Department of Physics Engg.

Physics – II Course Material UNIT - V

V – UNIT Modern Engineering Materials

Introuduction:

Material science is a branch of science which deals with the properties of

materials. The continuous developments in the field of science and engineering have
given the way to new technologies and applications. Scientists and technologists are
finding out new materials for „high – tech‟ applications.

The Fast growing fields such as electronics, photonics, photoelasticity, fibre optics
and laser technology require efficient and stable new materials.

Hence, they must posses novel properties like large optical non-linearity‟s,
optoelectronic property, high sensitivity to light and large thermal and electrical
conductivities. They should also have good mechanical strength, toughness, ductility and
lightness.

Materials used in „High – tech‟ applications are usually designed for maximum
performance and they are normally expensive. Examples of such materials include
titanium alloys for supersonic airplanes, magnetic alloys for computer discs, spherical
ceramics for the heat shield of space shuttle, etc.,

Let us discuss some of the newly developed enegineering materials, their properties and
applications.

SHAPE MEMORY ALLOYS

Definition
Shape memory alloys (SMA) are the alloys that changes its shape to new shape and while
heating/cooling it will return to its original shape.

Transformation temperature
The range of temperature at which the SMA switches from new shape to its original shape
is called transformation temperature or memory transfer temperature.
Phases of Shape memory alloys (SMA)
MARTENSITE:

1
Department of Physics Engg. Physics – II Course Material UNIT - V

Martensite is an interstitial super solution of carbon in α-iron and it cyrstallizes into twinned
structure. The SMA will have this structure generally at lower temperatures and it is soft in this
phase.AUSTENITE:
Austenite is the solid solution of carbon and other alloying elements in γ-iron and it
cyrstallizes into cubic structure. The SMA will attain this temperatures and it is hard in this
phase.

TYPES OF SMA

• One way SMA- Though there is some change in the temperature the SMA remains in the
phase.

2
Department of Physics Engg. Physics – II Course Material UNIT - V

• Two way SMA- The type of materials which produces spontaneous and reversible
deformation just upon heating and cooling even without load

6. 6 CHARACTERISTICS OF SMAS:

1. Shape memory effect

At lower temperatures the SMA will be in martensite structure and when it is heated then it will
change its shape to austenite structure and while cooling it will again return to martensite form.
Explanation:
The original shape is recovered due to two different solid phases of material, namely
martensite and austenite. The martensite structure is a low-temperature phase and it is
relatively soft. The austenite structure is a high-temperature phase and it is hard

 On heating , martensite deformed and becomes austenite (shape recovery) and upon
cooling gets transformed to twinned martensite (fig 6.5)

3
Department of Physics Engg. Physics – II Course Material UNIT - V

Fig. 6.5 Material crystalline arrangement during shape memory effect.

Transformation occurs over a range of temperatures.

 Psuedoelasticity
It occurs in some type of SMA in which the change will occur even without change in
its temperature.

 Super elasticity

The shape memory alloys which change their shape at constant temperature.

 Hysterisis

The temperature range for the martensite to austenite transformation which takes
place upon heating is somewhat higher than that for the reverse transformation upon
cooling.

Hysteresis is generally defined as the difference between the temperature at which

the material is 50% transformed to austenite upon heating and 50% transformed to
marteniste upon cooling. The difference can be upto 20-30oC.

4
Department of Physics Engg. Physics – II Course Material UNIT - V

Fig. 6.7 Hysteresis curve for SMA‟s

6. 7 PROPERTIES OF Ni-Ti ALLOY

• High shape memory strain [8.5%]

• Density is 6.45gm/cm3
• Flexible
• High melting point [1300oC]
• Transformation temperature varies from -200oC and 110oC
• High thermal stability
• High corrosion resistance

6. 8 APPLICATIONS OF SHAPE MEMORY ALLOYS:

