12/14/2023

Nanomaterials

1
 12/14/2023

Nano materials
 Nano materials are materials with atoms in nano sized
clusters which become the constituent grains or building
blocks of material.
(or)
Materials possessing grain sizes on the order of billionth
of a meter (all materials composed of grains which in turn
comprising many atoms).
(or)
Any material with at least one dimension in nano meter
range.
 Conventional materials have grain size ranging from microns
to millimeter and contain billion of atoms in each grain.
 Nano meter sized grains contain only 900 atoms each. These
grains are usually invisible to the naked eye, depending on
their size.
 1 nm =10Å, hence in 1 nm, there may be 3-5 atoms depending
on atomic radii.

2
 12/14/2023

 Small features permits more functionality in a given

space. Materials in μm scale mostly exhibit physical
properties same as that of bulk form.
 However, materials in nanometer scale may exhibit
physical properties distinctively different from that of
bulk.
Ex: i) Crystals in nm scale have low melting points.
ii) Ferro electrics and ferro magnetics may loose
their ferro electric and ferro magnetism when
they shrunk to the nanometer scale.
iii) Semiconductors in bulk nature become
insulators in nm scale.
 Nanocrystalline materials are exceptionally strong and
hard, ductile at high temperatures and chemically
active.

Nano Science: Nano Science is the study and understanding the

properties of Nano Particles.
Nano Technology: Nanotechnology can be defined as the design,
characterization, production and application of structures
devices and systems by controlling shape and size at a Nano
meter Scale.
(OR)
Nanotechnology is the manipulation of matter at the atomic
scale to create materials, devices, or systems with new properties or
functions, with potential applications in energy, healthcare, industry,
communications, agriculture, consumer products, and other sectors.

3
 12/14/2023

• Properties of material at reduced size

Can small things make a big difference? Yes at nanoscale every thing
will change.

•The fig. shows that nearly all

properties (some are shown) change for
nanomaterials

 Thus at nanoscale the properties electrical, mechanical, optical,

chemical and magnetic etc., which are said to be macroscopic
properties meet the more exotic properties of the atomic and
molecular world (microscopic world) such as wave-particle duality
and quantum effects.

 Coupling of size, with the most fundamental, chemical, electrical

and physical properties of materials is the key to all nano science.

4
 12/14/2023

Why Properties of Nano Materials are different ?

The properties of Nano Materials are very much different from

those at a larger scale.
Two principal factors cause the properties of Nano Materials to
differ significantly from other materials.

1.Increase in surface to volume ratio.

2.Quantum confinement effect.

Increase in a Surface Area to Volume ratio

Nano Materials have a 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”.

Its Surface Area =4πr2.
Its volume= 4/3πr3
Surface Area to Volume Ratio= 3/r.
Thus when the radius of the Sphere decreases ,
its Surface to Volume ratio increases.

5
 12/14/2023

1
m
2

surface area  6  1m 2  6 m 2

1
surface area  6  ( m) 2  8  12m2
2
1
m
3

1
surface area  6  ( m) 2  27  18m2
3

 Let us consider one Cubic Volume shown in figure its the Surface
Area is 6m2 .
 When it is divided into eight pieces its Surface Area becomes 12 m2,
similarly When the same volume is divided into 27 pieces its Surface
Area becomes 18 m2.
 Thus we find that when the given volume is divided into smaller
pieces the Surface Area increases.
 Hence as particle size decreases a greater proportion of atoms are
found at the surface compared to those inside.
 Nano particles have a much greater surface area per given volume
compared with larger particles. It makes materials more Chemically
reactive.

6
 12/14/2023

• Consequences of surface to volume ratio

• Chemical reactivity increases
Ex. Gold become extremely reactive at nano scale and can be
used as a catalyst to speed up reactions. Where as bulk gold is
chemically inert.
Examples in nature
The improved reactivity is the use of nano materials as catalysts in the
oil and chemical industries.
1. Catalytic converter in a car, which reduces the toxicity of the
engine’s fumes.
2. The nano-engineered batteries, fuel cells and catalysts at nano
scale posses enhanced reactivity which resuts in cleaner, safer
and more affordable modes of producing and storing energy.
3. Large surface to volume ratio also makes nano materials ideal
candidates for water treatment and desalination.
4. These also find wide applications in drug delivery, clothing
insulation as well as in solar cell photo-anodes and nano-
photoelectronic devices.

• Siegel classified nano structured materials into

‘4’ categories according their dimensionality.

