Nano-powders and

Nano-materials

In this chapter you will find out about different types of

nanomaterials and how they are formed, what methods are used
for different materials and how the new materials can be used.

III.1. Introduction
All materials are composed of grains, which in turn comprise many
atoms. These grains can be visible or invisible to the 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.

CeO2 ZnO

Nanocrystals of cerium oxide (CeO2) and zinc oxide (ZnO).

Interest in nanomaterials defined the new age of nanotechnology. In

typical nanomaterials, the majority of the atoms are located on the
surface of the particles, whereas they are located in the bulk of
conventional 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 ultimate
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.

Example: 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.

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 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-resistant, erosion-resistant and corrosion-
resistant, but this resistance is usually imparted by some sort of
protection mechanism.

III.2. Preparation

There are six widely known methods to produce nanomaterials. These

are plasma arcing, chemical vapour deposition, electrodeposition,
solgel 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 manner 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 nanoparticles can reform into new materials, which
involve breaking the original crystallite bonds.

III.3. Plasma Arcing

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.
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 potential difference.

A plasma rotating electrode system

Schematic diagram of set-up conventional

(a) and new (b) arc discharge electrodes

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 Example: 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 electrodes
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
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
nanomaterial 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.

III.4. Chemical Vapour Deposition

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 deposition 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.

Plasma Enhanced CVD and Thermal CVD systems

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
structures grow vertically.
Ex: Growth of vertically aligned CNTs, the properties of the surface will
be different in the z axis than the x, y plane. This gives the surface
unique characteristics.

Model (a) and real

structure of aligned
carbon nanotubes (b)

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 CVD is particularly useful when nanosites have first been engineered
on a surface and the material is subsequently placed on the sites. This
is normally done by electron lithography or etching. CVD can be used to
build structures on these surfaces, so there is structure in both the
micro- and the nano- domain;
Dip pen nanolithography (DPN) can be used to write on the surface.
The advantage of CVD over DPN is that it can build nanostructures
rapidly by self assembly. The disadvantage is that the molecules cannot
be directed. In DPN, the molecules can be precisely placed.

Diagram to illustrate methodology for forming nanopillars by CVD (a)

and example of carbon forest (b)

III.5. Sol-Gel
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
reactive species, which are called ligands.

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.
SnO2 sol with pH = 10,5

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 Example:

Metal alkoxides and alkoxysilanes are most popular because they

react readily with water. The most widely 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 facilitated by the presence
of this homogenising agent.

SILICA GELS
The formation of SiO2 gels can be discussed above. It also depends on
some factors, such as:
• 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 catalyst, H2O/Si
molar ratio [H2O/Si], and temperature have been identified as most important.
By controlling these factors, it is possible to vary the structure and properties of
the sol-gel-derived inorganic network 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 spherical nanoparticles are
produced.

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HYDROLYSIS
In hydrolysis the reaction occurs through the addition of water, which
results in the replacement of alkoxide groups (OR) with hydroxyl
groups (OH). Under most conditions, condensation commences before
hydrolysis is complete. However, conditions such as pH, H2O/Si molar
ratio, and catalyst can force completion of hydrolysis before
condensation begins.

H2O + ROSi(OR)3 ------> R OH + HOSi(OR)3

where R = alkyl groups of various types.

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).

Although hydrolysis can occur without the addition of external

catalysts, 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 (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
protonated in a rapid first step. Electron density is withdrawn from the
silicon 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.

CONDENSATION AND POLYMERISATION OF MONOMERS

TO FORM PARTICLES
Polymerisation to form siloxane bonds occurs by either an alcohol-
producing or a water-producing condensation reaction. The monomer
HOSi (OR)3 reacts:

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

condensation mechanism involves a protonated silanol species.
Silica solubility is also important when the pH is changed. In
polymerisations 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
exceeding 2 nm in diameter.

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Between pH 2-6, condensation preferentially occurs between more
highly condensed species and those less highly condensed. 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 2-6
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 number as
highly soluble small particles dissolve and re-precipitate on larger, 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.

FORMING NANOSTRUCTURED SURFACES USING

THE SOL-GEL PROCESS

From gel stage, the spheres can be collected 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 networks 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.

SUMMARY OF SOL-GEL PROCESS

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III.6. Electrodeposition
Electrodeposition 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.