• Eye glass frames

• Toys
• Helicopter blades
• Blood clot filter
• Fire safety valves
• Coffee makers
• Cyrofit hydraulic couplings
• Circuit edge connectors

6. 9 ADVANTAGES AND DISADVANTAGES OF SHAPE MEMORY ALLOYS:

ADVANTAGES
• Compact
• Safe and smart
• Flexible
• Non-corrosive
DISADVANTAGES
• High cost
• Low efficiency
• Gets deformed
• Tranformation occurs over a range of temperatures.
5
Department of Physics Engg. Physics – II Course Material UNIT - V

7. 1 NANO MATERIALS

Basic of nano-materials:

There exist a special clause of materials in which the atoms do not move away
form each other and its size will be in the order of 1 to 100 nano-meters. These new materials
are called nano-materials.

Definition

Nano-phase materials are the materials in which the atom/grain size is in the order of 1 to
100 nano-metres and these atoms will not move away from each other.

Examples: ZnO, Cu-Fe alloys, Ni, Pd, etc.

SYNTHESIS OF NANO MATERIALS

Nanophase materials can be synthesised in any of the two ways viz.,

i. Top down approach, in which bulk materials are breaked into nanosizes.
ii. Bottom up approach, in which nano materials are made by building atom by atom.
Various techniques are adopted for the synthesis of nano-phase materials viz

Using the above techniques it is possible to produce nano-phase materials in the form of
nano-particles, nano-powders, nano-crystals, nano-films, nano-wires, nano-tubes, nano-dots etc.

The methods for the synthesis of nanomaterials are broadly classified into two ways

(i) Top-down process

(ii) Bottom-up process

Synthesis nanostructured
material

Top-down process Example: Bottom-up process

(Ball milling) Examples:
Chemical vapour dopositor sol-gel

6
Department of Physics Engg. Physics – II Course Material UNIT - V

(i) Top-down process

In this process, the bulk materials are broken into nano sized particle as shown fig. 7.1

Fig. 7. 1 Synthesisi from bulk materials.

Top – down process is an example of solid-state processing of materials.

Example: Mechanical alloying

(ii) Bottom – up Process:

In this process, nano materials are produced by building of atom by a atom as shown fig.
7.2

Fig. 7. 2 Synthesisi from individual materials.

Examples: Chemical vapour deposition

7. 2 TECHNIQUES FOR SYNTHESIS OF NANO MATERIALS

There are few widely known methods to produce nanomaterials. They are

i. Ball milling
ii. Plasma – arching
iii. Chemical vapour deposition
iv. Sol-gel technique
v. Electro-deposition
vi. Mechanical srushing (or) Ball milling
vii. Laser synthesis
viii. Inert gas condensation etc.
7
Department of Physics Engg. Physics – II Course Material UNIT - V

7.3 BALL MILLING:

Principle
In ball milling, small hard balls are allowed to rotate inside a container (drum) and ten it
is made to fall on a solid with force to crush the solid into nano crystal.
Construction and working
The hardened steel or tungsten carbide balls are put in a container as shown in fig. 7.3(a)
along with powder of particles (< 50  m) of a desired material.

Container

Tungsten Carbide balls

Fig. 7.3 (a) A Schematic diagram of ball mill vessel

The container is closed with tight lids. When the container is rotating around the central axis, the
material is forced to press against the walls. The milling balls impart energy on collision and
produce smaller grain size of nano particle (fig . 7.3(a)).

Ball milling is also known as Mechanical alloying or crushing.

8
Department of Physics Engg. Physics – II Course Material UNIT - V

Development of laminar structure and grain

Size refinement

Powders

Hard steel of WC balls Repeated fracture and cold

Welding

Fig. 7.3 (b) Principle of ball milling

Advantages
(i) Few milligram to several kilograms of nanoparticles can be synthesized in a short time.

(ii) This technique can be operated at large scale.

Applications

(i) This method is preferred mainly in the preparation of elemental and metal oxide nano
crystals like Co, Cr, Al-Fe and iron.

