B.E.

FIRST YEAR (SECOND SEM)

O p t i c a l F i b e r & N a n o s c i e n c e |Unit-4

Nanoscience
Introduction
Nanotechnology is an advanced technology, which deals with the synthesis
of nano particles, processing of nano materials and their applications. "Nano"
in Greek means dwarf. One nanometer is equal to one-billionth (1nm = 10 -9m)
of a meter. Nano-materials are 5,000 to 50,000 times smaller than the
diameter of a human hair. The Nano scale involves the range from
approximately 100 nm to 1 nm.
The application of Nanotechnology has opened new avenues of research in the
world of science and engineering in almost every field, from medicine to
fabrics. Nanotechnology is basically the technology involved in the designing
and manufacturing of engineering and functional systems at the sub-atomic
or sub-molecular level. Nano science is a. product of nanotechnology. As the
word indicates, Nanoscience is the branch of science dealing with the issues of
Nanotechnology. Nanoscience can be defined as the field of science that
deals with atoms, molecules and other objects which; vary in terms of
nanometers.
The nano structured materials may be metals, alloys, ceramics, or biological
materials. Generally the nano structured materials exhibits greatly altered
properties (like physical, chemical, and mechanical) when compared with their
normal bulk materials having same chemical compositions. The surface area
effects, quantum effects dominate the optical, electrical and magnetic
properties dramatically. For ex. the nano gold particles exhibit 100

'*

coefficient of absorption of light, while the bulk gold particles glittering effect
is only due to their reflection properties. Metals with grain size of 10 nm are
as much as seven times harder and tougher than their ordinary counterparts
with grain size of 100 nm.

Ms. Swati Thakre, (Lecturer| GNIEM)

B.E.FIRST YEAR (SECOND SEM)

O p t i c a l F i b e r & N a n o s c i e n c e |Unit-4
8.2 | Engineering Physics
8.1 Classification of nano materials
The classifications of nano structured materials are based on the cry stall in grain
size and shape. The different forms of nano materials are zero, one, two and
three dimensions.
I)

Zero dimensions: nano scale in three dimensions: for ex. nano particles,

precipitates,
colloids , quantum dots, fullerenes, dendrimers etc.
Nano particles are often define as particles of less than 100 nm diameter that
exhibit new size dependent properties compared to larger size particles of the
same material. They can also be arranged in layers on surfaces. The nano particles
of semiconductor are known as quantum dots.
Fullerenes : A fullerene is a molecule composed entirely of carbon, in the form of
a hollow sphere, ellipsoid or tube. Spherical fullerene are also called buckyballs,
and cylindrical one are called carbon nano tubes or bucky tubes. Fullerene are
similar in structure to graphite, but they may contain pentagonal rings. The first
fullerene discovered was buckminster fullerene Ceo.
Dendrimers: They are spherical polymeric molecule, formed through a nano scale
self assembly process.
II)

One dimensions -

nano scale in one dimension

: such as thin films

or surface
coating.They are used in silicon integrated circuit industry as many devices rely
on thin
films for their operation.

II ) Two dimensions - nano scale in two dimensions :

nano wires and nano

tubes, biopolymers etc.

Nanowires : When two lengths of three dimensional nanostructure is of nano
dimension then the structure is known as nano wire. Nanowires are ultrafine wires
or linear arrays of semiconductor, formed by self assembly. Semiconductor nano
wires (made up fo Silicon, gallium nitride and indium phosphide ) have remarkable
optical, electronic and magnetic properties).

B.E.FIRST YEAR (SECOND SEM)

O p t i c a l F i b e r & N a n o s c i e n c e |Unit-4

B.E.FIRST YEAR (SECOND SEM)

O p t i c a l F i b e r & N a n o s c i e n c e |Unit-4

Carbon nano tubes are found in 1985. The molecule discovered was named as C^.
Its
composition was similar to the graphite atom which was already present but this
was

new composition because it has better properties than graphite. The famous
Japanese
researcher Sumio Lijima discovered carbon nanotubes were double layered tubes
having
diameter about 30 nm and were closed from both the ends. Biopolymers such as
DNA
molecule off er a link between

nanotechnology and biotechnology.

IV) Three dimensions- Equiaxed nanometer sized grains (bulk structure)

8.2 Reasons for the difference in material properties by applying

nano scale
j
Increased relative surface area of nano material and quantum effects can change
or enhance properties such as reactivity, strength, and electrical properties.
Surface Area: The nano particles have greater surface area per given volume
ratio compared with larger particles. It makes material more chemically reactive.
As growth and catalytic chemical reactions occur at surfaces, the given mass of
material in nano particle form will be much more reactive than the same mass of
larger particles. In some cases the materials that are inert in their larger form are
reactive when produced in their nanoscale form. This affects their strength or
electrical properties.
Nano materials have relatively larger surface area when compared to the same
volume
or mass) of the material produced in a larger form. Let us consider a sphere of
radius 'r'.
?
4 3
Its surface area = 4n r . Its volume = - n r
Therefore surface to volume ratio
- n r3
r

B.E.FIRST YEAR (SECOND SEM)

O p t i c a l F i b e r & N a n o s c i e n c e |Unit-4

Thus when radius of sphere decreases, its surface area to volume ratio increases.
Hence a greater proportion of atoms are found at the surface compared to those
inside . It makes

B.E.FIRST YEAR (SECOND SEM)

O p t i c a l F i b e r & N a n o s c i e n c e |Unit-4
8.4 I Engineering Physics
material more chemically reactive. As growth and catalytic reactions occur at
surfaces . the nanomaterial are more reactive than the same mass of material
made up of larger size particles.
Quantum effects:
When the atoms are isolated the energy levels are discrete. When very large
number of atoms are closely packed to form a solid, the energy levels splits and
bands are formed Nano materials represents intermediate stage. When the
dimension of potential well is of the order of de Broglie's wavelength (i.e. within
few tens of nanometer) energy levels of electron change. This effect is called
Quantum confinement. When the material is of sufficiently small size typically
of 10 nm or less, it affect the optical, electrical and magnetic behavior of
material.

