IV| Engineering Materials ----Polymers and Nano Materials

1. Classification of polymers Based on polymerization reaction

i). Addition polymers polymers formed by chain wise addition reaction. An
addition reaction is, two or more molecules combine to form large molecule with no
elimination of small molecules. Molecules needs a double or triple bond. Total
molecular weight of polymer chain segment is an exact integer multiple of molecular
weight of monomers.

ii). Condensation polymers polymers formed by step wise condensation reaction. A

condensation reaction is, two or more molecules combine to form large molecule
with elimination of small molecules like water, ammonia etc.

Addition Polymerization Vs Condensation Polymerization

Ans. i). Addition or chain polymerization

Repeated addition of monomers to yield long chain.

>>
No elimination of small molecules like water or HCl etc during the progress of reaction.

It takes place only with compounds having double or triple bonds such as ethylene, vinyl
chloride etc.

Total molecular weight of polymer chain segment is an exact integer multiple of molecular
weight of monomers.

ii). Condensation or Step polymerization

Step by step condensation of monomers to yield long chain.

>>
The reaction is accompanied by elimination of small molecules like water or HCl etc.
>>
Total molecular weight of polymer chain segment is not an exact integer multiple of
molecular weight of monomers.
>> It takes place when condensing functional group pairs are present like -OH and -COOH or -NH2
and -COOH etc

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Co polymerization

Two or more different types of monomers undergo polymerization together to give co

polymer.
Example BuNa-S (Addition Co-polymer)

Example Kevlar (Condensation Co-polymer)

Copolymer

I. BUNA-S BS RUBBER
Random copolymer of butadiene and styrene.
BuNa-s is a trade name. Bu stands for butadiene, Na stands for sodium(Na) initiator, S for
styrene. It was initially synthesised using sodium initiator. Other trade names are GR-S (Govt. Rubber
styrene) SBR (styrene butadiene rubber).
Synthesis: Formed by addition co-polymerization between Butadiene (75 %) and styrene (25%) By
emulsion polymerization of butadiene and styrene using peroxide initiator and a temperature of
about 5C. Therefore it is also called cold rubber.

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Properties of BuNa-S
It is a synthetic replacement of natural rubber (it is not a chemically synthesised natural rubber).
It is vulcanizable with sulphur (but requires only little amount).
It is sensitive to ozone.
It is electrically non-conducting.
It has good adhesive properties

Uses of BuNa-S
Replacement for Natural Rubber
Make light duty tyres.
Making Gaskets, foot wares, shoe soles, conveyor belts etc
Used as a binder in adhesives
Used for electrical insulation.
Used for making tank lining.

II. ABS Acrylonitrile Butadiene Styrene Plastic

It is formed by addition polymerization. It is a ter-polymer of Acrylonitrile, butadiene
and styrene

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Properties and applications of ABS Plastic

High Impact Strength (Making Automotive parts)
Electroplatable (metallic finish can be obtained -- Shower heads, door handles etc)
Scratch and wear resistant (TV cabin, radio casing, Key board caps, musical
instrument casing etc)
Electrically non-conducting

ADVANCED POLYMER -

KEVLAR

(invented by Stephanie Kwolek)

Kevlar is a condensation copolymer of 1,4-phenylene-diamine and terephthaloyl

chloride. It is a poly-Aromatic-Amide (Aramides). It is a super strong plastic.

Wet spinning of the synthesized Kevlar will result in fibre.

Fibers are long thread like material having high tensile strength. The polymer chain
segments are held together by very strong intermolecular interactions (Hydrogen
bonding and aromatic pi pi interaction.

