a result, regions containing the superparamagnet-
ic contrast agent appear darker in MRI than regions without the agent.
For instance, when iron oxide nanoparticles are delivered to the liver,
healthy liver cells can take up the particles, but diseased cells cannot.
Consequently, the healthy regions are darkened, while the diseased
regions remain bright.
These iron oxide particles have many advantages over other con-
trast agents. Unlike agents like perfluorochemicals, oils, and fats, they
are miscible with aqueous systems, which means they can mix with
material in the bowel and be used in small volumes. (Immiscible agents
must be used in sufficient quantity to displace intestinal matter). This
miscibility also allows them to be used intravenously. Compared with
other magnetic contrast agents they are much more potent.
Nanoparticles are commonly used for laboratory studies as well as
in vivo. Tagged to a biomaterial of interest they can be dispersed effec-
tively, coated with a monoclonal antibody for a cell-surface antigen.
The antibody-tagged particles are then incubated with a solution con-
taining the cells of interest. The microparticles bind to the surfaces of
the desired cells, and these cells can then be collected in a magnetic
field. Methods of this type have been used to isolate or remove numer-
ous cell types, including lymphocytes (cells that control immune
response) and tumour cells.
Particles with truly nanoscopic dimensions have also been used in
the ‘First Response’ home pregnancy test, which uses conventional
micrometre-sized latex particles in conjunction with gold nanoparticles
(less than 50 nm diameter). Gold nanoparticles have a characteristic
visible absorption band called the plasmon resonance absorption,
which makes them pink (plasmons are described in Chapter 7). The

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84 • N A N OT E C H N O L O G Y

micro- and nanoparticles are derivates with antibodies to human chori-

onic gonadotrophin, a hormone released by pregnant women. When
mixed with a urine sample containing this hormone, the micro- and
nanoparticles coagulate and the resulting clumps are coloured pink.
Nanogold particles have been used extensively as specific staining
agents in biological electron microscopy (Chapter 2). The small sizes of
these particles allow them to be physically close to the structures that
they stain, providing high resolution. Because these nanoparticles are
gold, which has a high backscatter coefficient, they appear bright in a
scanning electron microscope image. In contrast, the high density of
gold makes them appear dark in a transmission electron microscope
image. Site-specific staining is obtained by labelling the nanogold par-
ticles with antibodies directed against a protein in the region of inter-
est. Antibody-labelled gold nanoparticles are commercially available,
and unlabelled gold nanoparticles can also be purchased and then
labelled with a specific antibody by the investigator.

YOU SHOULD NOW KNOW:

1 That a plasma is an ionised gas. A plasma is achieved by making a gas
conduct electricity by providing a potential difference across the two
electrodes so that the gas yields up its electrons and thus ionises. In a
vacuum or in an inert gas the electrodes can be made volatile. Heat is
produced and other material can be volatilised and ionised using this
heat. Plasma arcing has been important in forming carbon nanotubes.
2 Chemical vapour deposition is a method of making nanoparticulate
material from the gas phase. Material is heated to form gas and then
allowed to deposit as a solid on a surface, usually under vacuum.
There may be direct deposition or deposition by chemical reaction
to form a new product that differs from the material volatilised.
Chemical vapour deposition is particularly useful for making aligned
materials on surfaces
3 The sol-gel process, as the name implies, involves the evolution of
networks through the formation of a colloidal suspension (sol) and
gelation of the sol to form a network in a continuous liquid phase
(gel). The precursors for synthesising these colloids consist of ions of
a metal or metalloid element surrounded by various reactive ligands.
Sol-gel processes can preserve the voids in solution in the solid state
thereby producing nanoholes.
4 In nanoelectrodeposition, the aim is to place only a single layer or
more of coverage on a surface in a very controlled way.
Nanostructured films of platinum can be produced by electrodepo-
sition from liquid crystalline mixtures. Electrodeposition can be
used to fill holes to make dispersed nanomaterials.

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N A N O P O W D E R S A N D N A N O M AT E R I A L S • 85

5 In ball milling, small balls are allowed to rotate around a drum and
drop with gravity force on to a solid enclosed in the drum. Ball
milling breaks down the structure into nanocrystallites. Ball milling
is the preferred method of preparing nanometal oxides.
6 Nanoparticles can also be prepared by altering the pore spaces in
phyllosilicates by means of various surfactants and then filling them
if required.
7 Nanomaterials have found applications as insulators, batteries,
machine tools, phosphors and magnets. They are used in aircraft,
building structures and medicine.