8.3 Comparison of properties of nano material with bulk

Physical properties:
When we reduce the size of bulk material to nano particle size , the surface area
increases Hence surface to volume ratio increases . This changes the surface
pressure and results in a change in the inter particle spacing. The inter atomic
spacing decreases with size. The change in inter particle spacing and the
large surface to volume ratio in particles ha\ e combined effect on material
properties
Variations in the surface free energy

Size A

change the chemical potential. This

affects

the

melting

point

of

the

Meltin
g p<

material. For ex, the melting point of

Fig. 8.1

Au n decreases with size and at very

small

sizes

isfaster(Fig.8.1).

the

decrease
Melting point
(K)

Chemical properties
The large surface to volume ratio , the variation in geometry and structure have a strong
effect on catalytic properties. For ex: 1 ) The reactivity of small clusters has been found to
vary by orders of magnitude when the cluster size is changed only a few atoms. 2) It is
well known that most metals do not absorb hydrogen, and even among those that do ,
hydrogen is typically absorbed dissociatively on surfaces with a hydrogen to metal atom
ratio is of one. This limit is significantly enhanced in small sizes. It has been shown that
small positively charged clusters of Ni, Pd , Pt containing 2 to 60 atoms can absorb up to
eight hydrogen atom per metal atom. The number of absorbed atoms decreases with
increasing cluster size.This shows that small particles are useful in hydrogen storage
devices in metals.
Optical properties
Optical properties are among the most fascinating and useful properties of nano materials
and have been extensively studied using a variety of optical spectroscopic techniques.
If the semiconductor particles are made small enough, quantum effects come into play
irhich limits the energies at which electrons and holes can exist in the particles. As energy
IB

related to wavelength, the optical properties can be finely tuned with the size of

particles. Thus particular wavelength can be made to absorb or emit by controlling their
Wire. Gold nano spheres of 100 nm appears orange in colour while 50 nm nano spheres
!^>pear green in colour. The linear and nonlinear optical properties can be tailored by
nntrolling the size and dimensions of such particles.
[ An electronic device consists of materials in which an optical absorption band can be
[ troduced or existing band can altered by passage of current through the materials or
by
the application of electric field. They are similar to liquid crystal display (LCD). The
esolutions, brightness, contrast of these devices depends upon the tungstic acid gel's
wain size. Hence nanomaterials such as tungstic oxide gel are used .

8.6 I Engineering Physics Electrical Properties

The electrical properties depends upon the size. We know that the resistance
of material is due to scattering of conduction electrons with vibrating atoms
and impurities and hence a the mean free path or scattering length. When
the dimensions of solid are comparable to] mean free path the scattering
probability decreases and hence the electrical properties] changes. When
the size of solid is of the order of mean free path or de Broglie wavelength] of
electrons or holes which carry current, electronic structure of the system
changes] completely. The density of states of conduction electrons is
strongly affected when the dimensions of the material changes from bulk to
quantum dots.
In nanoceramics and magnetic nanocomposites the electrical conductivity
increases with reduction

in particle size whereas in metals conductivity

decreases.
Magnetic properties
Magnetic nanoparticle show a variety of unusual magnetic behavior when
compared withj the bulk material. This is mostly due to surface / interface
effects, including symmetry-breaking, charge transfer and magnetic
interactions. (For ex. ferromagnetism of buk materials disappeared and
transfers to super paramagnetism in the nanometer scale due to huge surface
energy.)
It has been observed

that as the

coordination number decreases , the

''
\

Fe

magnetic moment increases in case of

\
Bulk magnetic
\
V
Ni, Co and Fe(Fig.8.25). Thus small
moment (An) \
x^^
Ni ^^^^
^
particles are more magnetic than the
^^~^~~^^^~~~~~-~
bulk material. The magnetic moment
of cobalt having particle size 2nm
number
exhibited 20 % higher value than that

Coordination

Fig. 8.2 of bulk.

Manotechnology | 8.7
Nano-particles of even nonmagnetic solids are found to be magnetic.
It has been observed that magnetism is special to small sizes and
disappears in clusters containing more than 80 atoms . At small sizes
the clusters becomes spontaneously magnetic.
Mechanical properties :
Most metals are made up of small crystalline grains. If these grains are
nano scale in size , the interface area (grain boundary) within the
material greatly increases, which enhances the strength. For ex :
nanocrystalline nickel is as strong as hardened steel. Because of nano
size, many mechanical properties such as hardness, , elastic modulus,
fracture toughness, scratch resistance, fatigue strength and are
modified.
Reduction in grain size lowers the transition temperature in steel from
ductile to brittle. The nano phase material are also termed as super
plastic materials, since they exhibits all -common micro structural
features of super plastic materials, such as extensive tensile deformation
without cracking or fracture. In case of nano materials , the occurrence
of super plastic temperature is decreased due to decreases in grain size ,
which results in an increase in the strain rate.
8.4 Synthesis of nano materials
As the application of nano materials are diverse hence one has to select
the appropriate method for synthesis of nano materials to suit their
requirement. Therefore the nano particles can be synthesized in two
broad ways namely, top-down (producing very small structures from
larger pieces of material.) and bottom-up approaches(to arrange
themselves into atom by atom or molecule by molecule).
1 .Top-down approach - Mechanical alloying, Lithography, Erosion
2.Bottom-up

approach-

Chemical

precipitation,

Gas

phase

agglomeration, self assembly etc.