1. Zero dimensional – Quantum dot (0D): A material having

three sides reduced below the critical characteristic length
and thus with its electrons confined in three directions and
free to move along no dimension.

2. One dimensional – Quantum wire (1D): A material having

two sides reduced below the critical characteristic length
and thus with its electrons confined in two directions and
free to move along one dimension.

7
 12/14/2023

2. Two dimensional – Quantum well (2D): A material having

one side reduced below the critical characteristic length
and thus with its electrons confined in one direction and
free to move along two dimensions.
3. Three dimensional (3D): Three dimensionally modulated
micro structures or nano phase materials consisting of
equiaxed nano meter sized grains.

Synthesis of nanomaterials

Top Down method Bottom Up method

Bulk Nanoparticles

Powder Clusters

Atoms
Nanoparticles

8
 12/14/2023

 Top down method

Ex: i) Mechanical grinding
 Bottom up method
Ex: i) Sol-gel method, ii) Pulsed laser deposition, iii) Sputtering
iv) Chemical vapour deposition (CVD), v) Chemical precipitation
vi) Aerosol technique, vii) Gas phase condensation

 If you take a sheet of paper and tear it half and tear it pieces in
half and so on, you will soon find that it becomes increasingly
difficult to produce small pieces. Similarly it is quite difficulty to
produce nanomaterials by breaking down larger particles. Now
just a wall may be built up by piling bricks one over the other.
Similarly nanoparticles may be created by assembling together
their building blocks which may atoms or molecules.
 Hence bottom up method is easier.

Sol-Gel Method

Supercritical
drying

9
 12/14/2023

Sol-Gel Method
It is a bottom-up process. It is a long established industrial process for
preparation of colloidal nano-particles from liquid phase. It involves, the
evolution of (inorganic) networks through the formation of colloidal
suspensions known as sol and gelation of sol to form a network in a
continuous liquid phase called the gel.
The stages of the Sol-Gel process are:
1. Hydrolysis 2. Polycondensation 3. Aging 4. Drying 5. Calcination
Hydrolysis:
The precursor is an aqueous solution of the metal alkoxides (M-OR). The
metal alkoxide reacts with the surrounding water and forms the colloidal
suspension (sol) of the metal hydroxide (M-OH) according to the hydrolysis
reaction.
M-OR + H-OH = M-OH + R-OH
During hydrolysis, addition of water results in the replacement of OR
group with hydroxyl group (OH). This process makes the solution active.
where M = Si, Ti, Zr, Al, Sn, Ce ; R = alkyl group
Polycondensation:
Polycondensation process results in the formation of Gel - a rigid 3-D
network built of polymeric molecules and surrounded with the solvent, as a result
of removal water.
M-OH + M-OH = M-O-M + H2O

10
 12/14/2023

Aging:
During the aging stage the polycondensation reactions continue
completing the formation of the gel. The gel structure is reinforced with
additional cross-links, which cause contraction of the gel matrix and
expulsion of the solution from the shrinking pores.

Drying:
The water and other liquids entrapped within the pores of
the gel structure are removed during this stage. Drying is performed at a
temperature of about ~200ºC. Drying at super-critical conditions
preventing collapsing of the gel network results in a formation of a
macro-porous low density structure called Aerogel. If the gel undergoes
thermal drying, it converts into a monolith micro-porous structure
called Xerogel.

Calcination:
During the calcination stage the dry gel structure is dehydrated
and finally we will get naoparticles. Calcination is performed at higher
temperatures within the range 400-800ºC.

Chemical vapour deposition

11
 12/14/2023

The deposition of films from gaseous phase by thermal

decompositions (pyrolysis) or chemical reaction on high
temperature substrate surface is known as “chemical vapour
deposition”. The basic principle involved in this technique is
decomposition or partial dissociation of vapour phase species
and their subsequent deposition on substrate gives thin film.
Depending on type of thin film to be grown, the
respective substances in the form of chloride should be taken.
The vapours of these react in chamber and film deposition takes
place.

