Nanotechnology and New Engineering Materials

Nanomaterials
The materials in which the grain size or crystallite size is less than 100nm are said to be nanomaterials

In ordinary or bulk materials, the grain size is in the range of millimetre

or micrometre and each grain has nearly billions of atoms. In
nanomaterials, the grain size is in the range of 1-100 nm and each grain
contains only few hundreds or tens of atoms.

In nanomaterials, there are more grains, so there are more grain

boundaries and hence number of atoms present at the grain boundaries is
large. This makes the surface to volume ratio large(atoms lying on the
surface to inside the grains). This large surface to volume ratio is
responsible for the unique properties exhibited by nanomaterials which
are completely different from their bulk counterparts.

Grain boundary

Grain

Large grain size Small grain size

 The methods used to prepare nanomaterials are broadly classified under two main headings as

 Top down approach

 Bottom up approach

Top down approach

In this bulk material is taken and crushed or broken into pieces continuously till the crystallite size reduces
to a value less than 100nm.

E.g. : Ball milling, photolithography etc.

Bottom up approach

In this individual atoms or molecules are arranged so as to obtain a material with a grain size less than
100nm.

E.g. : Sol-gel method , chemical vapour deposition, electrodeposition, etc.

 Physical Vapour deposition
In this method a material is heated using resistive heating or electron beam bombardment method. The
material is converted to vapour. The atoms or molecules of the vapour are allowed to condense on a cold
substrate forming a nanocrystalline material on the substrate .

The physical vapour deposition system

consists of vacuum chamber in which the
pressure is reduced to a value less than
10-7 m bar. The material is placed on a boat
of molybdenum or tungsten which can be
heated using resistive heating method. An inlet
is available through which an inert gas is
introduced into the chamber. A cold finger
arrangement with liquid nitrogen is positioned
at a suitable distance above source heater.

Resistive heating
arrangement
To vacuum pump
 A current is passed through resistive heating arrangement which heats the material placed on the boat.
The material gets heated and starts to evaporate. The atoms in the vapours formed collide with the
inert gas atoms and lose their kinetic energy. This results in the formation of supersaturated vapour.
The vapour condenses on the cold finger (substrate)and results in nucleation of grains.

As temperature of cold finger is very low and as the atoms have less kinetic energy they are not able
to move on cold finger and this restricts grain growth. So the formed grains are not able to grow in size
and hence crystallites or grains of small size are formed. Hence material with crystallite size less than
100 nm is formed on the surface of cold finger. The nano crystalline material is removed using a
scrapper and is collected

Sol-gel method
Sol gel method is a wet chemical method and is a solution growth technique by which nanocrystalline
materials can be prepared.

It is a simple and economical method and does not require any vacuum arrangement.
In this method nanocrystalline materials with different structures like nanocrystalline materials made of
particles, nanotubes, nanorods, nanoflowers, nanofibers etc. can be easily synthesized.
In this method,

 The starting materials or precursors used are metal alkoxides in the form of oxides, nitrates,
chlorides etc.

 Water is used as hydrolysis agent.

 Alcohol is used as solvent and a suitable acid or base is used as catalyst.

 The process of reaction sequence is hydrolysis and polycondensation, resulting in sol

formation.

 Then by gelation process , gel is formed from the sol.

 From the gel, aerogel and xerogel are formed by suitable heat treatment.

Sol is one which contains suspended particles having their size lying in nanometer range and are
present in a liquid medium. This is similar to a colloidal solution. The particles are dispersed in a
liquid medium and the particles exhibit Brownian movement
 Sol-gel method

Spray pyrolysis

Dense thin film

Nanocrystalline thin film is obtained from the sol by
 dip coating (immersing or dipping a glass plate in the sol)

 spin coating (a drop of sol is introduced on a rotating glass plate, the sol spreads due to
centrifugal force and forms a thin layer)

 by spray pyrolysis (sol is sprayed on the glass plate).