(ii) A variety of intermetallic compounds of nickel and aliminium can be formed.

(iii) The ball mill is the key equipment for regrinding. It is widely used for the
preparation of cement, the silicate product, new type building materials, fire – proof materials,
chemical fertilizer, black and non – ferrous metal, glass ceramics, etc.

9
Department of Physics Engg. Physics – II Course Material UNIT - V

Vapour phase deposition method:

Vapour phase deposition techniques is used to fabricate thin films, multilayers,

nanotubes, nanofilaments and nanosized particles of different materials. These materials can be
organi or inorganic. There are generally two types of vapour phase deposition techniques used in
electronic industry. They are
(i) Physics Vapour Deposition (PVD) and
(ii) Chemical Vapour Deposition (CVD)
PVD involves the direct deposition of gaseous phase on the substrate surfaces. CVD on the
other hand involves diffusion with chemical reactions at the substrate surfaces. CVD is a
complex process then PVD.

7. 5. CHEMICAL VAPOUR DEPOSITION:

The deposition of nano films from gaseous phase by chemical reaction on high
temperature is known as chemical vapour deposition.

This method is used to prepare nano-powder.

Principle:
In this techniques, initially the material iis heated to gaseous state and then it is deposited
on a soldi surface under vacuum condition to form anno powder by chemical reaction with the
substrate.

Description and Working:

The CVD reactor built to perform CVD prcesses is shown in fig. 7.5

Chemical vapour deposition (CVD) involves the flow of a gas with diffused reactants
(substances to be deposited in the vapour) over a hot substrate surface.

Resistance heater By-products and gas out

H2 Intert gas
Hydrocarbon
Organometal
(floating catalyst)

Fig 7.5 CVD system

10
Department of Physics Engg. Physics – II Course Material UNIT - V

The gas that carries the reactants is called the carrier gas. While the gas flows over the hot solid
surface, the heat energy increases chemical reactions of the reactants that form film during and
after the reactions.

The byproduct of the chemical reactions are then removed. The thin film of desired
composition can thus be formed over the surface of the substrate.

Advantages
(i) The CVD method is used to produce defect free nanoparticles.
(ii) Due to the simplicity of the experiment, the scaling up of the unit for mass production
in industry is achieved without any major difficulties.

PROPERTIES OF NANO-PHASE PARTICLES

As the size of the nanoparticle is very very less, these materials exhibits pecular physical,
electronic, magnetic, mechanical and chemical properties. Some of them are discussed below.

(i) Physical properties:

(a) The interparticle spacing is very less in nano- materials

(b) It does not have any dislocation in it and they have high strength and super hardness
(c) The melting point of nano-materials will be very less.

(ii) Electrical Properties:

The energy bands in these materials will be very narrow.

(b) The ionization potential is found to be higher for nano- material.
(c) They have more localized molecular bonds.
(d) Nano-materials are capable of storing hydrogen atoms.

(iii) Magnetic Properties:

(a) The posses local magnetic moment within themselves

(b) Exhibits spontaneous magnetisation at smaller sizes
(c) Multi-layer nano-materials has GMR(Giant magneto Resisitance) effect.

S. Material Bulk state Nano-phase state

No.
1 Iron, Ni, Cobalt Ferro-magentic Super Para-Magnetic
2 Sodium, Potassium Para-Magnetic Ferro-magentic
3
Chromium Anti-ferromagnetic Frustrated Para-Magnetic

11
Department of Physics Engg. Physics – II Course Material UNIT - V

(iv) Mechanical properties:

The hardness of nano-phase materials varies from materials to material. This may be due to
the phase transformation, stress relief, density and grain boundaries.

(b) They exhibit super plastic behaviour.

7. 9 CARBON NANOTUBES (CNT)

A group of nanostructures with large potential applications are carbon nanotubes.