Ball milling (Attrition milling)

Refractory
or
Steel balls
Preferably
Inert
atmosphere

12
 12/14/2023

It is a typical top down method of synthesis of nanomaterials. It is

very popular, simple, inexpensive equipment. It is used to produce nano
crystalline or amorphous materials.
In this method nanomaterials are prepared by structural
decomposition of coarser grained structures as result of severe plastic
deformations. In this method we can use either refractory balls or steel
balls or plastic balls depending on the materials to be synthesized.
When the balls rotate at particular rpm, the necessary energy is
transformed from balls to powder of the coarse grain size structure and
reduces the material into ultrafine nanorange particles. The nano
particles are produced due to the shear action as shown in figure. The
energy transferred to the powder from balls depends on many factors.
Such as
a) Rotational speed of the balls
b) Size of the balls
c) Number of the balls
d) Milling time
e) Ratio of the balls to powder mass
f) Milling medium

One can also use cryogenic liquids to increase the brittleness of

the powders. During milling process we have to prevent oxidation.
i.e., use an inert atmosphere during milling.
The selection of material of the balls place an important
role. Generally a harder material will be selected to synthesize the
softer material.

Advantages
The main advantage of this method is scaling upto
tonnage quantity of materials for wider applications.

Disadvantages
 Contamination of milling media and atmosphere

13
 12/14/2023

Carbon Nano Tubes

So far we know only 3 forms of carbon namely Diamond, graphite and
amorphous carbon. Now we came to know that there is other form of
carbon known as “Carbon Nano Tube (CNT)”, which are related to
graphite. Carbon nano tubes were first observed in 1991.

Discovery::
Discovery

They were discovered In 1991 by the

Japanese electron microscopist
SUMIO IIJIMA NEC Laboratory in Tsukuba--
used high-resolution transmission electron
microscopy to observe carbon nanotubes,
And into the awareness of the scientific
community .

A Carbon Nanotube is a tube-shaped material, made of carbon,

having a diameter measuring on the nanometre scale.

Nanotubes are members of the fullerene structural family.

Their name is derived from their long, hollow structure with the walls
formed by one atom thick sheets of carbon, called graphene.

Structure of graphite is a planar network of interconnected

hexagonal rings of carbon atoms. In conventional graphite, sheets of
carbon easily slide over each other. So graphite is not hard, used as
lubricant. When graphite sheets are rolled in to a cylinder and edges joined
they form Carbon Nano Tubes, i.e., CNTs are extended tubes of rolled
graphite sheet.

14
 12/14/2023

Based on number of walls present:

Classified mainly in two types:

1. SINGLE WALLED CARBON NANOTUBES
2. MULTI WALLED CARBON NANOTUBES

Other related structures:

TORUS, NANOBUD, GRAPHENATED CARBON NANOTUBES (g-CNTS), NITROGEN DOPED

CARBON NANOTUBES (N-CNTS), PEAPOD, CUP-STACKED CARBON NANOTUBES

 Based on direction of rolling:

i) Arm Chair ii) Zig-Zag iii) Chiral

15
 12/14/2023

 Single-walled carbon nanotubes are

composed of a single layer of graphene which
forms a cylindrical shape.

 SWCNT’s has the diameter of 1-2nm.

 SWCNTs are strong but elastic and have

excellent electronic properties. Therefore, they
can be used in many applications in
electronics, such as smart textiles, transistors,
RFID chips, information storage devices,
integrated circuits.

A scanning tunnelling microscopy image of SWNT

16
 12/14/2023

 Multi-walled carbon nanotubes made of multiple layers of graphene, which

formed in a concentric pattern around the smallest nanotube.

 MWCNT’s has the outer diameter of 50-80nm and inner diameter of 5-15nm.
Therefore the thickness if the wall is about 45-65nm.

 Multi-walled carbon nanotubes are remarkably stronger than the single-

walled carbon nanotube. As a result MWCNT’s used in applications that require
high mechanical strength.

 MWCNTs have high thermal conductivity and can be used in normally

insulative materials to increase their ability to transmit heat. This can be useful
in applications where heat needs to be dissipated.

Graphite sheet
 Based on direction of rolling:
30o

17
 12/14/2023

Properties of CNTs:

1. Mechanical Property: CNTs show impressive elastic behavior,

able to stretch more than 5 times to their initial length.

2. Electrical Property: CNTs are metallic or semiconducting in

nature. Metallic or semiconducting depends on diameter and
nature of rolling tube.
Arm chair structure – CNTs are metallic
Chiral Structure - CNTs are semiconducting

3. Optical Property: While illuminating CNTs, they show the

phenomenon of fluorescence.

4. Thermal Property: Study of thermal conductivity of CNTs showed

that, thermal energy travels with a velocity of 10,000 m/s along
the tube. Heat energy in CNTs is carried by sound waves in one
direction.

Applications of CNTs:

• Analytical instruments like MRI

•Water purification process
•Car bumpers
•Water proof and stain resistant fabrics
•Opto electronic devices

18