Nano fibers are obtained by allowing the sol to undergo a spinning process(electro spinning) . Powder can
be obtained by allowing the sol to dry.
The sol is converted into gel by gelation process. Gelation can be achieved by using a suitable reagent
like polyvinylalcohol or by changing the pH, temperature, etc. The particles in the sol are linked
together and form the gel in which they form a less dense three dimensional network.

Super critical drying of the gel forms aerogel. Aerogel is a material which is less dense in nature having a
density of 10-20% of bulk.

By allowing the gel to dry normally xerogel is formed which has a density of 30-50% of bulk.

Nano crystalline powder can be obtained by allowing gel to dry and by crushing it. Sol-gel process takes
place at room temperature.
Properties of nanomaterials

1. In nanomaterials the interatomic distance is less.

2. The melting point of the material decreases with decrease in grain size.

Melting point
Normal Nanocrystalline gold with Normal Nanocrystalline CdS with
gold crystallite size 10 - 20 nm CdS crystallite size 10 - 15 nm
1300 K 700 K 1700 K 600 K

3. In normal metals, energy levels are closely spaced forming energy band, but in nanocrystalline
materials, the band becomes narrower. The energy level is discrete in nature and are well spaced
forming discrete energy levels.

4. Ionization potential of nanocrystalline materials is high.

5. Chemical reactivity and catalytic activity of nanocrystalline material are high.

6. There is 30% to 50% reduction in moduli of elasticity in nanomaterials.

7. Strength is higher by 2 to 7 times. Strength and hardness increases with decrease

of crystallite size up to 10nm. When crystallite size goes below, 10nm, strength
starts to decrease.

8. Some of ceramic nanocrystallite materials exhibit superplasticity. (> 100% deformation).

9. Nano crystalline tungsten or titanium or tantalum carbide exhibit very high strength, high corrosion
resistance, high wear resistance and long life time
10. Carbon nanotube exhibits high strength and good electrical conductivity.

11. Nanocrystalline Fe, Ni cobalt are not ferromagnetic but are super paramagnetic.

12. Nano crystalline Na, K, Rh are ferromagnetic.

13. The magnetic moment of nanocrystalline magnetic materals is high.

14. Some of the materials like copper nanowires are transparent which are opaque in bulk form.
15. The optical band gap of nano crystallite material is greater than that of bulk and band gap increases with

decrease in crystallite size.

16. The color of nano materials depends on crystallite size. Gold in nanocrystalline form appears blue,
green, orange, red, purple depending of crystallite size.

17. Nano crystallite Ni, Pt, Pd are capable of absorbing H 2 and storing it within them. If these materials are

made of crystallite grains which have 1 to 60 atoms only then each host atom can absorb 8 hydrogen
atoms. So it is used as a hydrogen storage device.
Applications of nanomaterials
1. Nanomaterials exhibit excellent magnetic properties and are used in magnetic memories,
magnetic read head/write head etc. Nanocrystalline Iron – copper alloy is used as R/W head and
also in magnetic memories.

2. Nanocrystalline Yttrium Samarium Cobalt is used to produce magnetic field in MRI scanning
device which is a diagnostic tool in medicine.

3. Nanocrystalline nickel metal hydride based batteries require less frequent recharging and they
are able to retain the charge for a longer time and hence they have long life time.
4. Nanocrystalline ZnSe, ZnS, CdS and PbTe are used in display screens (TV Monitors) and they exhibit
very high resolution.

5. NEMS – Nano electro mechanical system. The electronic circuitry and associated
mechanical components are integrated and lie within nano scale size regime, which
can acts as a sensor or activator. Mass sensor based on NEMS technology can
measure a mass of 10-27 kg.

6. In the piston cylinder arrangement of a diesel engine, when interior of cylinder is coated with
nanocrystalline zirconia or alumina, it is able to retain heat effectively and this improves fuel
combustion efficiency.

