UNIT – II

POLYMERS & COMPOSITES

Polymers - definition – polymerization – types – addition and condensation polymerization –

free radical polymerization mechanism – Plastics, classification – preparation, properties and
used of PVC, Teflon, polycarbonate, polyurethane, nylon-6,6 , PET – Rubber – vulcanization
of rubber, synthetic rubbers – butyl 1 rubber, SBR, Composites – definition, types of
polymers matrix composites – FRP only.

Introduction:
In this modern world, polymers are an integral part of every one’s life style. They have
different structures and applications ranging from domestic articles to sophisticated scientific
and medical instruments. These materials are used as fibres, rubbers, plastics, adhesives,
paints, etc. Infact, the existence of life is virtually the formation, transformation and
decomposition of bio-polymers viz. Carbohydrates, Proteins and Nucleic acids. Hence, in
view of their importance, a proper understanding of polymeric materials is very essential.

The word Polymer is derived from two Greek words, Poly - Many and Meros - Units.
A polymer is a macro-molecule (giant molecule) which is formed by the repeated linkage of a
large number of small molecules (monomers). Example: Polythene is a polymer formed by
repeated linkages of a large number of Ethylene molecules. Where n – degree of
polymerization, it can be 104 or more.

TERMINOLOGY:

POLYMER: polymer can be defined as, a macromolecule of high molecular weight which is
formed by the combination of large number of small molecules of low molecular weight.

MONOMER: A large number of small molecules repeatedly combine to give a macro molecule
(polymer) of high molecular weight are called monomers.

DEGREE OF POLYMERISATION: The number of monomeric units contained in a polymer is

called degree of polymerization.

POLYMERIZATION:
The chemical process which leads to the formation of polymer is called polymerization.

TYPES:
Based on the synthesis in which elimination of by products formed, polymerizations are
broadly classified into addition polymerization and condensation polymerization.

ADDITION POLYMERISATION: It is also called chain polymerization. The process in which

large number of identical monomers repeatedly combines to give a polymer without the
elimination of any by-products is called addition polymerization.
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Example:

Example for addition polymers: Polythene (PE), Polyvinyl chloride (PVC), Polystyrene (PS),
Polypropylene (PP), etc.

CONDENSATION POLYMERISATION: It is also called step polymerization. The process in

which large number of two or more different types of monomers combines to give a polymer
with the elimination of by-products like H2O, HCl, methanol, etc is called condensation
polymerization.
Example:

Example for condensation polymers: Nylon, Bakelite, Polyethylene terephthalate (PET), etc

Sl.No ADDITION POLYMERISATION CONDENSATION POLYMERISATION

1 It requires the presence of double
bond in monomer.
2 No by-product is formed.
3 Homo-chain polymer is formed.
4 Thermoplastics are formed.
5 The growth of chain is at one
active centre.
6 The molecular weight of the
polymer is a multiple of that of the
monomer.
It requires two reactive functional
(same/different) groups to be present at
both ends of the monomer.
By-product is formed.
Hetero-chain polymer is formed
Thermosetting plastics are formed.
The growth of chain occurs at minimum
of two active centres.
The molecular weight of the polymer is
not a multiple of that of the monomer.

PLASTICS: Plastics are high molecular weight organic materials which can be moulded into
any desired form by the application of heat and pressure in the presence of a catalyst. In
recent years, plastics have attained great importance in day to day’s life, due to their certain
unique properties.

Advantages of plastics:
1. They are light in weight.
2. They have low melting point and easy to fabrication.
3. They are highly resistant to corrosion, shock absorption and abrasion.
4. They can be cast/mould into any desired shapes easily.
5. They have high refractive index and tensile strength (5500kg/sq.cm)
6. They never react with water and not affected by microbes.
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 7. They have good dimensional stability.
8. They do not react with light, oils, acids and dampness, etc
9. The shades/colours do not fade easily.
10. Plastic surfaces possess shining and glossy surfaces, which appeal eyes.

Disadvantages: High cost, combustibility, poor ductility, softness, deformation under load,
embrittlement at low temperatures and low heat-resistance, etc.

