Module - 5 : Functional materials

Functional materials 6 hours

Composites - types and properties; Polymers (ABS and BAKELITE)-
synthesis and application; Conducting polymers- polyacetylene and effect
of doping; Nano materials – introduction, top-down and bottom-up
approaches for synthesis - bulk vs nano (gold); Materials for OLED
Global Advanced Functional Materials Market Segmentation
Based on product type •Advanced functional composites
• Metal matrix composites
• Fibre reinforced plastics
•Advanced functional ceramics
•Nano-materials
•Advanced energy materials
•Conductive polymers
•Others
Based on end users •Healthcare
•Pharmaceuticals
•Energy
•Automobile
•Electrical & electronics
•Chemical
•Aerospace
•Manufacturing
•Building & Construction

India

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What is a Composite Material?
 DEFINITION: A composite material is a combination of two materials with different physical and
chemical properties.
 The materials combined to produce a new material which is specific to a definite work, for instance, to
become stronger, lighter, or resistant to electricity and also improve strength and stiffness.
 The components maintain their identity within the composite, i.e. they do not dissolve or completely
merge into one another.

Fiber reinforced glass

 Constituents of composites
Applications:
Matrix (Continuous phase) :  In automobile industries, transportation
Continuous or bulk material
industries, turbine engines, sports goods (lawn
Reinforcement (Dispersed Phase) : tennis racket) etc
Added primarily to increase the strength and
 Marine applications like propellants, shafts, hulls
stiffness of matrix etc
 Aeronautical applications such as aircrafts,
The reinforcement can be in the form of fibres, interiors, rockets, helicopters, missiles etc,.
particles, whiskers or flakes  Communication antennae, electronic circuit
boards
 Safety equipments like ballistic protection

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Example for composites showing superior properties

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 1. Matrix unfolded: continuous body which encloses the
Constituents of composites
composite and give its bulk form.
Metal matrix composite (MMC)
Ceramic matrix composite (CMC)
Polymer Matrix composite (PMC)
Functions:
Binds the dispersed filament made of Carbon, Glass or
2. Fiber or dispersed medium: It polymer fiber (10µm)
can be a glass fiber, carbon fiber and Transmits and disperse the load to the composite
Aramid fiber filaments
Protects the fibers from chemical action
Prevents cracks due to its elasticity

E
x
a
m
p
l
e
6
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 Synthetic composites
Classification (Man-Made)
of composite Mud Bricks = Mud+ Straw
Reinforced Concrete
materials Fibre glass etc.

Natural Composites
(Exist in animal and plants)
Wood = Cellulose + Lignin
Bone= Hydroxyapatite + Collagen

Based on the
Based on the
geometry of
matrix materials
reinforcement

⮚ Polymer matrix composite (PMCs)

⮚ Particulate reinforced composites
⮚ Metal Matrix composite (MMCs)
⮚ Whisker /Flakes reinforced
⮚ Ceramic matrix composite (CMCs)
composites
⮚ Carbon/carbon composites (c/Cs)
⮚ Fibre reinforced composites
I. Polymer- matrix composites (PMC) Applications of polymer composites

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Types of polymer composites

1. Fiber-reinforced composites
2. Particulate composites
3. Layered composites

1. Fiber-reinforced composites
In this type of composites a filament (glass or metallic fibres) are encapsulated in a
polymer matrix with the help of a bonding agent.
This type of composite posses high tensile strength, elastic modulas, stiffness and lower
overall density (light weight)

1. Glass fibre reinforced 3. Armid-Fibre reinforced

polymer composites polymer composites

2. Carbon fibre reinforced 4. Al2O3 and or/Carbon

polymer composites reinforced metal composites
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1. Glass fibre reinforced polymer composites
It contains glass fibers for improving the characteristics of polymer matrices comprising nylon
and polyester etc.
Properties:

Low density
High tensile strength
High impact resistance
Excellent resistance to corrosion and chemicals

Limitations/Drawback:
Deteriorates at high temperature i.e melts at high temperature – limited application
No stiffness and rigidity and hence can not be used for structural components

Applications:
Automobile parts, storage tanks, plastic pipes etc

Glass fibre products, such as endless glass fibres,

chopped strands, mats, rovings, yarns, milled glass
fibres, glass wool etc. are used as reinforcing materials
in plastics. The strength imparted to the plastic by the
glass fibre and the protection afforded to the glass fibre
by the plastic, provide high profile properties. 10
2. Carbon fibre reinforced polymer composites
Other names : Advance polymer matrix composites and high performance composites

Properties:
Excellent corrosion resistance
Lighter density
Retention of required properties even at elevated temperature
High cost

Applications:
Structural components (wings, body, stabilizer of aircraft) both military and commercial
Helicopters
Recreational equipment (fishing rods)
Sport materials (golf clubs)

Aircraft Brakes

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Main Properties of Carbon Fibre:

High Modulus of Elasticity 200 – 800 GPa.