7. Nanocrystalline zirconia is a very good bio-compatible material and is used for manufacture of
medical implants.

8. Nanocrystalline SiC4 is used in the manufacture of artificial heart valves

9. Some of the nanocrystalline materials(semiconductor quantum dots) are used as luminescent tags,
in medical diagnostic field and are used in targeted drug delivery system.

10. Nanocrystalline , TiO2 is mixed with paints to make dirt repellent paints.
11. Nanocrystalline ZnO is used in sun screen creams as it fully absorbs UV radiation.

12. Nanocrystalline Ag exhibits very good antibacterial and antifungal activity and is used in textile
fibers, food containers etc.

13. Cutting tools (drill bits etc.) made of nanocrystalline tungsten carbide, tantalum carbide, and
titanium carbide have very good strength, good wear resistance, good corrosion resistance and
long life time. It is possible to have drill bits with less than 1µm dimension.

14. Aerogels are used in smart windows, which is used to control and maintain the intensity of light
inside the room.

15. SiC4 and SiN3 in nanocrystalline form are used to make hard springs, ball bearings etc.

16. Nanocrystalline materials are used as catalysts and they exhibit very good catalytic activity and are
used to convert toxic gases like CO2 , CO and nitrous oxide emitted by automobiles as pollutant into
other non-toxic forms.

17. Nanocrystalline Ni, Pt and Pd are capable of adsorbing hydrogen and are used as hydrogen storage
device.
 Metallic glasses
Metallic glasses are metal alloys in which atoms or molecules are arranged in random manner or
atoms/molecules are arranged in amorphous manner as seen in glasses.

Metallic glasses are prepared by having the metal alloy in molten liquid state and then allowing the molten
liquid to cool rapidly (quenching) i.e. the rate of cooling is 10 6 K/s. As the molten liquid metal is cooled
rapidly it forms a solid in which atoms are arranged in a random manner as seen in amorphous materials.

Metallic glass

Metal alloys with properties of Atomic arrangement as in

metals like malleability, ductility, glasses
opaque etc.

Glass transition temperature is the temperature at which material is frozen to solid state on cooling.
 Metallic glasses are classified as

 Metal – Metalloid type

Metal (Fe, Ni, Co)
Metalloid (Si, C, P, S)

 Metal - Metal type

(CuZn, MnZn, NiZn)

 Rare earth based metallic glasses

(GdCo, GdNi)
Metallic glasses are prepared by melt spinning method
Melt Spinning Method
It consists of a tubular furnace made of
refractory material and bottom of the furnace is
tapered and has a nozzle. This tubular
arrangement is heated by a coil wound along the
tube. A copper disk is positioned below the
nozzle of tubular furnace and disc is rotated with
the help of a motor. The disc rotates with a rim
speed of nearly 50m/s.
 The metals in required proportion are introduced into the
furnace and is heated using a heater coil. The metal is
converted to molten liquid form and by using inert gas like
Ne/Ar, from the top of the furnace, pressure is exerted on the
molten metal and the liquid metal is forced to eject out of the
furnace through the nozzle. The ejected molten liquid metal
alloy then falls on the rotating copper disc as shown in the
diagram.

The disc absorbs heat and cools the molten liquid metal
rapidly and molten metal is frozen into a solid on the disc.
Because of centrifugal force of rotating disc the solidifying
metal alloy is carried by the rotating disc through some
distance and is thrown out in the form of ribbon. This results
in formation of metallic glass of the alloy in ribbon form. The
width and thickness of metallic glass formed is nearly 15cm
and 0.0025cm.

The quality and nature of metallic glass formed depends on the

 pressure of the gas.
 distance between nozzle and disc
 speed of rotating disc.
Properties
Metallic glass

 Very good mechanical strength and tensile strength.