The hexagonal lattice of carbon is simply graphite. A single layer of graphite is called graphene.
(fig. 7.15)
The carbon nanotube (CNT) consists of a graphene layer which is roiled up into a
cylindrical shape.

Fig. 7.15 Graphene sheet

When the graphene layer is rolled, the structure is tube like and it is a single molecule.
Each single molecule nanotube is made up of a hexagonal network of covalently bonded carbon
atoms.

In some case, the hexagons are arranged in a spiral form. The layer appears like a rolled-
up chicken wire with a continuous unbroken hexagonal mesh with carbon molecules at the
apexes of the hexagon.

The carbon nanotubes are hollow cylinders of extremely thin diameter 10,000 times
smaller than a human hair.

7.10 STRUCTURES OF CNT:

The CNTs have many structures on the basis of their length, type of spiral and number of
layers. Their electrical properties depend on their structure and they act as both a metal or a
semiconductor.

There are a variety if structures of carbon nanotubes with different properties.

12
Department of Physics Engg. Physics – II Course Material UNIT - V

Types CNT structures:

Three types of nanotube strucres can be considered by rolling a graphite sheet with
different orientations about the axis.

There are
(i) Armchair structures
(ii) Zig-zag structures
(iii) Chiral structures

Armchair structures:

When the axis of the tube parallel to C-C bonds of the carbon hexagons, the structures
shown in fig. 7.17(a) is obtained. It is referred as “armchair” structure.

Zig-zag structures and Chiral structures;

The tubes sketched in figs. 7.17(b) and 7.17(c), referred as zig-zag and Chiral structure.
They are formed by rolling graphene sheet such that the axis of the tube is not parallel to C-C
bonds.

Zig-zag structures consists of tube axis perpendicular to C-C bonds.

In chiral structure, C-C bonds is inclined towards the axis of the tube.

Generally, nanotubes are closed at both ends with half of fullerence structures.

Classification of CNT:

Based on the number of layers, the carbon nanotubes are classified as

(i) Single-walled (SWNTs)

(ii) Multi-walled(MWNTs)

In multi-walled nanotubes, more than one CNTs are coaxially arranged.

13
Department of Physics Engg. Physics – II Course Material UNIT - V

Fig. 7.18 SEM image of CNTs

7.11 FABRICATION OF CARBON NANOTUBES:

Carbon nanotubes are produced mainly by three methods. They are

(i) Electruc arc duscgarge method

(ii) Pulsed Laser deposition
(iii) Chemical vapour deposition

7.14 CHEMICAL VAPOUR DEPOSITION

Principle

The hydrocarbon gas is decomposed at suitable conditions which is used to form carbon
nanotubes on the hot substrate.

Chemical vapour deposition of carbon nanotube is essentially a two-step process

(i) Catalyst preparation.

(ii) Actual synthesis of the nanotubes.

Construction

The experimental set-up used for synthesizing the CNT by CVD is shown in fig. 7.21

Fig. 7.21 Chemical vapour deposition – CNT

It consists of a high temperature vacuum furnace with a provision to maintain the inert
atmosphere. The solid substrate which contains catalyst like cobalt, nickel and iron is kept inside
the furnace. The hydrocarbon and nitrogen gas containers are connected to the furnace.

Working:

14
Department of Physics Engg. Physics – II Course Material UNIT - V

The hydrocarbon gas like mthane (C2H2) is passed into the furnace which is kept at
1373K.
At this high temperature, the methane gas decomposes into carbon atoms. These carbon atoms
condense on a cold substrate which contains the catalyst and forms nano tubes.

The catalyst plays a dominant role in forming the carbon nanotubes. The above process
is continuous and hence, it produce the nanotubes continuously.

Advantages:
1. The purity of the nanotubes produced by this method is very high when compared to
other methods.
2. As the method is a continuous one, the same can be used for mass productions of
nanotubes.
3. The diameter of the carbon nanotubes depends on the thickness of the catalytic film.
4. It is possible to produce carbon nanotubes of diameter 30 to 40 nm of a catalytic film of
thickness 13 nm.
5. In this technique, the carbon nanotubes formed are multiwalled.