Tensile Strength 2500 – 6000 MPa.
Density 1750 – 1950 Kg / m3.
Ultimate Elongation 0.3 – 2.5 %.
Carbon fibres do not absorb water.
Carbon fibres are resistant to many chemical solutions.
Carbon fibres withstand fatigue excellently.
Carbon fibres do not show any creep or relaxation.
Carbon fibre is electrically conductive.

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 PANOX® fibers are the precursor
material for this application. Their
excellent textile processing properties
make it possible to produce brake
disks that can withstand
temperatures of over 1000°C.
Our brake disks are manufactured from
preformed nonwoven products, which
are then carbonized into a strong C/C
material. Break Technology

Materials and designs for the aerospace industry must be lightweight,

but at the same time reliable, rigid and strong under extreme strain.
This problem is solved with carbon fiber reinforced composite materials . The process
takes carbon fibers directly from the bobbin and is accomplished mainly without the 13
use of costly textile semi-finished products
The performance of a sports car is shown not just by its acceleration but also by its deceleration values.
The carbon-fiber-reinforced silicon carbide brake disks weigh around 50 percent less than
conventional gray cast-iron brake disks. Other advantages include much better braking response,
higher fading stability, very good control, better directional stability and prevention of brake dust. High
thermal stability, corrosion resistance and wear resistance ensure an exceptionally long brake disk life.

Carbon-fiber-reinforced silicon carbide brake

disks weigh around 50 percent less than
conventional gray cast-iron brake disks.

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3. Aramid-Fibre reinforced polymer composites 2. Long fibre reinforced composites

1. Short fibre reinforced composites These are metal like ductile, respond
catastrophically to compressive
Short Aramid fibre gives effective stress, they are capable of absorbing
reinforcement due to their high energy.
aspect ratio, high surface area,
inherent toughness, heat stability Applications:
and high wear resistance Excellent structural and advanced
Applications: Automobile clutches and engineering materials
brakes Used in commercial and business
Better than the composite containing aircrafts as structural materials,
asbestos helicopters blades, motor housing,
thermal and ballistic protective
apparels

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Example: Boeing 747 and airbus 320 uses composite
3. Aramid-Fibre reinforced polymer composites

Kevlar® and other

polyaromatic amides are
also used as fibres in
fabrics for protective
clothing.
Their fire resistant
properties lead to their
use by firefighters and
their strength means
they are used for body
armour.

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4. Al2O3 and or/Carbon reinforced metal composites

It posses improved specific strength, stiffness, abrasion and creep

resistance, dimensional stability
e.g.1 Al alloy matrix reinforced with Al or C fiber
Ow density, wear resistance, resistant to thermal distortion
Application: Components of engine in automobile industry

e.g. 2. Ni and Co based Alloy matrix reinforced with Al2O3 or W

fibers
Excellent resistant to impact strength, creep and rupture, and high
temperature
Applications: components of turbine engine

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Carbon fibre reinforced with tubular steel

Markets include; telecommunications, automotive (HEV), power semiconductor,

opto-electronics, military and aerospace, heavy transportation, space systems
and satellites, medical, and industrial lighting. Applications within these markets
include; microwave, RF, IGBT, micro-electronic packaging, laser diode, HB-LED’s,
and advanced radar.

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II. Metal- matrix composites (MMC)

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II. Metal- matrix composites (MMC)
❖ Metal Matrix Composites are composed of a metallic matrix (Al,Mg,Fe,Cu etc) and
a dispersed ceramic (oxide, carbides) or metallic phase( Pb,Mo,W etc).

❖ Ceramic reinforcement may be silicon carbide, boron, alumina, silicon nitride,

boron carbide, boron nitride etc.,whereas metallic reinforcement may be
tungsten, beryllium etc.

❖ From a material point of view, when compared to polymer matrix composites, the
advantages of MMCs lie in their retention of strength and stiffness at elevated
temperature, good abrasion and creep resistance properties.

❖ Most MMCs are still in the development stage or the early stages of production
and are not so widely established as polymer matrix composites. The biggest
disadvantages of MMCs are their high costs of fabrication.

❖ There are also advantages in some of the physical attributes of MMCs such as no
significant moisture absorption properties, non-inflammability and resistance to
most radiations.
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Metal- matrix composites (MMC)
❖ Only light metals are responsive, with their low density proving an advantage.
Titanium, aluminium and magnesium are the popular matrix metals currently in
vogue, which are particularly useful for aircraft applications.

❖ If metallic matrix materials have to offer high strength, they require high modulus
reinforcements.