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Properties: High strength to weight ratio than steel, stronger than steel, Heat
resistant, light weight, Difficult to cut and drill,...
Applications: Bullet proof cloths, light weight body armour, Cut resistant gloves, Fire
proof Clothing,
What is Wet Spinning?
Wet Spinning is a manufacturing process for creating polymer fibres. The polymer is
converted into visco-fluid state by heating, then the molten polymer is passed through a
spinneret and allowed to cool. The liquid-to-fibre formation process is similar to the
production process for cotton candy (Panji Muttai)

ADVANCED POLYMER -

POLYBUTADIENE (PBD) RUBBER

A synthetic rubber
Homo polymer made monomer 1,3-butadiene by addition polymerization.
1,3-butadiene can polymerize in 3 different ways,

Depending on the percentage of each fragment on the polymer chain the properties
changes.
High cis-polybutadiene: Ziegler-Natta polymerization yields high cis variety. Catalyst is
combination of transition metal halide + organometallic compound. Neodymium metal
halide gives 99% cis and straight chained polymer, where as copper catalyst highly
branched structure.
Organo-lithium catalyst gives a mixed product with 40 % cis, 50 % trans and 10 % vinyl
Vinyl content increases the Tg and plasticity.
Transition Metal catalyst gives high trans polymer. But it is a plastic material.

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Properties: High cis variety is an elastomer.

It has better green resistance (it is resistant to deformation and fracture before
vulcanization)
It has cut growth resistance (Tear and crack wont propagate during dynamic operation.
It has high elasticity and resilience and good abrasion resistance.
Applications of PBD
Manufacture of tyres (tyre treads and side walls)
Vulcanized PBD is used to make bouncy balls
Golf ball inner core is made using PBD.

ADVANCED POLYMER -

SILICONE POLYMER

Silicone polymers have Siloxane bonds (-Si-O-Si-O-Si-O-Si-) . Siloxane bonds are highly
stable than -C-C- bonds. Therefore silicon polymers have higher heat resistance, better
electrical insulation property and high chemical stability.
Preparation

:
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Depending on the degree of polymerization and percentage of above fragments in a

polymer chain, silicon polymers can be in liquid, semisolid, rubber like or hard material.

Silicone polymers on vulcanization/curing (linking) give silicone rubber.

Vulcanization/Curing methods to produce silicone rubber:
Method 1: Peroxide Curing:
Vinyl terminated silicone poymers on treatment with a peroxide gives silicone rubber.

Method 2: Addition Curing:

H-Terminated silicone polymer adds to a Vinyl
terminated silicone polymer in 1,2-addition.

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Method 3: Condensation Curing: Acetate [CH3-COO-] terminated silicone polymer

condenses with OH terminated silicone polymer with the elimination of acetic acid.

Properties and application of silicone rubber:

Elastic rubber like nature --- Used to make air craft tyres.
They have adhesive properties, water repellent nature
bathroom fittings, fish tanks etc.

--

Used as sealants for

They have excellent heat resistance Used to make pastry brush.

They have high chemical stability and bio compatible Used to make baby teether,
artificial heart valves etc
They are used as drying oil in paints to get protection against weather changes.
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Conducting polymers

Polymeric materials that conduct electricity.

The conducting polymers are of two basic types,

Intrinsically conducting polymers Where the polymer material itself conducts. The
conductivity can be semiconducting or metallic like conducting.

Extrinsically conducting polymers Here polymeric material is non-conducting. Polymer on

which conductivity is induced by adding graphite or aluminium powder or a conducting polymer.

Intrinsically conducting polymers Where the polymer material itself conducts. Two types
A. Conjugated -electron conducting polymers: Polymers having large number of conjugated
double bonds (alternating single and double bond). The band gap of these polymers is in
between 1 to 2 eV. So they are semiconducting in nature.

B. Doped Conducting Polymers: By removing electrons (creating holes) by oxidation or

inserting electrons by reduction into the material makes the band gap smaller and enhances
the conductivity. This process is called doping. By doping conductivity can be improved up to
metallic regime.
Types of doping
p-doping :
Some electrons are removed from the semiconducting polymer chain by oxidation.
The radical cation produced is called polaron. If two radical centres are created then it is a bipolaron.
The polarons are mobile and can move along the polymer chain by resonance delocalization. Hence
the polymer becomes conducting.
The oxidation process can be brought about by chemically by allowing the polymer to react with
Lewis acids FeCl3 or with oxidizing agents like (I2, Br2, AsF6 etc)

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n-doping :
Some electrons are inserted to the semiconducting polymer chain by reduction. The
reduction can be brought by an electrode process or treating the semiconducting polymer with
Lewis bases like sodiumnaphthalide or alkali metals.