Metal plastic nanocomposites for selective

ion separations

Ví dụ:

Tính cường độ dòng điện để điện hóa tạo lớp Cu, khối lượng 5g,
lên đế kim loại trong 1h. Biết hằng số Farađây F = 96.485 C.
Có lượng điện tích đi qua dung dịch (Culông) = I (amp) x t (sec)
Biết 1 mole electrons = 96.485 C
Số mole k/l Cu sẽ tạo trên đế phẳng là 5(g) / 63,546 (at.num.)
=0,07868 mole
Phản ứng tạo Cu: Cu2+ + 2 e -----> Cu
Do đó số mole electrons: 2 x 0,07868
Lượng điện tích đi qua = 2 x 0,07868 x F = 1,52 . 104 (C);
Cường độ dòng điện trong 1h (3600 sec): 1,52.104 / 3600 = 4,2 A

III.7. Ball Milling

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. It is useful for
preparing other types of
nanotubes, such as boron nitride
nanotubes and a wide range of
elemental and oxide powders.

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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.
Ex: In the production of nanocrystalline Zirconia (ZrO2) zirconium
chloride is treated with magnesium oxide during milling to form
zirconia and magnesium chloride:

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
developed to ensure that each crystal receives the same energy, rather
than relying on ‘cook and look’ processes.

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III.8. Using natural nanoparticles

The formation of nanostructured

phyllosilicates. Phyllosilicates, which
consist of layers of silicate tetrahedra and
aluminium octahedra, have potential but
consist of many individual stacked plates.

Nanoparticles can also be prepared

by altering the pore spaces in
phyllosilicates by means of various
surfactants and then filling them if
required.

III.9. Applications of nanomaterials

1. Machine tools: Some nanomaterials are harder than conventional
materials. Cutting tools and drills made of nanocrystalline materials,
such as tungsten carbide, tantalum carbide, and titanium carbide, are
much harder, much more wear-resistant, erosion-resistant, and last
longer than their conventional (large-grained) counterparts. They also
enable the manufacturer to machine various materials much faster,
thereby increasing productivity and significantly reducing manufacturing
costs.
On the other hand, some nanomaterials are softer than
conventional materials. Conventional ceramics are very hard, brittle,
and difficult to machine. 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.

Applications of nanomaterials (continue)

2. Insulation materials: Nanocrystalline materials synthesised by

the sol-gel technique result in aerogels. 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 cooling bills are drastically reduced, thereby
saving power and reducing the attendant environmental pollution;
3. Phosphors: Nanocrystalline ZnSe, ZnS, CdS, PbTe synthesised
by the sol-gel technique improve the resolution of monitors. The use
of nanophosphors would reduce the cost of making high resolution
televisions;
4. Batteries: Nanocrystalline materials synthesised by sol-gel
techniques are used as separator plates, which can hold
considerably more energy than conventional plates. Nickel metal
hydride (Ni-MH) batteries made of nanocrystalline Ni and MH
require far less frequent recharging and much longer;

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Applications of nanomaterials (continue)

5. High power magnets: It has been shown that magnets made of

nanocrystalline yttrium- samarium-cobalt nanoparticles possess very
unusual magnetic properties due to their extremely large surface
area. Typical applications for these high power rare-earth magnets
include automobile alternators, power generators, motors for ships,
ultra-sensitive analytical instruments, and magnetic resonance
imaging (MRI) in medical diagnostics;
6. Motor vehicles and aircraft: Motor cars waste significant
amounts when thermal energy generated by the engine is lost. To
prevent this waste, the engine cylinders are coated with
nanocrystalline ceramics, such as zirconia and alumina, so that they
retain heat much more efficiently and result in complete and efficient
combustion of the fuel.
7. Medical uses: Some nanoparticles are used: gold, iron oxide, SiC,
TiO2... to make antibody-label, to form strong magnets or DNA
separation...

WHAT YOU SHOULD KNOW IN THE CHAPTER

- A plasma (ionised gas) 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;
- 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;
- The sol-gel process 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;

YOU SHOULD KNOW (continue)

- 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 can be produced by electrodeposition
from liquid crystalline mixtures. Electrodeposition can be used
to fill holes to make dispersed nanomaterials;
- 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;
- Nanoparticles can also be prepared by altering the pore spaces
in phyllosilicates by means of various surfactants and then
filling them if required;
- Nanomaterials have found applications as insulators, batteries,
machine tools, phosphors and magnets. They are used in
aircraft, building structures and medicine.

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