❖ The strength-to-weight ratios of resulting composites can be higher than most

alloys.

❖ The melting point, physical and mechanical properties of the composite at various
temperatures determine the service temperature of composites.

❖ They can withstand elevated temperature in corrosive environment than polymer

composites. However, practically, the choices for low temperature applications are
not many.

❖ The choice of reinforcements becomes more stunted with increase in the melting
temperature of matrix materials. 21
Applications of Metal matrix composites (MMC)

o Carbide drills are often made from a tough cobalt matrix with hard
tungsten carbide particles inside.

o Modern high-performance sport cars, such as those built by Porsche, Military vehicle
use rotors made of carbon fiber within a silicon carbide matrix. brake drums

o Metal Matrix Composite (MMC) are used in Diesel Piston, disk break

o The F-16 Fighting Falcon uses monofilament silicon carbide fibres in

a titanium matrix for a structural component of the jet's landing gear.

o Today these applications are found most often in aircraft components,

space systems and high-end or "boutique" sports equipment.

o MMCs are used for Space Shuttle, commercial airliners, electronic

substrates, bicycles, automobiles, golf clubs and a variety of other
applications.
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III. Ceramic Matrix composite (CMC) Carbon fiber-reinforced silicon carbide
(Cf/SiC) ceramic matrix composites have
promising engineering applications in many
fields.
Among these advanced materials, ceramic
matrix composites (CMCs) are drawn great
attentions for their engineering applications
under extreme conditions because they can
maintain
 Low density
 High strength
 Wear resistance
 Oxidation resistance
 Thermal shock resistance
 Corrosion resistance

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III. Ceramic Matrix composite (CMC)

o A given ceramic matrix can be reinforced with either discontinuous

reinforcements, such as particles, whiskers or chopped fibres,
particulates having compositions of Si3N4, SiC, AlN, titanium diboride,
boron carbide, and boron nitride or with continuous fibres.

o Characteristics of CMC
❖ High-temperature stability
❖ High thermal shock resistance
❖ High hardness
❖ High corrosion resistance
❖ Light weight
❖ Nonmagnetic and nonconductive properties
❖ Versatility in providing unique engineering solutions

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 Ceramic matrix composites (CMC)
❖ Ceramic-matrix composite development has continued to focus on achieving
useful structural and environmental properties at the highest operating
temperatures. The high risk associated with this task foreshadows the relatively
small number of commercial products.

❖ However, development of CMCs for other uses has also been pursued, and
significant commercial products now exist.

❖ Ceramics can be described as solid materials which exhibit very strong ionic
bonding in general and in few cases covalent bonding.

❖ High melting points, good corrosion resistance, stability at elevated temperatures

and high compressive strength, render ceramic-based matrix materials a favourite
for applications requiring a structural material that doesn’t give way at
temperatures above 1500ºC.

❖ Naturally, ceramic matrices are the obvious choice for high temperature
applications.
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Applications:

❖ CMCs find promising applications in the area of cutting tools and in heat
engines where the components should withstand aggressive
environments.

❖ In Aircraft engines - use of stator vanes formed of CMC in the hot

section of the F136 turbofan engine is under consideration.

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Applications of CMC
• Exhaust nozzle flaps and seals in the F414 engine of the Navy F-18 E/F.
The exhaust temperature of the F414 is over 800C (1450F) higher than the F404 engine used in
the previous version of the F-18. As a result, the metal flaps and seals were failing in tens of
hours. The CMC parts consist of a Nicalon (Dow Corning Corp.) fiber with an inhibited carbon
matrix. A thick SiC overcoat and glaze provide protection from oxidation.

Insertion of the CMC flaps and seals has produced a weight savings of nearly 1 kg (2 lb) per
engine relative to the metal parts. Because this mass is at the very back of the aircraft,
additional weight savings can be obtained by removing ballast to shift the center of gravity of
the aircraft. The CMC flaps have a useful life that is at least double the design requirement of
500 hours.

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Applications of CMC

• Ceramic-matrix composites are now also commercially available as brake rotors

for automobiles.

✔The new Porsche braking system uses an MMC brake pad.

✔Ceramic-matrix composite brake rotors have also been demonstrated for the
Inter-City Express high-speed trains in Germany, where a total weight savings of
5.5 metric tons is obtained per train set.
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CLASSIFICATION OF
POLYMERS

Polymers

Natural polymers Synthetic polymers

Ex: Rubber, Wool Ex: Bakelite, PVC, PE

1. Homo polymers – same monomers, Ex: PE

2. Hetero (or) Copolymers – two or more different
monomers, Ex: Nylon 6:6, SBR

1. Linear chain polymers

2. Branched chain polymers
3. Cross linked polymers

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Properties - General

 Chemical and Solvent resistance

 Generally resistant to alkalis and acids but not concentrated oxidizing acids.
 Dissolved by many aromatic and chlorinated hydrocarbons, esters and
ketones.

