Unit –V

Nanomaterials
Contents: Properties of materials at reduced size: electrical, optical, mechanical and magnetic
properties –Surface to volume ratio at nano scale –Quantum confinement –preparation of
nanomaterials – Bottom-up-methods(sol-gel and CVD methods)-Top-down methods (Ball
milling)-Elementary ideas of carbon nanotubes –Applications.

Introduction
In 1959, Richard Feynman made a statement ‘there is plenty of room at the bottom’. Based
on his study he manipulated smaller units of matter. He prophesied that “we can arrange the
atoms the way we want, the very atoms, all the way down”. The term ‘nanotechnology’ was
coined by Norio Taniguchi at the University of Tokyo. Nano means 10-9. A nano metre is one
thousand millionth of a metre (i.e. 10-9 m).
Nanomaterials could be defined as those materials which have structured components with
size less than 100nm at least in one dimension. Any bulk material we take, its size can
express in 3-dimensions. Any planer material, its area can be expressed in 2-dimension. Any
linear material, its length can be expressed in 1-dimension.

Materials that are nano scale in 1-dimension or layers, such as thin films or surface coatings.
Materials that are nano scale in 2-dimensions include nanowires and nanotubes.
Materials that are nano scale in 3- dimensions are particles like precipitates, colloids and
quantum dots.
Properties of nano particles:
The properties of nano scale materials are very much different from those at a larger scale. Two
principal factors that cause that the properties to differ significantly are increased relative surface
area and quantum effects. These can enhance or change properties such as reactivity, strength and
electrical characteristics.
1. Increase in surface area to volume ratio
Nano materials have relatively larger surface area when compared to the volume of the bulk
material.

Consider a sphere of radius r Its surface area =4Πr2 Its volume = 4Πr3 /3

Thus when the radius of sphere decreases, its surface area to volume ratio increases.

Example :

For a cubic volume,

Surface area = 6x1m2 =6m2

When it is divided it 8 pieces

 Its surface area = 6x (1/2m) 2x8=12m2

When the same volume is divided into 27 pieces,

Its surface area = 6x (1/3m) 2x27=18m2

Therefore, when the given volume is divided into smaller pieces, the surface area increases.
Hence as particle size decreases, greater proportions of atoms are found at the surface compared
to those inside. Thus nano particles have much greater surface to volume ratio.

As growth and catalytic chemical reaction occur at surfaces, then given mass of material in
nano particulate form will be much more reactive than the same mass of bulk material. This
affects there strength or electrical properties.

2. Quantum confinement effects

When atoms are isolated, energy levels are discrete or discontinuous. When very large number of
atoms is closely packed to form a solid, the energy levels split and form bands. Nano materials
represent intermediate stage.
When dimensions of potential well and potential box are of the order of deBroglie wave length
of electrons or mean free path of electrons, then energy levels of electrons changes. This effect is
called Quantum confinement effect.
When the material is in sufficiently small size, organization of energy levels into which electrons
can climb of or fall changes. Specifically, the phenomenon results from electrons and holes being
squeezed into a dimension that approaches a critical quantum measurement called the exciton
Bohr radius. These can affect the optical, electrical and magnetic behaviour of materials.

Variations of properties of nano materials

The physical, electronic, magnetic and chemical properties of materials depend on size.
Small particles behave differently from those of individual atoms or bulk.
Physical Properties
Crystal structure of Nano particles is same as bulk structure with different lattice parameters.
The inter atomic spacing decreases with size and this is due to long range electrostatic forces
and the short range core-core repulsion. The Melting point of Nanoparticles decreases with
size.
Chemical Properties
The Electronic structure of Nanoparticles is dependent on its size and the ability of Nano cluster to
react, depends on cluster size. The large Surface area to volume ratio the variations in geometry and
the electronic structure of Nano particles have a strong effect on catalytic properties.

Electrical Properties
The electronic structure of Nano materials is different from its bulk material. The density of the
energy states in the conduction band changes when the energy spacing between two energy levels is
more than KBT , energy gap is created. Nano clusters of different sizes will have different electronic
structures and different energy level separations. The ionization potential at small sizes is higher
than that for the bulk and show marked fluctuations as function of size. Due to quantum
confinement the electronic bands in metals become narrower. The delocalized electronic
states are transformed to more localized molecular bands and these bands can be altered by
the passage of current through these materials or by the application of an electric field. In
nano ceramics and magnetic nano composites the electrical conductivity increases with
reduction in particle size where as in metals, electrical conductivity decreases.

Optical properties
Depending on the particle size, different colours are same. Gold nano spheres of 100nm appear
orange in colour while 50nm nano spheres appear green in colour. If semiconductor particles are
made small enough, quantum effects come into play, which limits the energies at which electrons
and holes can exist in the particles. As energy is related to wavelength or colour, the optical
properties of the particles can be finely tuned depending on its size. Thus particles can be made
to emit or absorb specific wavelength of light, merely by controlling their size.
An electro chromic device consist of materials in which an optical absorption band can be
introduced or existing band can be altered by the passage of current through the materials, or by
the application of an electric field. They are similar to liquid crystal displays (LCD) commonly
used in calculator and watches. The resolution, brightness and contrast of these devices depend
on tungstic acid gel’s grain size.