7.15 PROPERTIES OF CNTs

(a) Electrical Properties

(i) Carbon nanotubes are metallic or semiconducting depending on the diameter and
chirality (ie., how the tubes are rolled).
(ii) The energy gap of semiconducting chiral carbon nanotubes is inversely
proportional to the diameter of the tube as shown in fig 7.22
The energy bandgap decreased with increase of diameter of the CNTs.
(iii) The energy gap also varies along the tube axis and reaches a minimum value at
the tube ends. This is due to the presence of localized defects at the ends due to
the extra energy states.
(iv) In SWNTs, conduction occurs through discrete electronic states that are coherent
between the electrical contacts (hundreds of nanometers). This means that
nanotubes can be treated as quantum wires atleast at very low temperatures.

0.6
Energy gap(eV)

0.4

0.2

15
Department of Physics Engg. Physics – II Course Material UNIT - V

0 1 2 3 4
100/D [1/A]

Fig. 7.22 Plot of the magnitude of the energy band gap of a semiconducting, chiral
carbon nanotube versus the reciprocal of the diameter of the tube
(10 A=1 nm).

(b) Mechanical Properties

(i) The strength of the carbon-carbon bond is very high therefore any structure based
on aligned carbon-carbon bonds will ultimately have high strength.
(ii) Young‟s modulus of CNT is about 1.8 TPa (1012 Pa about 10 times larger than
that of steel).
(iii) One of the important properties of nanotubes is their ability to withstand extreme
strain.
(iv) The carbon nano tubes can recover from severe structural distortions. This is due
to the ability of carbon atoms to rehybridize.

(c) Physical Properties

(i) Nanotubes have a high strength-to-weight ratio (density of 1.8 g/cm3 for MWNTs
and 0.8 g/cm3 for SWNTs ). This is indeed useful for lightweight applications.
This value is about 100 times that of steel and over twice that of conventional
carbon fibres.
(ii) The surface area of nanotubes is of the order of 10 – 20 m2 /g which is higher than
that of graphite.

(d) Chemical properties

Nanotubes are highly resistant to any chemical reaction. It is difficult to oxidize them and
the onset of oxisation in nanotubes is 100C higher than that of carbon fibres. As a result,
temperature is not a limitation in practical application of nanotubes.

(e) Thermal properties

Nanotubes have a high thermal conductivity and the value increases with decrease in
diameter.

7.16 APPLICATIONS OF CARBON NANOTUBES

The unusual properties of carbon nano tubes have many applications such as battery
electrodes, electronic devices and reinforcing fibers for stronger composites etc.,

(i) Electrical and Electronics applications

16
Department of Physics Engg. Physics – II Course Material UNIT - V

(i) When a small electrical field is applied parallel to the axis of a nanotube, the
electrons are emitted at a very high rate from the ends of the tube. This is called
field emission and it is used in development of flat panel displays.
(ii) Vacuum tube lamps that are as bright as conventional light bulbs with long life
time and more efficient can be produced using CNT.
(iii) Semiconducting carbon nanotubes connecting two gold electrodes from field
effect transistors (FET) device as shown in fig. 7.23. The switching time of these
devices is very fast, with clock speeds of a terahertz which is 104 times faster than
present processors. Further small size allows a large number of component in a
chip.
(iv) Carbon nanotubes with diameters of 2 nm have extremely low resistance and thus
they can carry large currents without getting heated. So they can be used as
interconnects in chip.