 Maximum Service temperature

 Temperature index 60-75°C.
 Alloy with Polycarbonate may be as high as 95°C.

 Flammability
 Standard grades are considered as slow burning and usually meet the
requirement.
 The material burns with a smoky yellow flame emitting a pungent gas.

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Applications
Automobile
 Radiator grills, head light housing, seat belt, head lamp fixtures, door knobs, two wheeler front
noise, water panel, helmet, electroplated parts, mirror housing and wheel covers.
Agriculture
 Drinking water system, water vent systems and irrigation systems.

Household
 Plumbing fixtures, table edging, sliding doors, window trucks, refrigerators liners, refrigerator door
handles, pipe fittings, ventilator system components, picnic boxes, food processors, coffee maker
leads, microwave oven tops.

Medical
 IV fluid monitoring controllers, blood glucose meter, surgical clips, emergency intravenous infusion
pump, scanner body, ECG / EEG body frames, cabinets for medical kit, breathing exerciser

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Thermosetting resins or Thermosets

✔ Thermosetting resins can melt and take shape once; after they have solidified, they stay
solid.
✔ They are prepared by condensation polymerisation.
✔ Various polymer chains are held together by strong covalent bonds (cross links)
✔ These plastics get harden on heating and once harden, they cannot be softened again.
✔ They are almost insoluble in organic solvents.

Examples: Bakelite, Polyester

Thermoset Polymers whose individual chains have been chemically cross linked by covalent
bonds and form a 3-D cross linked structure.

⮚Therefore, they resist heat softening and solvent attack.

⮚These are hardened during the molding process and once they are cured, they cannot be
softened and they cannot be recycled and reused

Eg. Phenol-formaldehyde resins, urea-formaldehyde paints.

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Difference between Thermoplastic and Thermosetting Polymers………

Thermoplastic polymers Thermosetting polymers

Consists of long-chain linear polymers Have 3-Dimensional network structures joined by
with negligible cross-links. strong covalent bonds.

Soften on heating readily because Do not soften on heating; On prolonged heating,

secondary forces between the individual they are charred.
chain can break easily by heat or pressure.

By re-heating to a suitable temperature, they can be Retain their shape and structure even on heating.
softened, reshaped and thus reused. Hence, cannot be reshaped.

Usually soft, weak and less brittle. Usually, hard, strong and brittle.

Can be reclaimed from wastes. Cannot be reclaimed from wastes.

Usually soluble in some organic solvents. Due to strong bonds and cross-linking, they are
insoluble in almost all organic solvents.

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 Properties and engineering applications

Types of Thermoplastic resins:

Vinyl resins
(i)PVC
(ii)TEFLON or FLUON
(iii)ABS (Acrylonitrile Butadiene Styrene)

Types of Thermosetting resins:

Phenolic resins or phenoplasts

(iv)Bakelite
(v)Novolac

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 (ii) TEFLON or FLUON (polytetrafuloroethylene) PTFE

✔ Teflon is obtained by polymerization of tetrafluoro ethylene under pressure in the presence of benzoyl peroxide
as catalyst.

Properties:
✔ This polymer is a hard, strong, extreme toughness, High chemical resistance with a high [Link].
and very low surface friction.
✔ High softening point (350 C ), waxy touch, good mechanical and electrical properties.
Due to all these qualities, the polymeric material can be machined.
✔ Its softens at about (350 C ), hence at this high temperature it can be moulded applying high
pressure.

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Thermosetting Plastics:
(a) Phenolic resins or Phenoplasts : Novoloc and Bakelite
Phenolic resins are condensation polymerization products
of phenol derivatives and aldehydes.

At first, Phenol reacts with

Formaldehyde in presence of acidic
/alkaline catalyst to form
Monomethylnol phenol.

Monomethylol phenol further reacts with

Phenol to form a linear polymer “Novolac”.

Water is removed as the by-product.

Bakelite
Novolac 36
Leo Baekeland Bakelite
✔ bakelite is a cross- linked polymer
of phenol and formaldehyde

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Thermosetting Plastics:
Bakelite
✔ Further addition of HCHO at high
temperature and pressure converts Novolac
(soft and soluble) into cross-linked
“Bakelite” (hard and insoluble).

Bakelite

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Bakelite

Properties:
✔Bakelite is resistant to acids, salts and most organic solvents, but it
is attacked by alkalis because of the presence of –OH groups.
✔It possesses excellent electrical insulating property.
✔As thermoset it is difficult to recycle.