Magnetic properties:
The strength of a magnet is measured in terms of coercivity and saturation magnetization values.
These values increase with a decrease in the grain size and an increase in the specific surface
area (surface area per unit volume) of the grains. In small particle a large number or fraction of
the atoms reside at the surface. These atoms have lower coordination number than the interior
atoms. As the coordination number decreases, the moment increases towards the atomic value
there is small particles are more magnetic than the bulk material.
Nano particle of even non magnetic solids are found to be magnetic. It has been found
theoretically and experimentally that the magnetism special to small sizes and disappears in
clusters. At small sizes, the clusters become spontaneously magnetic.
Synthesis of nanomaterials:
Nanomaterials deal with very fine structures: a nanometer is a billionth of a meter. This indeed
allows us to think in both the ‘bottom up’ or the ‘top down’ approaches to synthesize
nanomaterials, i.e. either to assemble atoms together or to dis-assemble (break,or dissociate) bulk
solids into finer pieces until they are constituted of only a few atoms.This domain is a pure
example of interdisciplinary work encompassing physics,chemistry, and engineering upto
medicine.
Top-Down approach (Ball milling)

Mechanical attrition is a typical example of ‘top down’ method of synthesis of nanomaterials,

where the material is prepared not by cluster assembly but by the structural decomposition of
coarser-grained structures as the result of severe plastic deformation. This has become a popular
method to make nanocrystalline materials because of its simplicity, the relatively inexpensive
equipment needed, and the applicability to essentially the synthesis of all classes of materials.
The major advantage often quoted is the possibility for easily scaling up to tonnage quantities of
material for various applications. Similarly, the serious problems that are usually cited are;
1. Contamination from milling media and/or atmosphere, and
2. To consolidate the powder product without coarsening the nanocrystalline microstructure.
In fact, the contamination problem is often given as a reason to dismiss the method, at least for
some materials. Here we will review the mechanisms presently believed responsible for
formation of nanocrystalline structures by mechanical attrition of single phase powders,
mechanical alloying of dissimilar powders, and mechanical crystallization of amorphous
materials. The two important problems of contamination and powder consolidation will be
briefly considered. Mechanical milling is typically achieved using high energy shaker, planetary
ball, or tumbler mills. The energy transferred to the powder from refractory or steel balls depends
on the rotational (vibrational) speed, size and number of the balls, ratio of the ball to Milling in
cryogenic liquids can greatly increase the brittleness of the powders influencing the fracture
process. As with any process that produces fine particles, an adequate step to prevent oxidation is
necessary. Hence this process is very restrictive for the production of non-oxide materials since
then it requires that the milling take place in an inert atmosphere and that the powder particles be
handled in an appropriate vacuum system or glove box. This method of synthesis is suitable for
producing amorphous or nanocrystalline alloy particles, elemental or compound powders. If the
mechanical milling imparts sufficient energy to the constituent powders a homogeneous alloy
can be formed. Based on the energy of the milling process and thermodynamic properties of the
constituents the alloy can be rendered amorphous by this processing.
Bottup-Up Approach
Sol-Gel method
The sol-gel process, involves the evolution of inorganic 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 synthesizing these colloids consist usually of a metal or metalloid
element surrounded by various reactive ligands. The starting material is processed to form a
dispersible oxide and forms a sol in contact with water or dilute acid. Removal of the liquid from
the sol yields the gel, and the sol/gel transition controls the particle size and shape. Calcination of
the gel produces the oxide.
Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is widely
employed to prepare oxide materials. The sol-gel process can be characterized by a series of
distinct steps.
1. Formation of different stable solutions of the alkoxide or solvated metal precursor.
2. Gelation resulting from the formation of an oxide- or alcohol- bridged network(the gel) by a
polycondensation reaction that results in a dramatic increase in theviscocity of the solution.
3. Aging of the gel during which the polycondensation reactions continue until the gel transforms
into a solid mass, accompanied by contraction of the gel network and expulsion of solvent from
gel pores. Ostwald ripening (also referred to as coarsening, is the phenomenon by which smaller
particles are consumed by larger particles during the growth process) and phase
transformations may occur concurrently with synthesis. The aging process of gels can exceed 7
days and is critical to the prevention of cracks in gels that have been cast.
4. Drying of the gel, when water and other volatile liquids are removed from the gel network.
This process is complicated due to fundamental changes in the structure of the gel. The drying
process has itself been broken into four distinct steps:
(i)the constant rate period,
(ii) the critical point,
(iii) the falling rate period,
(iv) the second falling rate period. If isolated by thermal evaporation, the resulting monolith is
termed a xerogel. If the solvent (such as water) is extracted under supercritical or near super
critical conditions, the product is an aerogel.
5. Dehydration, during which surface- bound M-OH groups are removed, there by stabilizing the
gel against rehydration. This is normally achieved by calcining the monolith at temperatures up
to 8000C.
6. Densification and decomposition of the gels at high temperatures (T>800 0C). The pores of the
gel network are collapsed, and remaining organic species are volatilized. The typical steps that
are involved in sol-gel processing are shown in the schematic diagram below.