 Very good ductility .
 Very high corrosion resistance and wear resistance .
 High elastic limit.
 Low moduli of elasticity.
 High electrical resistivity.
 Variation of electric resistance with temperature is very small, some metallic glasses have zero TCR.
 Eddy current induced is very small and also eddy current losses is small.
 Some of the metallic glasses based on Mo, Ru, Rh alloys are super conductors at low temperatures.
:
 The magnetic permeability and susceptibility is very high. B Normal ferromagnetic
 Exhibits low hysteresis loss and coercivity is very low. alloy

 Some of the metallic glasses exhibit very good biocompatible nature. Metallic glass
 Some of the metallic glasses exhibit good catalytic activity . H
 They have low thermal conductivity.
 Applications

 In transform cores: as metallic glasses have high electric resistance, they have low eddy current loss and
low hysteresis loss. Thus the core loss is 5 to 10 times lesser than that of iron silicon alloys. So metallic
glasses are generally used as transformer cores

 Metallic glasses are used as reinforcement element in concrete, rubber, plastic and in high pressure vessels.
 As they have very good workability, they are used in manufacture of springs.
 They are used to make standard resistance.
 They are used as R/W head in memory storage devices and used as magnetic memory element to store
data.
 They are not affected by nuclear radiation and so are used as containers for nuclear waste disposal.
 Metallic glass vitreloy is used in knee replacement alloys .
 As they have high corrosion resistance they are used as 1. Marine cables (under water cables) 2. Coatings for
high reactor vessels 3. Medical implants 4. Surgical clips 5. Surgical devices .
 Vitreloy is used as a casing for pace maker devices.
 They are used in prosthetic devices .
Shape Memory Alloys (SMA)
Shape memory alloys are alloys which can be easily and severely deformed below a particular temperature and
are able to regain their original shape on heating

Examples :
 NiTi (Nitinol)
 AuCd
 CuZn
 CuAlZn
 CuAlNi etc.,

One way shape memory alloy: The alloys which are able
to regain their shape on heating alone.(memory is with
austenite phase)
Two way shape memory alloy : The alloys which are
able to regain one shape on heating and another
shape on cooling.(memory is with both austenite and
martensite phases)
Shape memory alloys exhibit two different phases (atomic arrangements) and they are
 Martensite phase
 Austenite phase

Shape memory alloy has martensite type of atomic arrangement in low temperature region. In martensite
phase, the material is very soft and can be easily and severely deformed.

Shape memory alloys have austenite type of atomic arrangement in high temperature region. In this
phase, the material is very hard.

In shape memory alloy, shape memory behavior

takes place due to phase transformation which
is from martensite to austenite on heating and
austenite to martensite on cooling.
Shape memory effect
It is observed in shape memory alloys that when the material is in
austenite phase, it is hard and when temperature is reduced, it goes to
martensite phase and it becomes soft and now it can be deformed
easily. When temperature is increased it returns back to austenite
phase and it regains its original shape. This is known as shape memory
effect.
In shape memory alloys, the shape memory effect occurs as shown in
the diagram due to phase transformation.

The alloy is in austenite phase (hard in nature) at high

temperature, by reducing the temperature the material
becomes soft and is in martensite phase. Now when a
load is applied, it is deformed and there is a change in
shape. When the material is heated it goes back to
austenite phase and it regains its original shape.

It is like the material keeps it original shape in memory and after

deforming the material by applying a force, if you heat the
material it recollects it shape from memory and regains its
original shape.
Hysteresis in Shape Memory Alloys

In shape memory alloys, the temperature required to transform the alloy from martensite phase to
austenite phase on heating and austenite phase to martensite phase on cooling is not same.

In shape memory alloys, the transformation from

martensite to austensite on heating and from austenite
to martensite on cooling does not take place at a
particular temperature but it is spread over a
temperature range.

The temperature range required to transform from

martensite to austensite phase on heating is greater than
that required for transforming from austenite to
martensite on cooling.