Uses:
✔Bakelite is used as an adhesive in plywood laminations & grinding
wheels, etc
✔It is also widely used in paints, varnishes,
✔It is used for making electrical insulator parts like plugs, switches,
heater handles, paper laminated products, thermally insulation foams
etc.

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SBR rubber - Co-polymerisation

SBR: It is a process of polymerization with two different monomers

CH2 = CH2 CH CH2 CH2 CH CH CH2

Catalyst
n + m CH2 CH CH CH2

Styrene Butadiene n m

Styrenebutadiene rubber

11/27/2024 40
Conducting Polymers
• Polymers with a conjugated pi-bond structure often
show higher conductivity when doped with conductive
materials.
• Combination of mechanical and electrical properties
can find good applications in conductive polymers area
as they posses poor mechanical strength.
• Sometimes, in a polymer blend, a bifunctional linker is
doped to increase the conductivity of Polyaniline
(PANI) (having conductivity) and poly-caprolactum
(PCL) (having mechanical strength) blend.
• Conductive polymers can be made using simple
procedures like melt blending, solution blending etc.,
and can be used for antistatic and electromagnetic 41
Some Examples of Conductive Polymers

42
Different Types of Conducting Polymers:
1. Intrinsically conducting polymers (ICP)
2. Doped Conducting polymers
3. Extrinsically conducting polymers (ECP)

Factors that affect the conductivity:

1. Density of charge carriers
2. Their mobility
3. The direction
4. Presence of doping materials
5. Temperature

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1. Intrinsically Conducting Polymers (ICPs)
⮚ Polymer consisting of alternating single and double bonds is called conjugated
double bonds.
⮚ In conjugation, the bonds between the carbon atoms are alternately single and
double. Every bond contains a localised “sigma” (σ) bond which forms a strong
chemical bond.
⮚ In addition, every double bond also contains a less strongly localised “pi” (π)
bond which is weaker.
⮚ Conjugation of sigma and pi-electrons over the entire backbone, forms valence
bands and conduction bands.
Eg: Poly-acetylene, poly-p-phenylene, polyaniline, polypyrrole polymers

Polyacetylene

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2. Doped Conducting Polymers
It is obtained by exposing a polymer to a charge transfer agent either in gas or
solution phase. ICPs possess low conductivity (10-10 S or Mho/cm), but they
possess low ionisation potential and high electron affinity. So they can be easily
oxidised or reduced.
DOPING:
The conductivity of ICPs can be increased by creating positive charges (oxidation)
or by negative charges (reduction) on the polymer backbone. This technique is
called DOPING .
In otherwords….
The polymer structure has to be disturbed - either by removing electrons
(oxidation) from or inserting them (reduction) into the materials. The
process is known as Doping.
There are two types of doping:
1. Oxidation with halogen (p-doping).
2. Reduction with alkali metal (n-doping). 45
(i)p-Doping:
⮚ It involves treating an ICP with a Lewis acid which leads to oxidation process and positive
charges on the polymer backbone are created.
⮚ Some of the p-dopants are I2, Br2, AsF5, PF5 etc.

2(C2H2)n + 3I2 2[(C2H2)n+ I3-

polyacetylene Lewis acid

(ii) n-Doping:
⮚ It involves treating an ICP with a Lewis base which leads to reduction process and
negative charges on the polymer backbone are created.

⮚ Some of the n-dopants are Li, Na, Ca, FeCl3, naphthylamine etc.
_
…-CH=CH-CH=CH-… + C10H7NH2 …-CH=CH-CH=CH- + C10H8
I
+
NH
46
• In p-type doping, the dopant (Iodine, I2) attracts an electron from the polyacetylene
chain to form (I3-) leaving a positive soliton (carbenium ion) in the polymer chain
that can move along its length.
• The lonely electron of the double bond, from which an electron was removed, can
move easily.
• As a consequence, the double bond successively moves along the molecule, and the
polymer is stabilized by having the charge spread over the polymer chain.

Doping in Trans-Polyacetylene 47
Mechanism of Conduction in Polyacetylene

48 48
Conductivity Mechanism in Polyacetylene:
•The mechanism followed by polyacetylene for the transfer of charge from one chain to another is called
intersoliton hopping.
•What is a soliton? The soliton is a charged or a neutral defect in the polyacetylene chain that propagates down the
chain, thereby reducing the barrier for interconversion.