(ii) Mechanical Engineering:

(a) Since they are stronger, lighter etc., they are used to make hard metals.
(b) Smart magnetic fluids are used in vacuum seals,magnetic separators etc.,
(c) They are also used in Giant Magneto Resistance (GMR) spin valves.
(d) Nano-MEMS (Micro-Electro Mechanical System) are used in ICs, optical switches,
pressure sensors, mass sensors etc.,

(iii) Electrical, Electronics and communication Engineering

(a) Orderly assembled nano-materials are used as quantum electronic devices and photonic
crystals.
(b) They are used in energy storage devices such as hydrogen storage devices, magnetic
refrigeration and in ionic batteries.
(c) Dispersed nano-materials are used in magnetic recording devices, rocker propellant, solar
cells, etc.,

(iv) Computer Science Engineering and IT:

(a) Nano-materials are used to make CD‟s and semiconductor laser.

(b) These materials are used to store the informations in smaller chips.
(c) They are used in mobiles, lap-tops etc.
(d) Further they are used in chemical/optical computers.

(v) Bio-medical and chemical Engineering:

(a) Consolidated state nano-particles are used as catalyst, electrodes in solar and fuel cells.
(b) Bio-sensitive nano-particles are used in the production of DNA – chips, bio-sensors etc.
(c) Nano-structured ceramic materials are used in synthetic bones.
(d) Nano-matellic colloids are used as film precursors.

7.17 APPLICATIONS OF NANOPHASE MATERIALS:

Nanoparticles are “the small particles with big future”. Because of their extremely small
particles size, they have extremely large specific surface area. Hence, they are chemically very

17
Department of Physics Engg. Physics – II Course Material UNIT - V

active. They are stronger and more ductile. Their electronic states are quite different from those
of bulk.

1. Materials Technology:

 We can synthesis harder metal having hardness 5 times higher than normal metals using
nanoparticles.
 Flexible/dense ceramics and insulators have started replacing metals.
 Stronger, lighter, wear resistant, tougher and flame retardant polymers are synthesized
with nanoparticles as fillers. They are used in replacement of body parts and metals.
 Nanometallic colloids are used as film precursors.
 Useful as magneto-resisitance spin valves.
 ZnO thermistors are used in thermal- protection and current-controlling devices.

2. Information Technology:

 Nanoparticles are used for data storage.

 Quantum electronic devices have started replacing bulk conventional devices.
 Nano dimensional photonic crystals are used in chemical/optical computers.
 Nanophase materials are used to produce very tiny permanent magnets of high energy
products. Hence, they are used in high-density magnetic recording.
 Magnetic devices made of Cu-Fe alloy are used in RAM, READ/WRITE heads and
sensors.

3.Biomedicals

 Biosensitive nanoparticles are used for tagging of DNA and DNA chips.
 Controlled drug delivery is possible using nanotechnology. Diffusion of medicine
through nanoporous polymer reservoir as per the requirement is very useful in controlling
the disease.
 Nanostructured ceramics readily interact with bone cells and hence finds applications as
an implant material.

4.Energy storage

 Since the hydrogen absorbing capability increases with decrease of size of nanoparticles,
nanoparticles of Ni, Pd and Pt are useful in hydrogen storage devices.
 Useful in magnetic refrigeration
 Metal nanoparticles are very useful in fabrication of ionic batteries.

5.Optical devices

 Nanomaterials are used in making efficient semiconductor laser and CD‟s.

 Nanoparticulate zinc oxide is used to manufacture effective Sunscreens.
 Nanoparticles are used in the coatings for eye glasses to protect from scratch or
breakage.

18
Department of Physics Engg. Physics – II Course Material UNIT - V

6. Transmission lines

Nanophase materials are used in the fabrication of signal processing elements such as
filters, delay lines, switches etc.

7. Nanomicro-Electro Mechanical Systems (Nano MEMS) have direct implications on

intergrated circuits, optical switches, pressure sensors and mass sensors.

8.Molecular Nano-Technology (MNT) is aimed to develop robotic machines, called

assemblers on a molecular scale, molecular-size power sources and batteries.

9. Underwater nanosensor networks are used to detect the movement of ships in an

efficient manner with faster response. They can also detect chemical, biological or
radiological materials in cargo containers.

19