In top down method , the bulk solids are dis-assembled into finer
pieces until the particles are in the order of nanometer. In the bottom up
approach different materials are synthesized by assembling the atoms
or molecules to form the nano materials. It is

g.g

Engineering Physics

essential to produce an optimized novel nano structured material for

potential applications. In view of this , in addition to the existing
techniques like physical, chemical and biological and hybrid techniques
are also developed. The classification of these techniques is as follows :

Techniques

Method

1 Physical

Mechanical :

High energy ball milling

Lithigraphy
Machining process

Physical vapour deposition

2 Chemical method

3 Biological

Chemical
vapour
Plasma
Enhanced
Colloids
Sol gel

deposition
vapour deposition

Inverse
micelles
Using biomembranes
DNA
Enzymes

4 Hybrid

8.5

Electrochemic
al
Chemical
deposition
vapour
Micro
emulsion

Some Specific methods of synthesis of nanomaterials

I) Vapour phase deposition (Physical method: Bottom up

approach )
This is the method of depositing thin films by condensation of a
vaporized form of a material onto various surfaces under high vacuum
condition. In this method the size, shape and chemical composition of a
nano structured material is controlled .Various methods of vapour phase
deposition involves : evaporation , sputtering , glow discharge , RF
sputtering, etc.

Evaporation: A evacuated chamber is filled with inert gas, the material

to be deposited is electrically vaporized. The evaporated atoms or
molecules are allowed to condense on a cold finger which is cooled
externally by liquid N2. The nano particles on cold finger are scraped
and then collected . This method is more suitable for non conductive
materials or high melting materials.
Sputtering : In case of compound materials , the materials will
dissociate

before

evaporation

and

hence

,the

proportion

of

constituents stoichiometric is not maintained in the final products .

Therefore it is advisable to use this method for deposion of
stoichiometric products.
An inert gas like argon is incident on the target material. The atoms
or molecules in the ionized form hit the target material and knock
out the surface atoms. The knocked out atoms are deposited on the
second Solid surface known as substrate. The removal of the atoms
from the target is known as erosion. The sputtering is achieved by
two different method namely DC voltage and RF voltage .
Pulse laser deposition : In this method , high power pulse laser
ablates the material from the target into a vapour and allowed to
deposit on substrate.
II) Sol gel process (Chemical method )
The sol gel process is the wet- chemical technique, i.e. chemical
solution deposition technique used for the production of high purity
and homogeneous nano materials , particularly metal oxide nano
particles. The sol gel technique is a long-established industrial
process for the generation of colloidal nano particles from liquid
phase, that has been further developed in the production of
advanced nanomaterials and coatings.The starting material from a
chemical solution leads to formation of colloidal suspensions known
as Sol. The suspension that keeps its shape is called gel. Thus solgels are suspensions of colloids in liquids that keep their shape.
The thermal treatment (firing/calcination) of the gels leads to
further poly condensation and enhances the mechanical properties
of the products. This method is typically used for the synthesis of
metal oxides where the typical precursors used are the metal
alkoxides and metal chlorides(Fig.8.3). The starting material is

processed with water or in alkaline solvent .The

8.10

Engineering Physics

material undergoes a hydrolysis and poly condensation reaction which leads

to formation of colloids . The colloid system composed of solid particles
dispersed in a solvent contains particles of size from Inm to 1 mm . The sol is
then evolved to form an inorganic network containing liquid phase (gel) . The
schematic diagram of the synthesis using sol gel method is shown in
figure(8.3).
I
calcine

m
) \
Dehydrat
Veaction

dipping

cpf
e
8%o

8
Aerogel
cP
Rapid

L surfactant organic suspension

'O

Xerogel
1

t^DO
calcine
calcine
Thin film coating
Powder

Dense
ceramic

Fig.8.3 Sol gel synthesis of nano particles

The sol can be further processed to obtain the substrate in a film , either by
dip coating :-spin coating, or cast into a container with desired shape or
powders by calcinations.
The sol-gel approach is a cheap and low-temperature technique that allows
for the firve control of the product's chemical composition. Even small
quantities of dopants, such 1$ organic dyes and rare earth metals, can be
introduced in the sol and end up uniforms dispersed in the final product. It
can be used in ceramics processing and manufacturing is an investment
casting material, or as a means of producing very thin films of metal oxides I

for various purposes. Sol-gel derived materials have diverse

applications in op: . electronics, energy, space, (bio)sensors, medicine
(e.g. controlled drug release) and I separation (e.g. chromatography)
technology. The main advantages of sol-gel techniques