• In n-type doping (This can be  It is obtained by exposing a

polymer to a charge
done by dipping the film in transfer agent in either gas
THF solution of an alkali phase or in solution
metal) soliton is a resonance-
stabilized polyenyl anion of  ICP possess low
approximately 29-31 CH units conductivity (10 Ω cm-1)
-10 -1

in length, with highest but due to their low

ionization potential and
amplitude at the centre of the high electron affinities
defect. based on which they can be
• The solitons (anions) transfer easily oxidized or reduced
electrons to a neutral soliton  Conductivity of ICP can be
(radical) in a neighboring increased by creating
either positive or negative
chain through an isoenergetic charges on the polymer
process. backbone by oxidation or
• The charged solitons are reduction
responsible for making
polyacetylene a conductor.49 49
3. Extrinsically Conducting Polymers
These are those polymers whose conductivity is due to the presence of
externally added ingredients in them.
Two types:
(1) Conductive element filled polymer:
▪ It is a resin/polymer filled with carbon black, metallic fibres, metal
oxides etc. Polymer acts as a binder to those elements.
▪ These have good bulk conductivity and are low in cost, light weight,
strong and durable. They can be in different forms, shapes and sizes.
(2) Blended Conducting Polymers:
▪ It is the product obtained by blending a conventional polymer with a
conducting polymer either by physical or chemical change.
▪ Such polymers can be processed and possess better physical,
chemical and mechanical strength.
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Conductivity of Polymers and Metals

Why doping is required? – to increase

the conductivity of polymers

51 51
Chemistry of display devices specific to OLEDs
An organic light-emitting diode (OLED or organic LED), also known as organic electroluminescent (organic EL) diode, is a light-
emitting diode (LED) in which the emissive electroluminescent (EL) layer is a film of organic compound that emits light in response to
an electric current. Quantum dots are phosphorescent semiconductor nanocrystals that can either emit or alter
light at different frequencies when subjected to electrical energy.

QLED
Flexibility

52
 Working principle of OLEDs
1. The holes lie in the valence band, while the free electrons
are in the conduction band of material.
2. When there is a forward bias in the p-n junction, the
electron which is a part of the n-type semiconductor
material would overrun the p-n junction and join with the
holes in the p-type semiconductor material. Therefore,
regarding the holes, the free electrons would be at the higher
energy bands.
3. When this movement of free electron and hole takes place,
there is a change in the energy level as the voltage drops
from the conduction band to the valance band.
In standard diodes, the release of energy is in 4. There is a release of energy due to the motion of the
the manner of heat. But in LED the release of
electron. (due to conduction of electrons)
energy in the form of photons that would emit
light energy. 5. In standard diodes, the release of energy in the manner
of heat. But in LED the release of energy in the form of
photons would emit light energy.
6. This entire process is known as electroluminescence, and
the diodes are known as a light-emitting diode.

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Nanomaterials

54
Introduction to Nanomaterials
•A nanoparticle is an entity with a width of a few nanometers to a few hundred, containing tens to
thousands of atoms. Their defining characteristic is a very small feature size in the range of 1-100
(nm).

•Nano size:
One nanometre is a millionth part of the size of the tip of a needle.
1 nm = 10-6 mm = 10-9 m

Table 1. Some examples of size from macro to molecular

Size Examples Terminology
(nm)
0.1-0.5 Individual chemical bonds Molecular/atomic
0.5-1.0 Small molecules, pores in Molecular
zeolites Bulk Gold
1-1000 Proteins, DNA, inorganic Nano
nanoparticles
103-104 living cells, human hair Micro
>104 Normal bulk matter Macro 55
Categories of Nanomaterials

56
 Properties of Semiconductor Nanomaterials
⮚The properties of nanosized semiconductor particles depend very
sensitively on the particle size.
⮚ The physical properties of semiconductor nanocrystals are dominated by
the spatial confinement of excitations (electronic and vibrational).
⮚ Quantum confinement that manifests itself in widening of HOMO-LUMO gap
or the bandgap increase with decreasing crystallite size and its implications
on the electronic structure and photophysics of the crystallites has generated
considerable interest.

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 Quantum Confinement

1. In the nanoparticles with some of its dimensions smaller than 10nm, show new effects, since the laws of
classical physics no longer valid and we need quantum physics to explain them.
2. For example, the minimum potential energy of an electron confined in a nanoparticle is higher than
expected in classical physics and energy levels of different electronic states are discrete.
3. Due to quantum confinement, the particle size has a drastic effect on the density of electronic states
and thus on the optical response

58
Size dependent colour of Au nanoparticles
 The enchantment of Au NPs since ancient times, as reflected in
their intense color, originates from the basic photophysical
response that does not exist to nonmetallic particles.
 When a metal particle is exposed to light, the oscillating
electromagnetic field of the light induces a collective coherent
oscillation of the free electrons (conduction band electrons) of
the metal.
 This electron oscillation around the particle surface causes a
charge separation with respect to the ionic lattice, forming a
dipole oscillation along the direction of the electric field of the
light (Fig. 1A).
 The amplitude of the oscillation reaches maximum at a specific
frequency, called surface plasmon resonance (SPR) .
 The SPR induces a strong absorption of the incident light and
thus can be measured using a UV–Vis absorption spectrometer.
 The SPR band is much stronger for plasmonc nanoparticles
(noble metal, especially Au and Ag) than other metals.
 The SPR band intensity and wavelength depends on the factors
affecting the electron charge density on the particle surface
such as the metal type, particle size, shape, structure,
composition and the dielectric constant of the surrounding
medium
59
Size dependent colour of Au nanoparticles