Factors affecting conductivity

1. Band gap : Band gap increases conductivity decreases.
2. Density of charge carriers. : Polaron density increases conductivity also increases.
3 . Temperature : The conductivity of a conducting polymer decreases with decrease in
temperature in contrast to the conductivities of metals which increases with decrease in
temperature
Advantages of conducting polymers.
1.
2.
3.
4.
5.

Low cost fabrication

Flexible
Polymers are easy to process.
Tuning of properties can be achieved by substitution.
Light weight.

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Applications of Conducting polymers.

1. Can be used as antistatic coating material.
By coating with a very thin layer of conducting polymer it is possible to prevent the build up
of static electricity. This is particularly important where such a discharge may be dangerous
in an environment with flammable gases.
2. Artificial nerves.
Due to the biocompatibility of some conducting polymers it can be used to transport small
electrical signals through the body. Ie they can act as artificial nerves.
3. Electroluminescent devices.
Electroluminescent means light emission stimulated by electric current. Electroluminescent
polymers can be used as display screens.
4. Photovoltaic cells.
Conducting polymers can be used to harvest light and convert it to electricity.
5. Electrochromic Screens. Fully oxidized form, partially oxidized form, fully reduced form and
partially reduced forms of conducting polymer have different colours. They can be used for
electro chromic screens.
6. Super Capacitors: rapid charge-discharge cycles and high capacitance.

Polyaniline conducting polymer PANI.

Chemical Synthesis

- is conducting
Amine monomer and oxidant is dissolved in 1M HCl and mixed. The reaction is highly exothermic.
Electrochemical Synthesis
Reactor vessel is equipped with 3 electrode assembly.
A working electrode (anode) on which the polymer is formed by oxidative polymerization.
Other two electrodes are a Pt electrode and reference Saturated Calomel Electrode.
Electrochemcial solution contains the monomer, supporting electrolyte and a solvent.

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Synthesis can be carried out either potentio-statically (constant voltage) or galvano-statically

(constant current). Potentio-static condition will give thin filims. Galvano-static condition will give
thick film.
Advantages of electrochemical Synthesis
Simple, Less expensive, no need of catalyst etc.
Properties and Applications of PANI
Light weight, Flexible, low cost etc.
By doping conductivity can be changed.
Has electrochromic properties.
Chemcial sensors, Electrochromic displays, Antistatic coating material, flexible electrodes,
Super capacitor etc
Polypyrole conducting polymer PA
Chemical synthesis by oxidative polymerization
Monomer pyrrole and an oxidant ammonium persulphate is mixed well at room temperature in a
suitable solvent.

Polypyrrol can be doped to increase their conductance by oxidation or reduction.

Electrochemical Synthesis
Reactor vessel is equipped with 3 electrode assembly.
A working electrode (anode) on which the polymer is formed by oxidative polymerization.
Other two electrodes are a Pt electrode and reference Saturated Calomel Electrode.
Electrochemcial solution contains the monomer, supporting electrolyte and a solvent.
Synthesis can be carried out either potentio-statically (constant voltage) or galvano-statically
(constant current). Potentio-static condition will give thin filims. Galvano-static condition will give
thick film.

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Advantages of electrochemical Synthesis

Simple, Less expensive, no need of catalyst etc.
Properties of PPY (Polypyrrole)
Light weight, Flexible, low cost etc.
By doping conductivity can be changed.
Has electrochromic properties.
Biocompatible
Applications of PPY
Catalyst support for fuel cells
Artificial muscles and nerves
Solar cells
Polymer LEDS

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OLED Organic Light Emitting Devices/Diodes

Works on the principle of electroluminescence
Certain materials can emit light in response to an electric current passing through it.
Basic Architecture of OLED

Mechanism

Hole and Electron recombine in the EML to produce light.

If all the layers are made of small organic molecules then we call it as Small Molecule OLED
If any of the layers is a conducting polymer then we call it as Polymer LED (PLED).
The device architecture can be simplified to a bilayer device if the EML material has either electron
transporting property or hole transporting property.

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If the EML material has both hole transporting and electron transporting property then the device
will be single layered one.