Manotechnology [ 8.11
for the preparation of materials are low temperature of processing,
versatility, allowing easy shaping and embedding. They offer unique
opportunities for access to organic-inorganic materials.
Ill)Mechanical Grinding (Ball milling): (Physical method: top down
method )
It is a typical example of top down method of synthesis of nano materials.
It is very popular, simple, inexpensive. In this method small balls are allowed
to rotate around the inside of drums and then fall on a Solid with gravity force
and crush the Solid into non crystallites. Ball milling can be used to prepare a
wide range of elemental and metal oxide
powders.
IV) Electrodeposition
Electrodeposition technique is used to electroplate a material. In many
liquids called electrolytes (aqueous solutions of salts , acids etc.), when
current is, passed through two electrodes immersed inside the electrolyte,
certain mass of the substance liberated at one electrode gets deposited on
the surface of the other. By controlling current and other parameters, it is
possible to deposit even a single layer of atoms. Nano structured films of
copper , platinum nickel, gold can be produced by electro deposition. The
film thus obtained are mechanically robust, highly flat and uniform. This
films exhibits favorable electrical properties.
V) Forced hydrolysis
The simplest method for the generation of uniformly sized colloidal metal
oxides is based on forced hydrolysis of metal salt solutions. It is well known
that most polyvalent cations readily hydrolyse, and that deprotonation of
coordinated water molecules is greatly accelerated with increasingly
temperature. Since hydrolysis products are intermediates to precipitation of
metal oxides , increasing temperature results in an increasing amount of
deprotonated molecules. When the concentration far exceeds the solubility ,
nucleation of metal oxides occurs. In principle, to produce such metal oxides
colloide , one just needs to age the hydrolysed metal solutions at elevated
temperatures. Thus hydrolysis reaction should proceed rapidly and
produce an abrupt supersaturation to ensure a burst of nucleation ,
resulting in the formation of a large number of small nuclei, eventually

8.12

Engineering Physics

leading to the formation of small particles. This principle is used for the
formation of

" silica spheres. In this method the reaction rate and particle

size were strongly dependent on the Solvents, precursors, amount of water and
ammonia.

VI )

Microwave

and

combustion method

Applied I
power
I alcnl I leal

Microwave reactor methodologies are unique in their

ability

to

effects,

be

scaled-up

providing

improvement
convective

without

in

potentially

nanocrystal

methods.

dispersity

nanoscale

been

prepared

via

precursors

direct
rather

the solvent.

InGaP,

of
InP,

microwave
than

thermal

gradient

industrially

synthetic

Synthesis

mono
molecular

suffering

important

methodology
high-quality,
and

near

CdSe

heating

convective

over

of
heating

have
the
of

p g84

Microwave dielectric heating not only enhances the rate of formation, it also
enhances the material quality and size distributions. The reaction rates are
influenced by the microwave field and by additives. The final quality of the
microwave-generated materials depends on the reactant choice, the applied
power, the reaction time, and temperature CdSe nanocrystals prepared in the
presence of a strong microwave absorber exhibit sharp excitonic features.
InGaP and InP are rapidly formed at 280 C in minutes, yielding clean reactions
and mono disperse size distributions that require no size-selective precipitation
and result in the highest out of batch quantum efficiency reported to date of 15%
prior to chemical etching. The use of microwave (MW) methodology is readiy
scalable to larger reaction volumes, allows faster reaction times, removes the
need for high-temperature injection, and suggests a specific microwave effect
may be present in these reactions.
Microwave-assisted process is a novel technique, used for rapid and
controlled processing of advanced ceramic materials. Many researchers used

microwave-assisted method for different types of ceramic materials . In the

microwave heating process, heat

Nanotechnology | 8.13
is generated internally within the material instead of originating from
external heating sources and hence is fundamentally different from other
heating processes. Microwave-flash combustion technique is the modified
combustion technique and is reported for the synthesis of Ni -Zn ferrite
nano powders in which the combustion process takes place by heating the
reactant mixture using the absorption of microwaves. This microwave
assisted flash-combustion process is simple and inexpensive due to energy
savings and shorter processing times. Furthermore, the synthesized
powder is generally more homogeneous, and the uniformity and yield are
high.
8.6 Some special
1
Fullerene

8.6.1
Fullerene:

nano materials :

2 CNT

3
Zeolites

4
Graphene

A fullerene is a molecule composed entirely of

carbon, in the form of a hollow sphere, ellipsoid or
tube. Spherical fullerene are also called bucky balls,
and cylindrical one are called carbon nano tubes
or buckytubes. Fullerene are similar in structure to
graphite, but they may contain pentagonal rings.
The first fullerene discovered was buckminster
fullerence C6o in 1985.

8.6.2

Carbon Nanotubes (CNT)

Carbon nanotubes are smallest molecule of graphite carbon with

outstanding characteristics. They are considered to be the most
strongest molecular structure which are known for their excellent
electronics characteristics and because of that they are having high
involvement in the industrial and commercial applications.

8.14 Engineering Physics

Historical

Background

Carbon nano tubes are found in 1985. Fullerenes played vital role in discovery of
carbon nanotubes. The molecule discovered was named as C 6o. Its composition
was similar to the graphite atom which was already present but this was a new
composition because it has better properties than graphite. Later on 1990 it was
proposed that C6o composition can be produced easily with the help of arc
evaporation setups in all the laboratories. The famous Japanese researcher
Sumio Lijima discovered the fullerene related carbon nanotubes in 1991. They
were double layered tubes having diameter about 30 nm and were closed from
both the ends.

