BNMIT, Bangalore Applied Physics (22PHC112/122) Study Material

Module-5: Modern Engineering Materials

Nano Materials

Introduction to Nanoscience and Nanomaterials:

Nanoscience is the study of material behavior at nanoscale. The word nano is from the Greek
word ‘Nanos’ meaning Dwarf. It is a prefix used to describe "one billionth" of meter, or
0.000000001 m=1nm.To get a feeling of how small nanometer is, take the example of human hair
which is about 75000 nm. 1nm size nanomaterial can have around 50 atoms, whereas 20nm size
nanomaterial can accommodate around 10000 atoms.
Nanoscience is an emerging, interdisciplinary science involving physics, biology, chemistry,
materials science, engineering, computer science etc. Richard Feynman was the first one to point out
the possibility of novel properties of a material when it is made in nanometer length scale during his
famous talk "There's Plenty of Room at the Bottom” at Caltech university on 29th December in 1959.
Nanotechnology is the creation of USEFUL/FUNCTIONAL materials, devices and systems (of any
size) through control/manipulation of matter on the nanometer length scale (1-100nm) and exploitation of
novel phenomena and properties which arise because of the nanometer length scale. The term nanotechnology
was coined in 1974 by Norio Toniguchi at the University of Tokyo. The physics of nanotechnology is also
sometimes called as mesoscopic physics.
Nanomaterial is one which has at least one of its dimensions in the nanometric regime and at least, one
of its properties is Size-dependent. The properties which could change are physical, chemical, biological,
magnetic, optical, electrical, mechanical etc.
Ex: Natural Nanomaterials- DNA, Virus.
Artificial Nanomaterials: Carbon nanotubes, fullerenes, inorganic nanowires, metal quantum
dots etc.
The properties of materials in the nanoscale changes mainly because of two reasons namely
quantum size effect and increase in surface to volume ratio.

Surface area to volume ratio:

The surface area to volume ratio for a material or substance made of nanoparticles has a significant
effect on the properties of the material.
Firstly, materials made up of nanoparticles have a relative larger surface area when compared to the
same volume of material made up of bigger particles.

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For example, let us consider a sphere of radius r
The surface area of the sphere will be 4πr2
The volume of the sphere = (4/3) πr3
Therefore, the surface area to the volume ratio will be 4πr2/(4/3πr3) = 3/r
It means that the surface area to volume ratio increases as the radius of the sphere decreases and vice
versa. It also means that when a given volume of material is made up of smaller particles, the surface
area of the material increases. Therefore, as particle size decreases, a greater proportion of the
particles are found at the surface of the material. So, materials made of nanoparticles have a much
greater surface area per unit volume ratio compared with the materials made up of bigger particles.
This leads to nanoparticles being more chemically reactive. As chemical reactions occur between
particles that are on the surface, a given mass of nanomaterial will be much more reactive than the
same mass of material made up of large particles. This means that materials that are inert in their bulk
form are reactive when produced in their nanoparticle form.

Density of states in 3D, 2D, 1D and 0D Quantum Structures (Quantum confinement):