Advantages of OLED:
Light weight.
Very Small thickness.
Flexible.
Less Power required.
Higher Brightness
Applications of OLED:
Full Colour Display Screens
White OLEDs for Solid state white lighting
Roll-up displays OLED printed in fabrics, flexible displays etc.

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Nanomaterials.
Materials with at least one external dimension in the size range 1 to 100 nm (nano-scale).
Examples DNA strand (width of DNA strand is approximately 2 nm), Fullerene (n nano size carbon
allotrope), nano gold etc

Classification of nanomaterials.
Based on dimension:
Zero dimension All three dimensions are in nano-scale (example nano-particles).
One Dimension One dimension is outside the nano-scale (example nanorod, nanowire,
nanotube).
Two Dimension Two of the dimensions are not confined to nano-scale (example
nanosheet, nanolayer, nanocoating).
Three Dimension - They are bulk nanomaterials. Example aggregates of nanocrystals to form
a bulk structure or a bundle of nanowires.
Based on the material:
Carbon based nanomaterial It contains only carbon. Examples are carbon nanotube,
fullerene, graphene sheet.
Metal based nanomaterial Contains metals. Examples are mono-metallic nano particles
like nano-gold, nano-silver etc, mixed metal nano particles like CdTe and GaAs semiconductors,
metal oxide semiconductor electrodes like TiO2 and ZnO nano particles.
Biological nanomaterials Materials in biology. Examples are DNA strand, protein strand etc.
Nanopolymers Polymers in nanoscale. Example dendrimers tree like polymers, they have
well defined cavities which find application as drug carriers in medicine.
Nanocomposites - Nanomaterials have high strength to weight ratio. Composites made of
nanomaterials as reinforcing agents are having light weight with good strength.

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Properties and applications of nanomaterials.

In catalysis: Nanoparticles have high surface to volume ratio. Hence they act as efficient catalyst.
High Technology application: Nanomaterials have interesting semiconducting and optical properties.
Therefore they find applications is solar cells, semiconductor devices, Non-linear optical devices etc.
Nanocomposites: Nanomaterials have high strength to weight ratio. Therefore they are used as a
reinforcing material to prepare nanocomposites having light weight and good strength.
In medical application: Biocompatible nanomaterials tagged drugs created the possibility of
diagnosing and treatment of cancer like diseases. Nanotechnolgy can be used for delivering drugs to
specific cells using nanoparticles. Thus overall drug consumption and side effects can be significantly
lowered.
In textiles: Adding nanoparticles enables anti odour functioning, wrinkle free functioning and stain
resistant functioning.

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Chemical Methods for preparation of nanomaterials.

Hydrolysis (Hydrothermal and Sol-gel methods)
Hydrothermal / Thermal Hydrolysis (For preparation of Metal Oxides nano particles)
Nanomaterials are synthesis under high Temperature and Pressure in water medium.
Precursor materials are insoluble at ordinary temperatures and pressures, but solubility
increases at higher temperature.
Synthesis is carried out in autoclaves (sealed steel cylinder) that can withstand high
temperature and pressure.

Precursor material along with mineraliser (to increase solubility) is placed in the bottom of
autoclave and is heated. The precursor material will dissolve.
The temperature in the dissolving region is relatively higher than the temperature at
crystallizing zone.
This temperature gradient results in a natural movement. The bottom warm solution is less
dense so moves upward to the crystallizing zone. The cooler temperature in the crystallizing zone
leads to super-saturation of solution. Nano sized materials precipitates out. The cool dense fluid
sinks to the dissolving region and the cycle continues.

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Aqueous sol-gel process. (For preparation of Metal Oxides nano particles)

In aqueous sol-gel process a precursor solution is converted into nano-sized inorganic solid
via polymerization reaction induced by water.
Common precursor materials are metal alkoxide or any metal salts.
Steps involved,
a. Preparation of a homogeneous solution of precursor material in water.
b. Conversion of the homogeneous solution into a sol by treatment with water
(Hydrolysis).
c. Further polycondensation results in a gel (interconnected, rigid and porous inorganic
networks enclosed in liquid phase).
d. Dry the gel. Removal of solvent in the gel by evaporation results in the shrinking of pore
volume of the gel structure and results in XEROGEL. If the solvent in the gel is removed
at super critical condition, the network structure is retained and results in AEROGEL.