Structure of cabon nanotubes

effect
Nanotubes have complex structure with sp2 bonding. Each of its atoms is forms.
attached to its neighbors similar to the graphite atom. They form a
sequence of layer when seen together. It has dual particles in its
structure which is divided into three classes. Specific terms are used to
represent nanotubes classes according to the arrangements.
The nanotubes are classified as - 1 The first one is known as
"armchair", 2 The second one is known as "Zig Zag" and it has high
symmetry. 3 The third is known as the "Chiral" which mean two mirror

Nanotechnology j 8.15
Properties of cabon nanotubes
1. Nano carbon tubes have many unique properties which makes them
superior than another
nano structures discovered. The most dominant property ofnano
carbon tubes is their highest
strength and stiffness in weight ratio.
2. Another useful characteristic of carbon nano tubes is their easy
penetration in the cellular
structures such as membrane. They look like smallest needles so it's
a possibility that they
can function like a needle in cells.
3. Carbon nanotubes also have unique and outstanding electronic
properties. Their electrical
resistance changes randomly when existing molecules are attached
with other carbon atoms.
This property of carbon nanotubes in building high performance
sensors that can detect
chemical vapors in the air.
The above properties of carbon nanotubes are very useful for developing
many extra ordinary machines in today's world. For example NASA space
craft centre is using carbon nanotubes to lighten the weight of their space
crafts, medical researchers are utilizing the properties to directly deliver
drugs to the infected area from cancer treatment.
Applications of carbon nano tube
Carbon nanotubes have diverse properties to be used in several work area.
Some of the developing applications are listed below.
1) Breast Cancer Tumor Destruction: Nanotubes are used to destroy the
breast cancer
tumors. They play like an antibody that is provided by the chicken. The
antibody along
with nanotubes is attracted to the proteins by the cancer cell in the
body and nanotubes
absorb laser beam killing the bacteria of tumor.
2) Wind Mill Blades: Nano tubes are also used in the wind mill blades
because of their

low weight it produce more electricity at faster rate.

3) Due to extra ordinary mechanical properties of carbon nanotubes
,they are used on
many structural applications like garments, sport gears and jackets
and also in space
elevators. Although space elevators requires other strong efforts to
get into action but
carbon nanotubes plays vital role in the functioning and structure of
space elevators.

4) 8.16

Engineering Physics

4) Electronics circuits: Nanotubes are also used in manufacturing

and arrangments of
electrical circuits. Nanotubes transistors are used which can
be operated at room
tempertaure and have the ability to get automatically switch on or
off. One thing which is
lacking is the involvement of other technology in the constrcution
of electrical circuits.
The very first carbon nanotube integrated memory circuit was
developed in 2004.
5) Solar cells : Nanotubes are also used in Solar cells. Specific
formula is used which is
prepared from carbon nanotubes and fullerenes which
empowers the Solar batteries.
Fullerenes are also known as carbon bucky balls, these bucky balls
traces electrons and
prevent them to flow further then add sunlight to the entire
structure and transmit it to the
terminals of the Solar batteries.
5) 6)

Capacitors : Nano carbon tubes have the property to store

electrical flow in them,

which makes best for the ultra capacitors. The activated and
concentrated charcoal used
in ultra capacitors has many tiny spaces of different sizes, which
create together a huge
surface to store electric charge. This charge is quantified into
different charges further
such as electrons, and elementary charge, the electrode surface is
not available for storing
charge in it

because they have

hollow spaces which are not

compatible with the

requirement of charge. With the help of carbon nano tube
electrode the spaces may be
minimized to a certain size which improves the storage capacity
and perform conduction
more efficiently.

6) 7) Other applications: There are many other applications in which

carbon

nanotubes

are

used

such

as

mechanical

memory

elements, electric conduction films, frequency distribution of

radio signals, bullet proof jackets and scratch free surfaces, kinetic
energy controlling, density and velocity measurements in the field
of physics etc.
7) 8.6.3

Zeolite (crystalline microporous material)

8) Zeolites are crystalline aluminosilicates with open framework

structure of three dimensional tetrahedral units generating a
network of pores and cavities having molecular dimensions. There
are about 34 naturally occurring and about 100 synthetic type
Zeolites. These materials are widely used in applications, such
as separations, catalysis, ion

9) "sjanoie< imiiiu^y .
10)

exchange and adsorption due to their unique properties

such as molecular sieving, high thermal stability, acidity,

adsorption capacities, shape selectivity and ion exchange. It is
generally recognized that particle size of zeolites have a
significant

influence

on

the

catalytic

performance,

particularly in reactions involving the external surface and

controlled by a diffusion process. Recently, nano-sized zeolite
crystals

have

received

attention

due

to

their

unique

physicochemical properties.
11)

Nanocrystalline zeolites are zeolites with discrete,

uniform crystals with dimensions of less than 100 nm that

have unique properties relative to conventional micrometersized zeolite crystals. Nanocrystalline zeolites have higher
external surface areas and reduced diffusion path lengths
relative to conventional micrometer-sized zeolites, which
made them promising catalytic materials and adsorbents. As
the particle size decreases, there is an increased ratio of
atoms at or near the surface relative to the number of atoms
on the inner part of the crystal. Therefore, ratio of external to
internal number of nano crystalline zeolite atoms increases
rapidly. The basic structural units for zeolites Y are the sodalite
cages, which are arranged so as to form supercages that are
large enough to accommodate spheres with 1.2 nm diameter.
The primary application for Y zeolites has been in catalytic
cracking of petroleum into gaSoline range hydrocarbons.
Among the zeolites used in industrial scale, zeolite Y (or
faujasite) including ultra-stable Y zeolite (USY) is the most
widely employed materials. It is the main component of fluid
catalytic cracking (FCC) catalyst at a volume above 100,000
tons/yr like refining processing in petrochemical industries .
12)