The density of states (DOS) for various quantum structures as a function of energy are shown in
below figure.
In 3-D structure i.e., in bulk material DOS represented as g(E) is
parabolic in shape. DOS varies continuously as a function of energy E.
Typically g(E) is of the order of 1026m-3eV. The expression for DOS in the
energy range dE in this case is given by
8 √2 𝜋 𝑚3/2
𝑔(𝐸)𝑑𝐸  =    [ 3
] 𝐸1/2  𝑑𝐸
ℎ
Where m is mass of electron and h is Planck’s constant.
When the reduction from the bulk material is in one direction, it results in 2-D structure and is
called quantum film. For 2-D quantum structure, the DOS represented as D(E) varies as a step
function i.e. there will be sudden rises in D(E) at certain energy values as shown in below figure.
Typically, D(E) is of the order of 1018m-2eV. The expression for DOS in the
energy range dE in this case is given by
 𝑚∗
𝐷(𝐸)𝑑𝐸  =    [ ] ∑ 𝐻(𝐸 − 𝐸𝑖 )  𝑑𝐸
𝜋ℎ2
Where m* is the effective mass of electron and, H(E-Ei) is the Heaviside step
function and its value is zero for E<Ei and, 1 for E>Ei. Ei is the ith energy level in
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the sub band.
When the reduction from the bulk material is in two directions, it results
in 1-D structure and is called quantum wire. For 1-D quantum structure, the
DOS represented as Ω(E) variation is not smooth as in case of 3-D structure, not
even constant over certain energy region as in 2-D structure. The density hits
peaks at certain energy values as shown in below figure and decreases rapidly in
the range in-between. Typically, Ω(E) is of the order of 109m-1eV. The
expression for DOS in the energy range dE in this case is given by
 √2𝑚 𝑛 𝐻(𝐸−𝐸𝑖 )
𝛺(𝐸)𝑑𝐸  =    [ ] ∑ 𝑖    𝑑𝐸
𝜋ℏ √𝐸−𝐸𝑖

Where m is the effective mass of electron and, H(E-Ei) is the Heaviside step function and its value is
zero for E<Ei and, 1 for E>Ei. Ei is the ith energy level in the sub band. ni is
degeneracy factor.
When the reduction from the bulk material is in all the three directions, it
results in 0-D structure and is called quantum dot. For 0-D quantum structure,
the permitted energy values are not continuous but form discrete bunches of
varying densities as shown figure below. This is because of the confined
condition for the electrons.

Figure: Density of states versus Energy for different quantum structures

Synthesis of Nanomaterials:
To synthesis nanoparticles, the two approaches used are top-down approach and bottom-up
approach.
These two approaches are briefly discussed below.
Top–Down Approach:
In this approach, the material is reduced from bulk size to nano-size.
Ex: Ball milling method and nanolithography.
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Bottom–Up Approach:
In this approach, the matter in atomic or molecular level is assembled to form tiny clusters which
grow to reach nano-size.
Ex: Arc discharge method, chemical vapour deposition method, physical vapour deposition method,
sol-gel method etc.
The top-down and bottom-up approaches are depicted in below figure.
Top-Down Approach Bottom-Up Approach

Ball Milling Method of synthesis of Nanomaterials:

This is one of the top-down approach methods to synthesise nanomaterials. It consists of a
hollow cylindrical chamber that can rotate about its
own axis as shown in below figure. The hard and
heavy balls made of tungsten carbide or steel are
placed inside the chamber. The chamber is mounted
such that, its axis is slightly inclined to the
horizontal to enable the material inside to slide and
accumulate around in one region.
Figure: Ball Milling
The given bulk material is crushed into small grain size by some conventional method and fed
into the chamber. As the cylindrical chamber is rotated around its axis, the balls get carried upwards.
But under gravity, they drop down and hit the sample with high speed. This happens repeatedly and

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the material will be crushed to get reduced to nano-size particles. In this method, the speed of rotation
of chamber should not cross certain critical speed beyond which, balls instead of falling down, will
be carried along the inner surface of the chamber. Then the material misses the hit by balls and
reduction in size stops before reaching nano-size.
This method is used to synthesise metallic and ceramic nanomaterials. The advantage of this
method is that it can be used for large scale production of nanomaterials at low cost. Further, it can be
used to grind material irrespective of its hardness. The disadvantage of this method is that, because of
nature of use purity of the material is affected.