Advantage of sol-gel process:

Shape the material into any desired forms such as films, fibres, mono-sized powders
etc.

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Reduction (Another Chemical Methods for preparation of

nanomaterials)
Chemical Reduction (For preparation of Metal nano particles Silver nano particles)
Metal salt solution is reduced by adding reducing agents such as Sodium borohydride,
glucose, hydrazine etc.
Steps:

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Electrochemical reduction:
Similar to electro plating an electrolysis cell is constructed
Steps:
The anode is the bulk metal copper for copper nano particle production. Oxidative dissolution take
place at anode. Cu Cu2+ + 2e
Migration of Cu2+ towards cathode.
Reductive formation of Cu metal at the cathode Cu2+ + 2e Cu
Aggregation of Cu to form Copper nano particles.
Arrest the growth and stabilize the nano particle by adding surface protecting ligands.

Advantages of electro Chemical reduction

Low cost, simple, pure product etc.

Carbon nano tube (CNT).

It is a carbon based nano tube. All carbon atoms are sp2 hybridized. All carbon atoms are in
hexagonal framework. The shape is like a graphene sheet rolled up into a seamless cylinder. Open
ends and closed ends are available. CNT with many radii can be found. Two types single walled CNT
(one atom thick sheet of graphene rolled into a cylinder) and multi walled CNT (contains many
concentric cylinder).

Properties of CNT
Their tensile strength is greater than steel of same dimension.
Youngs modulus is greater than steel.
They have high thermal conductivity more than silver.
They have light weight, density about 1/4th of steel.
Some of them conduct electricity better than metals.

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Applications of CNT:
Nanoelectronics: Depending on the size and structural variations their electrical conductivity
differs. Hence some are semiconductors and some are conductors of electricity. Therefore used in
semiconductor technology, display devices etc.
Strengtheners: CNT has the highest strength to weight ratio. So it can be used to make
nanocomposites to build light weight materials with good strength.
Medical Applications: CNT is helpful in diagnosing and treatment of cancer like diseases.
They are used for drug delivery. The overall drug consumption and side effects can be considerably
reduced.
Chemical and Bio-Sensors: CNT is chemically modified to obtain selectivity towards a
particular material. When this material makes an interaction with CNT, its electrical or optical
property changes. so we can identify the presence of that material.
Good Adsorbing Material: CNT has high surface to volume ratio and carbon has adsorbing
ability, so these materials are good adsorbent materials.
Probe tips for Surface Scanning Techniques: High resolution is obtained when using CNT as
probe tips.

Carbon Fullerene
Fullerene is a nanosize allotrope of carbon. Carbon atoms are linked together in hexagonal or
pentagonal framework. Examples are C60, C70, C76, C80.
In C60 fullerene there are 60 carbon atoms, all are in sp2 hybridization. There are twelve pentagons
and 20 heaxagons in C60 fullerene. Each pentagon is surrounded by five hexagons. Pentagons does
not touch each other.
Properties:
Thermally stable upto 400 C
Excellent photo-stability
Are electron acceptors
Applications
Super Conductor: Alkali metal doped fullerene behave like super conductor
Medical Application: Fullerene have antiviral activity. Chemically modified fullerene can
inhibit HIV.
Photodynamic Therapy: They can act as Photo-sensitizer, therefore used in photodynamic
therapy for the creation of singlet oxygen.
Good Adsorbing Material: CNT has high surface to volume ratio and carbon has adsorbing
ability, so these materials are good adsorbent materials.
Solar Cells: They have high electron affinity. They have electron transporting ability.
Fullerenes are used as electron acceptors in Bulk-hetero Junction solar cells.
Hydrogen gas storage:
Fullerene can reversibly store 18 molecules of hydrogen.

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Questions
Q1. Differentiate between 1,2- and 1,4 addition polymers by giving example of PBD rubber.
Q2. Distinguish between Addition and condensation Polymers.
Q3. Give the structure, properties and uses of Buna-S and ABS Co-polymers?
Q4. How are silicones prepared? Mention their important properties and applications?
Q5. Explain any two methods of Curing / Vulcanization of Silicone polymers to produce silicone
rubber?
Q6. Explain the functionality of monomers, taking silicone polymer as example?