8.6.4

Graphene

13)

The Nobel Prize in Physics for 2010 was awarded to

Andre Geim and Konstantin Novoselov " for ground breaking

experiments
graphene".

regarding

the

two-dimensional

material

14)

Graphene is an allotrope of carbon, whose structure is

one-atom-thick planar sheets of sp:-bonded carbon atoms that

are densely packed in a honeycomb crystal lattice. The term
graphene was coined as a combination of graphite and the
suffix -ene by Hanns-Peter Boehm, who described singlelayer carbon foils in 1962. Graphene is most easily

15)

8.18

Engineering Physics

16)

visualized as an atomic-scale chicken wire made of carbon

atoms and their bonds. The crystalline or "flake" form of graphite

consists of many graphene sheets stacked together.
17)

The carbon-carbon bond length in graphene is about 0.142

nanometers. Graphene sheets stack to form graphite with an

interplanar spacing of 0.335 nm, which means that a stack of three
million sheets would be only one millimeter thick. Graphene is
the basic structural element of some carbon allotropes including
graphite, charcoal, carbon nanotubes and fullerenes. It can also be
considered as an indefinitely large aromatic molecule, the limiting
case of the family of flat polycyclic aromatic hydrocarbons.
1)

18)

Graphene is one of the strongest, lightest and

most

conductive materials known to humankind. It's also 97.3 percent

transparent, but looks really
19)

cool under powerful microscopes.

20)

Applications of Graphene

21)

Super-Dense Data Storage:

22)

A Rice University team in 2008 created a new type of

graphene-based, flash-like storage memory, more dense and less

lossy than any existing storage technology. Two University of South
Florida researchers reported techniques to enhance and direct its
conductivity by creating wire-like defects to send current flowing
through graphene strips.
23)

Energy Storage:

24)

The energy applications of graphene are also extraordinarily

rich. Texas's Graphene Energy is using the film to create new ultra
capacitators to store and transmit electrical power. Companies

currently using carbon nanotubes to create wearable electronics

clothes that can power and charge electrical devices are beginning
to switch to graphene, which is thinner and potentially less expensive
to produce. Much of the emerging research is devoted to devising
more ways to produce graphene quickly, cheaply and in high
quantities.

25)

Nanoiecnnoiogy

26)

Optical Devices: Solar Cells and Flexible Touch screens

27)

Graphene has the ability to conduct light as well as

electricity. Strong, flexible, light-sensitive graphene could

improve the efficiency of Solar cells and LEDs, as well as aiding
in the production of next-generation devices like flexible
touch screens, photo detectors and ultrafast lasers. In
particular, graphene could replace rare and expensive metals
like platinum and indium, performing the same tasks with
greater efficiency at a fraction of the cost.
28)

High-Energy Particle Physics :

29)

In

pure

science,

graphene

makes

possible

experiments with high-speed quantum particles . Because

graphene is effective only two-dimensional, electrons can
move

through

its

lattice

structure

with

virtually

no

resistance. In fact, they behave like Heisenberg's relative

particles, with an effective resting mass of zero.
30)

The remarkable properties of graphene could lead to

the development of technology such as super-fast computers,

flexible mobile phones and even transparent planes among
other things.
31)

(Electrons squeezed through two-dimensional grapheme

have neither mass nor volume. In other words, the same

properties that makes graphene such an efficient medium for
storing and transmitting energy also demonstrate something
fundamental about the nature of the subatomic universe.)
32)
8.7 Application of nano materials in
Engineering
33)

Material Technology :Nano magnets used in MRI

technique, ceramic as super plastics, nano membrane used

in water purification, in sunscreens, Nano sized iron oxide is
in lipstics as a pigment, carbon nano particles are used as a
filler in reinforce car tires etc. Nano amplification and chip

embedding is used for building semiconductor devices which

can even maintain and neutralize the electric flow. Now
engineers are using integrated nano circuits in their silicon
chips to reduce the size of the processors.

34)

8.20 I Engineering Physics

35)

Information Technology: As data storage, in optoelectronic

devices, light emitting phosphors, low voltage field emission

displays etc. Silicon nano particles increase the storage capacity
and battery power of energy cells. Resolution of display devices is
getting better day by day with the help of nanotechnology. Nano
pixelation of these devices make the picture feel real. Similarly
frequency modulation in audio devices can be now digitized to
billionth bit of signals.
36)

Biomedical : Artificial heart valves, tagging of DNA and DNA

chips, controlled drug delivery

37)

Energy storage: It improves fuel economy, hydrogen storage

devices, useful in magnetic refrigeration, fabrication of ionic

batteries etc.
38)

Automotive

industry:

In

automobile

engineering

nano

science plays important role in making brakes of the vehicle more

efficient and soft and for improving the liquids of the disc brakes. In
ttie world of automobile industry, nanoscience is also used for
making engines stronger and reliable. Protective nanopaint for cars
are made that resist water and dirt, Resistant to chipping and
scratches, Brighter colors, enhanced gloss to cars all these
advancement came into being when nano science stepped into
field.
39)

Chemical industry: Fillers for paint system, coating system,

switchable adhesives, magnetic fluids etc.Gold nano particle are

used to maintain the volatile liquids at room temperature. They are
used to break down the acidic compounds in the air to neutralize
vaporization. They are used to find out the presence of fat hydrogen
especially in nuclear plants. When hydrogen is around then they
get swell to show the presence of gas. Iron nano particles are used
for cleaning up the carbon polluted water.
40)

Medicine: Nano particle is coated with a peptide that binds

to a cancer tumor to reduce the tumor effect to the nervous

system of the infected body. They are used to deliver drugs to .the

various parts of body for life saving purpose.