Sol–Gel Method of Synthesis of Nanomaterials:

This is one of the bottom-up approach methods to synthesise nanomaterials. This method is
mainly used to synthesise metal oxide nanomaterials.
The following steps are involved in the synthesis of nanomaterials by this process.
i. Preparation of sol
ii. Conversion of sol to gel
iii. Aging of gel
iv. Removal of solvent
v. Heat treatment

A sol which is a colloidal suspension of small solid particles in a solvent, is prepared by dispersing a
metal salt or metal alkoxide like chlorides, nitrates and acetates which are called precursors (staring
reactants) in a solvent. Sol is further converted into a gel by hydrolysis and condensation of
precursors. Hydrolysis and condensation reactions are initiated by addition of an acid or a base
catalyst. A gel is a state where both liquid and solid are dispersed in each other and is a solid
network capturing a liquid. Gel on ageing for a known period of time, finally condenses to nanoscale
clusters of metal hydroxides. The encapsulated liquid can be removed from gel by evaporative
drying. The sample thus obtained is heat treated (called calcination at high temperature) to obtain
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dense nanoparticles. By this method oxides like zinc oxide, tin oxide etc. are synthesised. This
method is depicted in figure above.
Carbon Nanotubes (CNTs):
CNT is configurationally equivalent to a two dimensional graphene sheet rolled into a tube.
CNT is a tubular form of carbon with diameter as small as 1 nm and length few nanometers to
microns.
Carbon nanotubes were discovered accidently by a Japanese scientist Iijima in 1991 when he was
synthesizing Fullerenes by arc discharge method.

Graphene Carbon Nanotube (CNT)

Types of CNTs:
There are two types of CNT depending on the number of rolled graphene layers namely;
Single Walled Nanotubes (SWNT): These CNTs have only one layer of rolled graphene sheet as
shown in below figure.
Multi Walled Nanotubes (MWNT): These CNTs have more than one rolled graphene sheets such that
bigger ones enclosing the smaller ones as shown in below figure.

SWNT MWNT
Structures of CNTs:
Three structures of CNTs are possible depending upon how the two ends of graphene sheet meet
along namely;

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1. Arm chair structure
2. Zig-zag structure and
3. Chiral structure
The resulting molecular structures are defined by what is called roll-up vector denoted by “T”. Roll-
up vector is the axis about which the sheet is rolled.
If the rolling vector T is parallel to C-C bonds in graphene sheet, the structure is called Arm chair
structure. All the arm structures have metallic character.
If the rolling vector T is making certain angle with C-C bonds, two structures are formed namely
Zig-zag structure and Chiral structure depending on the angles. 1/3 of these two structures are metals
and 2/3 of them are semiconductors.
These structures are shown in below figure.

Properties of CNTs:
CNTs exhibit the following excellent properties.
1. Mechanical properties: The tensile strength of CNT's is much higher than steel. They are 100
times stronger than steel. In addition to it, the weight of CNTs is about only one sixth that of
steel. They have the highest tensile strength of all known materials so far. They are also
highly elastic.
2. Thermal conductivity: They possess thermal conductivity which is twice that of diamonds.
They retain their physical structure in vacuum even up to 2800° C, i.e., they are thermally
very stable.
3. Electrical properties: They can be metallic or semiconducting depending on their structure,
size and how the two ends of graphene sheets are joined. Their current carrying capacity is
1000 times that of copper
4. CNT is excellent field emitter and can be used in Flat panel TV screens.
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5. CNT exhibits property of functionalization which means other chemical groups can be
attached to the tip or side wall easily.

Applications of CNTs:

The excellent properties of CNTs are used in the following applications.

1. Semiconductor CNTs are used in making electronic components such as logic gates and
transistors which can be used for computing purposes.
2. Excellent mechanical properties of CNTs are made use in making high strength composites,
cables, beams, body armors etc.
3. Excellent thermal conductivity property of CNT is used in heat exchangers.
4. The high current carrying capacity of CNTs is used as quantum wire interconnect in
semiconductor packages.
5. CNTs are used in making Flat panel TV screens because of their excellent field emission
property.
6. CNTs are used for hydrogen storage and in lithium-ion batteries.
7. CNTs are used as nano-electrode in biosensors and atomic force microscopy (AFM).
8. CNTs are used as chemical sensors to detect hazardous chemicals in the atmosphere.
Principle, Construction, Working and Applications of Scanning Electron Microscope (SEM):
Principle:
The principle used in the working of SEM is the wave nature of electrons. An electron accelerated
under a potential difference of V volts behave like a wave of wavelength given by