60 60
Size and shape dependent colors of Au and Ag nanoparticles

Note: nanomaterials scatter visible light rather than absorb

⮚ Distance between particles also effects colour

Surface plasmon resonance: Excitation of surface plasmons by light (visible

or infra red) is denoted as a surface plasmon resonance
Localized surface plasmon resonance (LSPR) for nanometer-sized metallic structures
61
61
Quantum Dots and applications
Quantum dots (QDs) are semiconductor particles of few nanometers (<10 nm) in size,
having optical and electronic properties that differ from larger particles.

5 nm

Cancer cell imaging Metal ions sensing Light emitting diode

62
Emission properties of Quantum Dots

1. Band gap decreases as the QDs size increases

2. Emission wavelength becomes red shifted with increase in size of QDs

63 63
Synthetic Procedures of Quantum Dots
1. High temperature synthesis

2. Hydrothermal synthesis 4. Ultrasonication synthesis

3. Microwave synthesis

64
Properties and Applications
•Nanomaterials show unusual
⮚ Mechanical
⮚ Electrical
⮚ Optical
⮚ Magnetic properties.

Hence it has potential applications in

⮚ Different industries
⮚ Biomedical
⮚ Electronic applications.
⮚ For example, long lasting medical implants of
biocompatible nanostructured ceramic and carbides,
⮚ Biocompatible coating
⮚ Drug delivery
⮚ Protection coatings
⮚ Composite materials
⮚ Anti fogging coatings for spectacles and car windows etc.
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⮚ At the nanomaterial level, some material properties are affected by the laws of atomic
physics, rather than behaving as traditional bulk materials.
⮚ Nanomaterials can be metals, ceramics, polymeric materials, or composite materials.
⮚ The beautiful ruby red color of some glass is due to gold nanoparticles (Au NPs) trapped
in the glass matrix.
⮚ The decorative glaze known as luster, found on some medieval pottery, contains metallic
spherical nanoparticles dispersed in a complex way in the glaze.

Rod shaped
Spherical nano Au
AuNPs

66
What makes these nanomaterials so different and so intriguing?

⮚ Deviation from the reduced size and dimensionality of the nanometer-sized building blocks
(crystallites), the numerous interfaces between adjacent crystallites, grain boundaries and
surfaces
⮚ These building blocks have different crystallographic orientation that may lead to incoherent or
coherent interfaces between them
⮚ Lead to inherent heterogeneous structure on a nanometer scale.
⮚ Grain boundaries make up a major portion of the material at nanoscales, and strongly affect
properties and processing.
⮚ Surfaces and interfaces- half or more than half atoms near to interfaces
⮚ Hence, surface properties such as energy levels, electronic structure, and reactivity are different
from bulk materials
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Band Gap in Nano and bulk materials
 In the nano range, one observes a size-
dependence of the emission of semiconductor
nanoparticles[1].
 This is due to the confinement (quantum
confinement) of the electrons and holes in either
one, two or three dimensions where quantum
mechanics predicts discrete energy levels
dependent on the size of the particle[1,2].
 The emission wavelength is proportional to the
square of the size of the particle: λem~ d².
 Nanoparticles are also called quantum dots.
[1]A. Eychmüller et al., Angew. Chem. Int. Ed.2008, 47, 6538.
[2] M. Fox, Optical Properties of Solids, 2nded., 2010, Oxford
University Press, Oxford

As the particle size decreases band gap increases i.e. energy gap
between valence band and conduction band increases due to
quantum confinement.

68
Schematic representation of the ‘bottom up’ and top down’
synthesis processes of nanomaterials

69
Nanoparticles preparation:
❖ Top-down approaches
Any fabrication technique should provide the
⮚ High-energy ball milling/Machining
followings:
⮚ Chemical Oxidation Process (CNTs to QDs)
⮚Identical size of all particles (also called mono sized or
⮚ Electrochemical Oxidation Process (Graphite rod to QDs)
with uniform size distribution
⮚ Lithography (photo- and electrochemical)
⮚Identical shape or morphology
⮚Identical chemical composition and crystal structure
⮚Individually dispersed or mono dispersed i.e., no
❖Bottom-up approaches
agglomeration
⮚Gas Condensation Processing (GCP)/Aerosol­Based Processes
⮚ Chemical Vapour Condensation (CVC)
⮚ Atomic or Molecular Condensation
⮚ Laser ablation
⮚ Supercritical Fluid Synthesis
⮚Wet Chemical Synthesis of nanomaterials (Sol-gel process)
⮚ Precipitation method