This fragment is responsible for

Chain growth.

This is responsible for branching of

polymer chains.

This
termination.

Q7. Write the structural formula of ABS, Kevlar and PBD rubber.

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is

responsible

of

Chain

IV| Engineering Materials ----Polymers and Nano Materials

Q8. Give an account of conducting polymers and their classification.

Q9. Give the mechanism of doping in conducting polymers to enhance conductivity.

p-Doping: Some electrons are removed from the semiconducting polymer chain by oxidation. The
radical cation produced is called polaron. If two radical centres are created then it is a bipolaron. The
polarons are mobile and can move along the polymer chain by resonance delocalization which result
in reduction of ban-gap. Hence the polymer becomes conducting.
The oxidation process can be brought about by chemically by allowing the polymer to react with
Lewis acids FeCl3 or with oxidizing agents like (I2, Br2, AsF6 etc)
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n-doping :
Some electrons are inserted to the semiconducting polymer chain by reduction. The
reduction can be brought by an electrode process or treating the semiconducting polymer with
Lewis bases like sodiumnaphthalide or alkali metals.

Q10. Explain the working of OLED.

OLED works on the principle of Electroluminescence. Certain materials can emit light in response to
an electric current passed through it.

Q11. What type of organic compounds are used in OLED

Ans:

Hole-transport materials: Easily oxidized and conduct positive charges (holes).

Electron-transport materials: Easily reduced and conduct negative charges (electrons).
Electro luminescent materials: Holes and electrons recombine and emit light in this region.

Q12. Give one example of an Emissive material, Electron Transporting material and Hole
transporting material used in OLED technology.

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Q13. Explain the Hydrothermal method of synthesis of metal-oxide nano particles.

Q14. Write a note on sol-gel hydrolysis of preparation of nano particles.
Q15. Explain electro-reduction and chemical reduction methods for the production of metal nano
particles.
Q16. Give the Structure, properties and applications of CNT.
Q17. Give the properties and applications of Fullerene.
Q18. Give the classification of Nano materials based on dimension and material.
Q19. Write the synthesis, properties and application of Silicone rubber.
Q20 Write the synthesis, properties and application of Kevlar.
Q21 Write the synthesis, properties and application of PBD rubber.
Q22 Write the synthesis, properties and application of ABS plastic.
Q23. Write the synthesis, properties and application of PolyAniline Conducting Polymer.
Q24. Write the synthesis, properties and application of Polypyrrole conducting polymer.
Q25. Write a note of Wet spinning technology in the production fibres from virgin plastic.
Q26. Butadiene and styrene can be co-polymerized to form BuNa-S rubber. Would this be an
addition or condensation polymerization?
Q27. What is the nature of bonding in carbon nano tubes? Give few applications.
Q28. Outline the structural features of Fullerene? Give two applications of fullerene.
Q29. Compare between SWCNT and MWCNT ?
Q30. Which structural feature of intrinsically conducting polymer gives them the conducting
property?
Q31. Carbon nanotubes and fullerenes are two giants in the world of nanomaterials, comment.
Q32. What are the major applications of Kevlar and ABS?
Q33. Write a short not one OLED.
Q34. Explain the conductivity of polyaniline and polypyrol with the help of its structure.
Q36. Explain the hydrolysis and reduction method of synthesis of nano particle.
Q37. Draw a neat sketch and explain the layered device architecture of an OLED. Give the
applications and advantages of OLED technology.

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Match the following

Polymerization

Applications

Properties

Applications

BuNa-S

Condensation
Co-Polymer

Bullet Proof
cloths

High Strength to weight ratio

and bullet resistant

bouncing
balls

PBD

Siloxane
bonding

Air craft tyres

Electroplatable

TV cabin,
radio casing

ABS

Addition
Homo-Polymer

Tire treads and

tire side walls

High elasticity and high

resilience

military
helmets

Silicone
Rubber

Addition Terpolymer

light duty tyres

High heat resistance and high

chemical stability

Fireproof
cloths

Kevlar

Addition Copolymer

Metal Finish to
door handles

Cut resistant and heat

resistant

pastry
brushes

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