12.26 o 1.226
= A= nm
V V

Construction &Working:
The typical block diagram of SEM is shown in below figure. It consists of a highly evacuated
chamber. Inside the chamber an electron gun which consists of filament and anode is placed at the
top. There are two magnetic lenses namely condensing lens ‘C’ and objective lens ‘O’. A scan coil
accompanies the objective lens. There is a spray aperture using which spherical aberration during
focussing is minimised. A flat surface called stage is provided at the bottom of chamber to place the
specimen under investigation. Three detectors namely x-ray detector, secondary electron detector and
back scattered electron detector are placed as shown in figure which could be used selectively
depending on the application. The most common mode used is by detection of secondary electrons.

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Figure: Scanning Electron Microscope

The sample to be investigated is placed on the stage provided and then chamber is evacuated
using vacuum pump. Electrons are emitted by filament by thermionic emission. A suitable positive
potential is applied to anode to get electrons of required energy or wavelength. These energetic
electrons are converged by condensing lens ‘C’ after passing through the spray aperture. The beam
then passes through objective aperture where the size of the beam can be controlled. A thinner beam
then enters into the field of objective lens ‘O’. The objective lens focuses the beam on to the desired
spot on the specimen. Scan coils attached to objective lens helps the beam to scan the specimen in a
particular way.
Upon incident on the specimen, electrons are knocked out from the specimen due to impact of
the beam. These are called secondary electrons. X-rays are produced when electron jumps from
higher shell fill up these knocked out electron position in the lower shells. Some incident electrons
are back scattered from the sample and are called back scattered electrons. The secondary electrons,
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X-rays and back scattered electrons are detected by respective detectors and corresponding signals
are produced. This signal is converted into a micro spot of corresponding brightness on a screen. The
beam focus is shifted from one spot to another in order to cover the entire specimen and in each case
micro spots are recorded on the screen. This way the image is built on the screen point by point.
SEM can achieve resolution better than 1nm.

Applications of SEM:
SEM has number of applications. Few of them are mentioned below.
1. SEM is used to morphological investigations of organic and inorganic specimens.
2. SEM is used to study chemical composition of materials.
3. SEM is used to study crystal structure of materials.
4. SEM is used in forensic investigations.
5. SEM is used to analyse fracture in materials.

Composite Materials
Introduction
The development of composite materials as well as the related design and manufacturing
technologies is one of the most important advances in the history of materials. Composites are
multifunctional materials having unprecedented mechanical and physical properties which can be
tailored to meet the requirements of a particular application. Many composites also exhibit great
resistance to wear, corrosion, and high-temperature exposure. These unique characteristics provide
the mechanical engineer with design opportunities which are not possible with conventional
materials.
In designing composite materials, scientists and engineers have ingeniously combined various metals,
ceramics, and polymers to produce a new generation of extraordinary materials. Most composites
have been created to improve combinations of mechanical characteristics such as stiffness, toughness,
and ambient and high-temperature strength.

Definition:
Composite materials can be defined as the mixture of two or more different constituents or materials
with significantly different chemical or physical properties.
Examples:

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• Concrete: Particulate composite of aggregates (limestone or granite), sand, cement and water.
• Plywood: Several layers of wood veneer glued together.
• Fiberglass: Plastic matrix reinforced by glass fibers.
• Fibrous composites: Variety of fibers (kevlar, graphite, nylon, etc bound together by a
polymeric matrix.
• Wood: Cellulose fibers bound by lignin matrix.

Note:
1. An alloy which has a two-phase microstructure which is produced during solidification from a
homogeneous melt, or by a subsequent heat treatment whilst a solid, is not normally classified
as a composite.
2. Composites have two (or more) chemically distinct phases on a microscopic scale, separated
by distinct interface, and it is important to be able to specify these constituents.

Classification of Composite Materials:

The classification of the composite materials depends on the type of the matrix (constituent is
continuous and in greater quantity) and the reinforcement (dispersed material may be continuous or
discontinuous) they are using.