41)

Iron oxide nano particle are used for magnetic resonance

through out the world, they are used for improving the scanning
ability of the scanning device .Iron oxide nano particle

42)
are used for magnetic resonance through out the
world, they are used for improving the
43) /
scanning ability of the scanning device Crystalline nano particles
which arc also known as
44)

Quantum dots care also used to find the cancer disease

in the body. Nano particles in the form of arsenic are used for
cleaning up the waters from the wells. Nano particles also
have the ability to destroy the cancer cells in the body in the
form of UV rays.
45)

Textile industry: Zinc oxide nano particles are used for

protective wood coatings and used in textiles and plastics

materials to ensure reliability. Silver nano particles are used to
kill the bacteria from garments and silk materials
46)

Cosmetics industry : Now a days nano particle

cream is available that is suitable for every skin type and

protect the rashes and damaged skin afrom getting infected.
Fungus does not affect the skin in the presence of nano
particles on skin. Beauty care and make up products with high
quality can be produced according to the skin tone and type of
the skin
47)

Food industry : Food products can be prevented well

with the help of nanotechnology. Preservative reactions and

more refined food color can be produced. Nutritive value of
eatables can also be improved.

48)

sports industry : Nanotechnology is being applied to

many areas of sport. Tennis and golf are traditionally two of

the main sports that embrace new technology, they have
started adding nanosize silicon dioxide crystals to their
racquets, offering increased power but not at the expense of
weight. In the world of competitive sport even the most
minimal changes in equipment can make all the difference
between winning and losing.
49)

Golf club manufacturer has invested heavily in

nanotechnology in recent years,

50)

rarticularly nanometal coatings. The nanometals have a

crystalline structure, and although
51)

they are hundreds of times smaller than traditional

metals, they are four times stronger. A

52)

rts company - have recently produced golf

balls with

nanoscale coating to reduce

53)

ng' and allow a truer contact with the club, producing

shots that do not go further, but
54)

do travel straighten

55)

8.22 | Engineering Physics

56)

Application

in

construction:

Nanotechnology

make

construction and engineering safer, cheaper and reliable, building

materials can create unbreakable bonds when molecular treatment
is given to them. Refining of elements and materials is highly
powered by nanotechnology. Essence of a material can be extracted
now.
57)

8.8 Scanning Electron Microscope

58)

SEM is one of the most widely used techniques used in

the characterization of nanomaterials and nanostructures . It is

a microscope that uses electrons instead of light to form an
image. The scanning electron microscope (SEM) uses a focused
beam of high-energy electrons to generate a variety of signals at
the surface of solid specimens. The signals that derive from
electron-sample interactions reveal information about the sample
including external morphology (texture), chemical composition, and
crystalline structure and orientation of materials making up the
sample.
59)

In most applications, data are collected over a selected area

of the surface of the sample, and a 2-dimensional image is

generated that displays spatial variations in these properties. Areas
ranging from approximately 1 cm to 5 microns in width can be
imaged in a scanning mode using conventional SEM techniques
(magnification ranging from 20X to approximately 30,OOOX, spatial
resol of 50 to 100 nm). The SEM is also capable of performing
analyses of selected point locations on the sample. This approach is
especially

useful

in

qualitatively

determining

chemical

compositions, crystalline structure, and crystal orientations.

60)
Fundamental Principles of Scanning Electron
Microscopy (SEM)
61)

Accelerated electrons in an SEM carry significant amounts of

kinetic energy, and this energy is dissipated as a variety of signals

produced

by

electron-sample

interactions

when

the

incident

electrons are decelerated in the solid sample. These signals include

secondary electrons (that produce SEM images), backscattered

electrons (BSE), diffracted backscattered electrons (EBSDthat

are used to determine crystal structures and orientations of
minerals), photons (characteristic X-rays that are used for
elemental

analysis

and

continuum

(cathodoluminescenceCL), and heat.

X-rays),

visible

light

62)
63)

Nanotechnology | 8.23

Secondary electrons and backscattered electrons are commonly

used for imaging samples. Secondary electrons are most valuable for
showing morphology and topography on samples and backscattered
electrons .are for illustrating contrasts in composition in multiphase
samples (i.e. for rapid phase discrimination). X-ray generation is
produced by inelastic collisions of the incident electrons with electrons
in discrete orbital's (shells) of atoms in the sample. As the excited
electrons return to lower energy states, they yield X-rays that are of a
fixed wavelength (that is related to the difference in energy levels of
electrons in different shells for a given element). Thus, characteristic
X-rays are produced for each element in a mineral that is "excited" by
the electron beam. SEM analysis is considered to be "nondestructive"; that is, x-rays generated by electron interactions do not
lead to volume loss of the sample, so it is possible to analyze the
same materials
64)

repeatedly.

65)

Electron
^H
Electron Gun
Beam

66)
67)

Fig.8.5

2) T

3) S

c
a

4) Backs coffered. Electron

5) "
"" "~ 3econ clary
6) ^Electron * Detector
7) Sta

8) im

68)

8.24 | Engineering Physics

69)

The scanning electron microscope has many advantages over

traditional microscopes. The SEM has a large depth of field, which

allows more of a specimen to be in focus at one time. The SEM also
has much higher resolution , so closely spaced specimens can be
magnified

at

much

higher

levels.