CHEMICAL VAPOUR DEPOSITION

In this method, nanoparticles are deposited from the gas phase. Material is heated to from a gas
and then allowed to deposit on solid surface, usually under vacuum condition. The deposition
may be either physical or chemical. In deposition by chemical reaction new product is formed.
Nanopowder or oxides and carbides of metals can be formed, if vapors of carbon or oxygen are
present with the metal. Production of pure metal powders is also possible using this method. The
metal is meted exciting with microwave frequency and vaporized to produce plasma at 15000c .

Schematic for CVD process

This plasma then enters the reaction column cooled by water where nanosized particles are
formed. CVD can also be used to grow surfaces. If the object to be coated is introduced inside
the chemical vapor, the atoms/molecules coated may react with the substrate atoms/molecules.

The way the atoms /molecules grow on the surface of the substrate depends on the alignment of
the atoms /molecules of the substrate. Surfaces with unique characteristics can be grown with
these techniques. The advantages of this method are

 An excellent control of size, shape, crystallinity and chemical composition

 Highly pure materials can be obtained
 Multi-component systems are relatively easy to form
 Easy control of the reaction mechanisms

Carbon Nanotubes
Carbon nanotubes (CNTs) are molecular-scale tubes of graphitic carbon having outstanding
properties. They are among the stiffest and strongest fibres known, and have remarkable
electronic properties. They also have many other unique characteristics. They belong to the
fullerence structural family.
CNTs are allotropes of carbon with a nanostructure that can have length-to-diameter ratio of upto
28,000,000 :1, which is significantly larger than any other material. These cylindrical carbon
molecular tubes have novel properties that make them potentially useful in many applications in
nanotechnology, electronics, optics, and other fields of materials science. These materials also
have potential applications in architectural fields.
Structure
The bonding in CNT is sp2 , with each atom joined to three neighbours, as in graphite. The tubes
can , therefore, be considered as rolled-up graphene sheets (grapheme is an individual graphite
layer). There are three distinct ways in which a grapheme sheet can be rolled into a tube. These
are shown schematically in the figure.

Types of CNTs.(a)Armchair(axis of CNT is parallel to C-C bonds of

graphene) (b) zig-zag (axis of CNT is perpendicular to C-C bonds of
graphene(c) Chiral (axis of CNT is inclined to C-C bonds of graphene)
Electrical conductivity of a CNT depends on its specific structure. Based on the number of layers
constituting them, CNTs can be classified as single walled or multiwalled. These two are shown
in figure below. A single-walled nanotube can be obtained by wrapping one atomic layer of
grapheme into a seamless cylinder. A multiwalled CNT, on the other hand, has more than one
surface within it.
 (a)Single walled CNT (b) Multiwalled CNT

Fabrication
Techniques have been developed to produce nanotubes in sizeable quantities. Some common
techniques include are
1.electric arc discharge
2. Laser ablation
3.Chemical vapor deposition (CVD)
Most of these processes take place in vacuum or with process gases. CVD growth of CNTs can
occur in vacuum or at atmospheric pressure. Large quantities of nanotubes can be synthesized by
these methods. Advances in catalysis and continous growth processes are making CNTs more
commercially viable by the day.
Properties of CNTs
Some of the properties of CNTs are as follows.
Strength
Strength of a CNTs can be expressed through the following features.
1. CNTs are one of the strongest and stiffest materials known, in terms of tensile strength
and elastic modulus, respectively. This strength results from the covalent sp2 bonds
formed between individual carbon atoms
2. The young’s modulus is the range of 1-5TPa for Singlewalled and tensile strength is
about 150GPa for multiwalled CNTs. These values are much greater than those for the
best-known materials, being comparable to high-carbon steel.
3. They can recover vrom severe structural distortions due to their ability to rehybridize
Electrical properties
1. CNTs can be either metallic or semiconducting, depending upon the structure. For
example, the arm chair form is metallic, whereas the zigzag form is found to be
semiconducting.
2. The energy gap of semiconducting CNT is inversely proportional to the diameter of the
tube. The energy band gap can also be affected by localized defects.
Thermal properties
1. CNTs are very good thermal conductors along the length of the tubes. The thermal
conductivity of a CNT is found to increase with its length.
2. It is predicted that CNTs will be able to achieve conductivities up to 20 times more than
that of copper, a metal well known for its conductivity.
3. The temperature stability of CNTs is estimated to be up to 2800 0C in vacuum and about
7500C in air.
Chemical properties
1. CNTs are resistant to chemical reactions.
2. They can be used as catalysts in chemical reactions due to their high surface area.
Applications
CNTs have wide-ranging applications. The strength and flexibility of CNTs make them
potentially useful in controlling other nanoscale structures. This suggests an important role for
CNTs in nanotechnology engineering. The different fields of applications of CNTs are
1.Structural – products ranging from clothes and sports gear to combat jackets and space
elevators.
2. Electrical circuits
3. fibres and fabrics
4.CNT composite
5. Drug delivery
6. computer applications.
7. Novel hard disk
8. CNT gas sensor