The classification of composite materials based on matrix:

Composites are usually classified by the type of material used for the matrix. The four
primary categories of composites are
1. Metal matrix composites (MMCs): Metal Matrix Composites are composed of
metals such as aluminum magnesium, iron, cobalt, copper etc. as a matrix material.
2. Ceramic matrix composites (CMCs): Ceramic Matrix Composites are composed of
ceramic as a matrix material.
3. Organic matrix composites (OMCS)
a) Polymer matrix composites (PMCs): Polymer Matrix Composites are composed
of polymer as a matrix material.
b) Carbon matrix composites (CAMCs): Ceramic Matrix Composites are composed
of Carbon as a matrix material.
The classification of composite materials based on reinforcing materials:

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1. Particulate Composites: Particulate Composites consist of a matrix reinforced by a dispersed
phase in form of particles.
a) Composites with random orientation of particles.
b) Composites with preferred orientation of particles. Dispersed phase of these materials
consists of two-dimensional flat platelets (flakes), laid parallel to each other.
2. Fibrous Composites:
i) Short-fiber reinforced composites: Short-fiber reinforced composites consist of a matrix
reinforced by a dispersed phase in form of discontinuous fibers (length < 100*diameter).
a. Composites with random orientation of fibers.
b. Composites with preferred orientation of fibers.
ii) Long-fiber reinforced composites: Long-fiber reinforced composites consist of a matrix
reinforced by a dispersed phase in form of continuous fibers.
a. Unidirectional orientation of fibers.
b. Bidirectional orientation of fibers (woven).
3. Laminate or structural Composites: When a fiber reinforced composite consists of several
layers with different fiber orientations, it is called multilayer (angle-ply) composite or
laminates.

Advantages and disadvantages of composites:

Advantages:
• Composites are light in weight, compared to most metals. Their lightness is important in
aircraft, where less weight means better fuel efficiency.
• Composites give designers nearly unlimited flexibility in designing shapes and forms. High
impact damage resistance.
• High resistant to fatigue and corrosion degradation.
• Composite materials are extremely strong for their weight compare to conventional metallic
design due to high strength-to-weight ratio.
• The fibre pattern can be tailored to efficiently sustain the applied loads. This directional
tailoring capabilities allow products to meet the design requirements.
• Structures made of composites have a long life and need less maintenance.
Disadvantages:
• Composites are more brittle than wrought metals and thus are more easily damageable.
• Matrix is susceptible to environmental degradation.
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• Transverse properties may be weak.
• Costs of raw materials and fabrication are expensive.
• Cracks and delamination in composites are mostly internal and hence damage inspection
require complicated inspection techniques.
• Reuse and disposal of composite material will be difficult.

Applications:
Composites offer many benefits such as corrosion resistance, light weight, strength, lower
material costs, improved productivity, design flexibility, and durability. Therefore, there are wide
range of applications of composite materials in various industries.
1. Space: Composite materials are used in building antenna, radar, satellite structures, solar
reflectors, etc.
2. Aerospace: Composite materials are being specified for aerofoil surfaces, compressor blades,
engine bay doors, fan blades, rotor shafts in helicopters, turbine blades, turbine shafts, wing
box structures, etc.
3. Automobiles: Composite materials are utilized in manufacturing of automobile body, bumper,
mudguards, door panels, dashboard, driveshaft, fuel tank, CNG cylinder, chassis, fender, etc.
4. Wind turbine blades: Composite material are used to manufacture rotor blades, nose cone,
nacelle cover, accessories for wind electric generators.
5. Sports: Composite materials have extensive applications in manufacturing of sports
equipment such as skis, surfboards, windsurfing, table tennis boards, slats, and gliding wing
spar, Tennis, badminton, fishing rods, golf clubs, baseball bats, hockey sticks, pole shaft,
Sword, etc.
6. Marine industry: The marine industry uses composites to help make hulls lighter and more
damage-resistant. With their corrosion resistance and light-weighting attributes, marine
composite applications include boat hulls, bulkheads, deck, mast, propeller, and other
components for military, commercial, and recreational boats and ships

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