Because

the

SEM

uses

electromagnets rather than lenses, the researcher has much more

control in the degree of magnification. All of these advantages, as
well as the actual strikingly clear images, make the scanning electron
microscope one of the most useful instruments in research today.
70)

The electron beam follows a vertical path through the

microscope, which is held within a vacuum. The beam travels through

electromagnetic fields and lenses, which focus the beam down
toward the sample. Once the beam hits the sample, electrons and Xrays are ejected from the sample.
71)
.
,. - Secondary electrons
9) Incident

72)
Auger
electrons
73) Sample
74)
75)

10) Primary

backscatt
ff^"^ v
Fig.8.6.

Detectors collect these X-rays, backscattered electrons, and

secondary electrons and convert them into a signal that is sent to a

screen similar to a television screen. This produces the final image.
76)
77)

Because the SEM utilizes vacuum conditions and uses electrons

to form an image, special preparations must be done to the sample. All

water must be removed from the samples because the water would
vaporize in the vacuum. All metals are conductive and require no
preparation before being used. All non-metals need to be made
conductive by covering the sample with a thin layer of conductive
material. This is done by using a device called a "sputter coater."

78)
79)

Nanotechnology I g.25

The sputter coater uses an electric field and argon gas. The

sample is placed in a small cfcamber that is at a vacuum. Argon

gas and an electric field cause an electron to be removed from
the argon, making the atoms positively charged. The argon ions
then become attracted to a negatively charged gold foil. The argon
ions knock gold atoms from the surface of the gold foil. These gold
atoms fall and settle onto the surface of the sample producing a
thin gold coating.
80)

8.9 Scanning Tunneling Microscope

81)

The scanning tunneling microscope (STM) is a type of

electron microscope that shows three-dimensional images of a

sample. In the STM, the structure of a surface is studied using a
stylus that scans the surface at a fixed distance from it. A
scanning tunneling microscope is an instrument for imaging
surfaces at the atomic level. With very high resolution, individual
atoms within materials are routinely imaged and manipulated. The
STM can be used not only in ultra-high vacuum but also in air,
water, and various other liquid or gas ambient, and at temperatures
ranging from near zero Kelvin to a few hundred degrees Celsius.
82)

Ordinary microscopes focus light which is emitted (or

reflected) from objects. The resolution of such a microscope is

limited by the wavelength of light. Microscopes which employ
visible light cannot resolve features smaller than about 500 nm.
Individual atoms are much smaller than that - just a few
nanometers in diameter. The scanning tunneling microscope (STM)
relies on two physical principles. 1 Quantum tunneling of electrons
across a potential barrier and 1 The piezoelectric effect.
83)

When a conducting tip(extremely sharp, tip being formed by

one single atom.) is brought very near to the surface to be

examined, a bias (voltage difference) applied between the two
can allow electrons to tunnel through the vacuum between
them. The resulting tunneling current is a function of tip position,
applied voltage, and the local density of states (LDOS) of the
sample. Information is acquired by monitoring the current as the
tip's position scans across the surface, and is usually displayed in

image form. STM can be a challenging technique, as it requires

extremely clean and stable surfaces, sharp tips, excellent vibration
control, and sophisticated electronics.

84)

8.26 | Engineering Physics

85)

The components of an STM include scanning tip, piezoelectric

controlled height and x, y scanner, coarse sample-to-tip control,

vibration isolation system, and computer. The tip is often made of
tungsten or platinum-iridium, though gold is also used. Tungsten tips
are usually made by electrochemical etching, and platinum-iridium
tips by mechanical shearing.
86)
-Tunneling
x
87)
13) Control voltages for
voltage
\
11)

14) Tunneling

Distance

control
12)88)
88)
15) tip
16) tj

88)

nr
eli
ng
el
ec
tr

Fig.8.7 Schematic view of an STM

89)

The STM works best with conducting materials, but it is also

possible to fix organic molecules on a surface and study their

structures. For example, this technique has been used in the study of
DNA molecules.
90)

Many other microscopy techniques have been developed based

upon STM. These include photon scanning microscopy (PSTM),

which uses an optical tip to tunnel photons. Scanning tunneling
potentiometry (STP), which measures electric potential across a
surface, spin polarized scanning tunneling microscopy (SPSTM),
which uses a ferromagnetic tip to tunnel spin-polarized electrons into
a magnetic sample, and atomic force microscopy (AFM), in which the
force caused by interaction between the tip and sample is measured.

91)

Nanotechnology

92)

Questions

93)

l.What is meant by nano ? What are nano materials ?

94)

2.Why do nano particles exhibits different properties ?

95)

3.How are optical, physical and chemical properties of

8.27

nanoparticles vary with their size ?

96)

4.Explain , the classification of nano material ?

97)

5.

What are the different methods of synthesis of nano

material ?
98)
6.
Explain the difference in top -down and bottom-up
approach needed for nano
synthesis.
7. What are fullerenes ?
8. What are carbon nano tubes? How are they produced ?
9. What are different types of carbon nano tubes ? What are their
properties ?
99) 10.

What are the different methods of preparation of nano

material?
11.What are applications of nano structured particles in
engineering?
12.What are important applications of nano materials in various
field ?