If a plot is drawn between temperature and phase

transformation as shown. The curve corresponding to Mf - Martensite finish
martensite to austenite transformation on heating and curve
Ms - Martensite start
corresponding to austenitic to martensite transformation on
cooling do not coincide or overlap and this results in As – Austenite start
hysteresis . Af - Austenite finish
Pseudoelasticity

Pseudoelasticity is observed in shape memory alloys only when the alloy is in austentie phase (high
temperature). Consider a shape memory alloy which is at a temperature slightly above austenite finish
temperature, now when a load is applied to shape memory alloy it gets deformed and when load is
removed, deformation also gets removed and shape memory alloy regains its original shape as
observed in elastic materials. This phenomenon is called pseudo elasticity.

Super elasticity: In shape memory alloys when they are in pseudo elastic region, deformation gets
removed only on removal of load as in elastic materials and is not due to rise in temperature. The
shape memory alloys can also be deformed by more than 100% by application of load and hence this
type of elastic behaviour is called as super elasticity.

Consider a shape memory alloy which is at a

temperature slightly greater than austenite finish
temperature Af as shown. When a load is applied, the
material starts to deform and as load is increased
deformation continues and the alloy enters into
martensite phase. Now when load is removed,
deformation is removed and material regains its shape,
enters into austenite phase as temperature is above
austenite finish temperature.
Thermo mechanical behavior
The mechanical behaviour of shape memory alloy at different temperatures and stress values is called as
thermo-mechanical behavior of shape memory alloy.

Consider a shape memory alloy which is at a lower temperature (T 1) the alloy is in martensite phase.
When a load is applied, alloy gets deformed and when load is removed deformation is not completely
removed as shown in curve A. The deformation is removed on heating.

Consider the shape memory alloy at a temperature

Austenite
slightly above austenite finish temperature (T2). When
load is applied the alloy is deformed and when the C T3
load is removed it regains its original shape as in elastic
T1 < T2 < T3
materials and this behaviour is called as pseudo
elasticity and is shown in curve B.
Pseudoelasticity
B T2
When shape memory alloy is at a high temperature T3,
it is in austenite phase and when a load is applied, it
gets deformed and when load is removed, deformation >
Martensite
is not removed and this is shown in curve C. A T1

Removal of strain or
deformation on heating
Properties
Shape memory alloys are
 highly flexible
 ductile
 bio-compatible
 exhibit high corrosion resistance.

Application
• Blood clot filters: Shape memory alloys are made to a particular shape and are introduced into
blood veins which acts as filters and filters out blood clot.
• Used in fire safety alarms.
• Used in safety valves to shut off flammable and toxic gases in case of fire accidents.
• Used in toys, force actuators, eye glass frames, etc.
• Used as retractable antennas in mobile phones.
• Used as shape wires(arch wires) in orthodontic correction treatment in dentistry.
• Used as guide wire to steer catheters in cathlab in cardiology.

• Cryogenic hydraulic coupling: Shape memory alloy is used in coupling or joining pipes. Shape
memory alloy in tube form with diameter slightly less than the diameter of pipes to be connected is
used. Temperature of the alloy is reduced so that the material is in soft martensite phase. Now the
two pipes to be joined are introduced into the shape memory alloy tube or coupling as the tube is
soft the two pipes enter into the coupling easily and after this the coupling is heated. The coupling
returns to its original size and thereby forms a very tight pipe fitting joining the two pipes.
Liquid Crystal Display(LCD)

Liquid crystal display is a device which does not produce light but only scatters or reflects light and produce
the required pattern. LCD consumes only less power and is used in watches, calculators, TV Screens,
computer screens, CRT display and advertising boards.

The important part of LCD is LCD cell. LCD cell consists of

a liquid crystal material placed between two glass plates
and the glass plates are coated with a transparent
conducting layer (Indium doped tin oxide, In2O3) to take
external electrical connections. The thickness of LCD cell
is less than 10µm.

Liquid crystal state is a phase of matter

exhibited by some organic materials over a
certain temperature range. Below that
temperature it is solid and above the
temperature it is a liquid.
Liquid crystals have their molecules arranged in a regular orderly, periodic manner as seen in crystals
but at same time they also exhibit the flowing nature or fluid nature associated with that of liquids.
So they are called as liquid crystals.