70
Schematic representation of the principle of mechanical milling

WC coated
ball
50 µm powder

71
Mineral, ceramic processing, and powder metallurgy industry

❖ Procedure of milling process

⮚ Particle size reduction, solid-state alloying, mixing or blending, and particle
shape changes
⮚ Restricted to relatively hard, brittle materials which fracture and/or deform and

cold weld during the milling operation

⮚ To produce nonequilibrium structures including nanocrystalline, amorphous and
quasicrystalline materials
⮚ Users are tumbler mills, attrition mills, shaker mills, vibratory mills, planetary
mills etc
⮚ Powders diameters of about 50 µm with a number of hardened steel or tungsten
carbide (WC) coated balls in a sealed container which is shaken or violently
agitated. The most effective ratio for the ball to powder mass is 5 : 10.
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• Shaker mills (e.g. SPEX model 8000) uses small batches of powder (approximately 10 cm 3 is
sufficient

❖ Advantage: High production rates

❖ Limitation
⮚ Severe plastic deformation associated with mechanical attrition due to generation of high
temp in the interphase, 100 to 200 oC.
⮚ Difficulty in broken down to the required particle size

⮚ Contamination by the milling tools (Fe) and atmosphere (trace elements of O2, N2 in rare
gases) can be a problem (inert condition necessary like Glove Box)(Fe <1-2% and Trace
elements<300 ppm)
⮚ Protective coating to reduce milling tools contamination (MTC) increases cost of the process
⮚ Working duration (>30 h) increases MTC (>10%)

73
sol-gel method Wet Chemical Synthesis of nanomaterials
Aerogels are gels with nanometer pores, low density, porosity, and high internal area. Due to these properties, aerogels
are widely used in applications that require sound insulation as well as high light transmittance. .e aerogel synthesis
process consists of two stages; in the first stage or the gel-making stage, the solvent penetrates the gel and in the next
stage the solvent is removed or dried.

74
sol-gel method

75
Specific Example : Preparation of SiO2 nanoparticles

Si-(OC2H5)4 can therefore be

regarded as the first
“precursor” for glassy
materials

76
Preparation of Si based nanoparticles

77
Preparation of Si based nanoparticles

78
Steps involved in Sol Gel Process
Step 1: Formation of different stable solutions of the alkoxide (the sol).

Step 2: Gelation resulting from the formation of an oxide- or alcohol-bridged network (the gel) by a
polycondensation or polyesterification reaction

Step 3: Aging of the gel, during which the polycondensation reactions continue until the gel transforms into a
solid mass, accompanied by contraction of the gel network and expulsion of solvent from gel pores.

Step 4: Drying of the gel, when water and other volatile liquids are removed from the gel network.

– If isolated by thermal evaporation, the resulting monolith is termed a xerogel.

– If the solvent (such as water) is extracted under supercritical or near super critical conditions,
the product is an aerogel.

Step 5: Dehydration, during which surface- bound M-OH groups are removed, thereby stabilizing the gel
against rehydration. This is normally achieved by calcining the monolith at temperatures up to 800 0C.

Step 6: Densification and decomposition of the gels at high temperatures (T>800 0C). The pores of the gel
network are collapsed, and remaining organic species are volatilized. The typical steps that are involved in sol-
gel processing are shown in the schematic diagram above.

79
• Sol/gel transition controls the particle size and shape. Calcination of the gel
produces the product (eg. Oxide).
• Sol-gel processing > hydrolysis and condensation of alkoxide-based precursors
such as Si(OEt)4 (tetraethyl orthosilicate, or TEOS).
• The reactions are as follows:
MOR + H2O → MOH + ROH (hydrolysis)
MOH+ROM→M-O-M+ROH (condensation)
• If the aging process of gels exceeds 7 days it is critical to prevent the cracks in gels
that have been cast
• Steps are:
Sol Gel Ageing Drying Dehydration Densification &
Decomposition Product

80
Advantages
• Synthesizing nonmetallic inorganic materials like glasses, glass ceramics or ceramic materials at very
low temperatures compared to melting glass or firing ceramics
• Monosized nanoparticles possible by this bottom up approach.
Disadvantages
• Controlling the growth of the particles and then stopping the newly formed particles from
agglomerating.
• Difficult to ensure complete reaction so that no unwanted reactant is left on the product
• Completely removal of any growth aids
• Also production rates of nano-powders are very slow by this process

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