3.10 EXERCISES
1 Web search the following words: nanometals, electrochromic windows,
imogolite, nanocomposites.
2 Select one reference in an area of interest, find it and read it.
3 Take a pack of cards and some carrots. Cut the carrots up and place
them as pillars between each of the cards to form a pillared clay struc-
ture. Try building a conventional house of cards. Why is this less stable
than a pillared clay structure?
4 Investigate the relationship between bulk and surface volume. Take a
carrot and cut it into a cylinder. Measure the volume as r2h where
h is the length of the pillar and r is its radius. Measure the surface cir-
cumference, 2rh. Then cut the carrot in half and do the same cal-
culation but add the two circumferences together. The volume is the
same of course. Plot circumference divided by volume versus number
of cuts. Extrapolate your data until you find the number of slices to
make the carrot only available in two-dimensional space. This exper-
iment demonstrates the potential value in increasing surface to bulk
space.
5 Find out more about zeolites or phyllosilicates, particularly kaolinite,
illite and montmorillonite.
6 Find a structure of imogolite showing bond linkages on the Web or in
a reference and see that one silicon oxygen is attached to one H and the
other three are attached to Al.
7 For an interesting article on nanotubes read Hulteen JC and Martin
CR (1997) A template-based method for the preparation of nanoma-
terials. J. Mater. Chem. 7: 1075–87.

3.11 REFERENCES
Most scientific journals in physical science do not use report titles of papers.
Therefore as the reader should now have been able to find articles the title for-
mat is dropped except obviously for books.

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1 Feynman RP (1960) Engineering and science. California Institute of

Technology, February edn.
2 Drexler K E (1990) Engines of Creation. Fourth Estate, London, 296 pp.
3 Pang LSK, Vassallo AM & Wilson MA (1992) Energy and Fuels 6:
176–79.
4 Cassell AM, Raymakers JA, Kong J & Dai H (1999) J. Phys. Chem. B 103:
6484–92.
5 Attard GS, Glyde JC & Göltner C (1995) Nature 378: 366–68.
6 Attard GS, Edgar M, Emsley JW & Göltner CG (1996) Materials
Research Society Symp. Proc. 425: 179–84.
7 Attard GS, Edgar M, Emsley JW & Göltner CG (1996) Materials
Research Society Symp. Proc. 425: 185–89.
8 Frisch HL, West JM, Göltner CG & Attard GS (1996) J. Polym. Sci. A,
Polym. Chem. 34: 1823–26.
9 Attard GS, Edgar M & Göltner CG (1998) Acta Materialia 46: 751–58.
10 Attard GS, Göltner CG, Corker JM, Henke S & Templer RH (1997)
Angewandte Chemie Intl. Edn. Engl. 36: 1315–17.
11 Attard GS, Bartlett PN, Coleman NRB, Elliott JM, Owen JR & Wang JH
(1997) Science 278: 838–40.
12 Chen Y, Fitzgerald J, Chadderton LT & Chaffron L (1999) Journal of
Metastable and Nanocrystalline Materials 2–6: 375–80.
13 Pierard N, Fonesca A, Konya Z, Willems I, Van Tenderloo G & Nagy JB
(2001) Chem. Phys. Letters 335: 1–8.
14 Chopra NG, Luyken RJ, Crespi VH, Cherrey K, Zettl A & Cohen ML
(1995) Science 269: 966–70.
15 Mitchell IV (1990) Pillared Layered Structures: Current Trends and
Applications. Elsevier Applied Science, 1990.
16 Zhu HY & Lu GQ (2001) Langmuir 17: 588–94.
17 Ben-Nissan B & Chai C (1995) Sol-gel derived bioactive hydroxyapatite
coatings. In R Kossowsky & N Kossovsky (eds) Advances in Materials
Science and Implant Orthopaedic Surgery. NATO ASI Series, Series E:
Applied Sciences, Kluwer Academic Publishers, 294: 265–75.
18 Ben-Nissan B, Chai C & Evans LA (1999) Crystallographic and spectro-
scopic characterisation and morphology of biogenic and synthetic apatites.
In Wise DL, Trantolo DJ, Altobelli DE, Yaszemski MY, Gresser JD &
Schwartz ER (eds) Encyclopedic Handbook of Biomaterials and
Bioengineering B: Applications, 5th edn. Marcel Dekker, New York:
191–221.

© 2002 by Michael Wilson, Kamali Kannangara, Geoff Smith, Michelle Simmons, and Burkhard Raguse