In liquid crystals, molecules are rod like in nature and called as cigar. The molecular arrangement and
orientation in liquid crystals are called as director. Based on orientation of molecules in liquid
crystals, they are classified as follows.

 Nematic : The molecules are arranged parallel to

surface length wise.

 Cholestric: The medium is divided into layers and

orientation of molecules are different in

different layers. But as we move from

one layer to another, there is gradual
rotation in orientation.

 Smectic : It consist of flat layers of cigar-shaped

molecules arranged in an orderly manner.
 Twisted nematic liquid crystal display
The most commonly used twisted nematic liquid crystal is 4-methoxy benzylidene - 40 butylanline
(MBBA). This liquid crystal behaves as a liquid crystal in temperature range of 20 o to 40oC.
In nematic liquid crystals, the molecules are arranged parallel to one another and there is molecular
movement. The orientation of molecules also depends on surface in contact. Generally, molecules are
oriented with respect to surface with which they are in contact in two different ways. This orientation is
called as ordering of molecules. The two different ordering are,

Homogeneous ordering: The molecules are arranged parallel to the surface.

Homeotropic ordering : The molecules are aligned perpendicular to surface.

It is possible to change from one orientation to another

by applying force or electric field.
Construction:
The nematic liquid crystal is placed between two glass plates which are coated with transparent
conducting layer and this forms the LCD cell. The glass plates are treated such that molecules are aligned
parallel to surface of glass plates. But the alignment of molecules at one glass plate and alignment of
molecules at next glass plate are at 90o to one another.
The molecules present in between two glass plates have their orientation gradually rotated as we move
from one glass plate to another.
When an electric field is applied between glass plates,
molecules of the liquid crystal align parallel to the
field. Liquid Crystal
When a plane polarized light, with direction of
polarization parallel to molecular orientation at glass Orientation of molecule
turned through 90°
plate is incident.
• In absence of electric field, the direction of
polarization of light emerging out of the cell is
rotated through 90o
Liquid Crystal
• when an electric field is applied between plates,
then the direction of polarization of light emerging
out of cell is not rotated through any angle. Orientation of molecule
aligned parallel to electric field
The LCD cell is placed between two polaroids. The direction of polarisation of the two polaroids are at 90 o to
each other. The direction of polarisation of polaroid I is parallel to alignment of molecules at front face of cell
and direction of polarisation of polaroid 2 is parallel to orientation of molecules at back face of the cell.

Reflector type LCD

Direction of polarization of
Without electric field light turned through 90°
Liquid Crystal

Reflector

Polaroid 1 Polaroid 2

With electric field Direction of polarization of

light remains same
Liquid Crystal

Reflector

Polaroid 1 Polaroid 2
Transmission type LCD
Working
In absence of electric field
Monochromatic light is incident on Polaroid - I and the light gets polarized and it enters into LCD cell
as its direction of polarisation is same as direction of polarisation of polaroid 1. As the light passes
through cell, its direction of polarization is rotated through 90° and light emerging out of cell has its
direction of polarisation rotated through 90o. Now light incident on Polaroid 2 has its direction of
polarisation parallel to that of polaroid 2. So the light passes through polaroid 2 and reaches the
reflector where it is reflected and it retraces its path and field of view at front face appears bright.
When an electric field is applied
When an electric field is applied the molecules in cell are aligned parallel to applied field. So the
polarized light passing through the LCD cell is not rotated through 90 o. The light entering into
Polaroid 2 has its direction of polarisation perpendicular to that of Polaroid 2. So no light emerges
out of Polaroid 2. So there is no reflected light and field of view is dark..
With no electric field – field of view is bright.
With electric field - field of view is dark

In transmission LCD s, there is no reflector and transmitted light is considered

The LCD cell is arranged in a seven segment format or matrix format and by exciting the required
pattern the alphabet or numbers or alphanumeric are displayed.
THANK YOU