Applications:
1. Used to make pipe lines, electrical goods, furniture, handles for tools & cover for
machines, house-hold articles like combs, toys, trays, etc.
2. Used to make special paints, bearing for propeller shafts, etc
3. Used as insulation material for heat and sound in cold storage, refrigeration and air-
conditioned auditoriums, etc.
4. Used to make synthetic fibres, terylene and nylon, etc.

CLASSIFICATION: Plastics are classified into thermoplastics and thermosetting plastics.

Sl.
No THERMOPLATICS
1 They are formed by addition
polymerization.
2 They have either liner or branched
structure.
3 Adjacent polymer chains are held
together by Vander Waal’s forces.
4 They soften on heating and stiffen on
cooling.
5 They can be re-moulded, re-shaped
and re-used.
6 They can be recycled.
7 They are soluble in organic solvents.
8 They are soft, weak and less brittle.
9 There is no change in their chemical
composition during the moulding
process.
THERMOSETTING PLASTICS
They are formed by condensation
polymerization.
They have three dimensional, cross-
linked network structures.
Adjacent polymer chains are held
together by strong covalent bond.
They do not soften on heating.
They can’t be re-moulded, re-shaped
and re-used.
They can’t be recycled.
They are insoluble in organic solvents.
They are hard, strong and more brittle.
There is a change in their chemical
composition during the moulding
process.

THERMOPLATICS: They have either linear or branched structures. Their polymeric chains are
held together by weak Vander Waals’ forces. There is no cross-link. On heating, they soften
readily and become hard and rigid on cooling. That’s why they can be remoulded, reshaped
and reused. They are soft, weak and less brittle; they are soluble in organic solvents.
Example: Polyethylene (PE), Polyvinylchloride (PVC) , Polypropylene (PP), Polystyrene (PS)
and Polymethylmethacrylate (PMMA), etc.

THERMOSETTING PLASTICS: They have three dimensional, cross-linked, networked

structures. Their polymeric chains are held together by strong covalent bonds. There are
many cross-links. Heating does not soften them, since softening would require breaking of
covalent bonds. That’s why they can’t be remoulded, reshaped and reused. They are hard,

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strong and more brittle. They are insoluble in organic solvents. Example: Bakelite &
Polyester, etc.

FREE RADICAL POLYMERISATION MECHANISM: It involves the following steps, chain

initiation, chain propagation and chain termination. The chain initiation includes the
production of free radicals by the hemolytic cleavage of an initiator followed by the addition of
first monomer to radical to produce the chain initiating species.

Chain initiation step: It involves two reactions.

The production of free radicals by the homolytic cleavage of an initiator to give a pair of
radicals, Ro. The addition of first monomer (M) to the radical to produce the chain initiating
species, M1o. Thus, the polymerization of monomer, CH2=CHY, takes in the form as follows.

Chain propagation step:

The growth of M1o occurs by the addition of large number of monomers.

Chain termination step: It involves coupling and disproportionation. The hydrogen atom of
one radical centre is transferred to another radical centre. This results two polymers, one is
saturated and another is unsaturated.

POLY VINYL CHLORIDE (PVC):

Preparation: PVC is obtained by heating water-emulsion of vinyl chloride in presence of a

small amount of benzyl peroxide or hydrogen peroxide in an auto-clave under pressure.

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The vinyl chloride is prepared by treating acetylene at 1 to 1.5 atm pressure with HCl at
60 – 80oC in presence of metal chloride as catalyst.
60 – 80oC
C2H2 + HCl CH2=CH—Cl
Acetylene VC
Properties:
1. It is colourless, odourless, non-inflammable and chemically inert powder.
2. It has excellent resistance to light, atmospheric oxygen, inorganic acids, alkalis & oils,
but soluble in hot ethyl chloride and THF.
3. It has very high strength, rigidity and stiffness.
4. It is partially syndiotactic.
5. It has high softening point (148oC).

Applications:
1. It is used for making sheets, which are employed for tank-linings, light-fittings, safety
helmets, refrigerator components, tyres, cycle & motor cycle mudguards, etc.
2. It is used for the production of pipes, cable insulations, rain coats, injection moulding
articles like toys, tool-handles, toiled-goods, radio components, chemical containers,
conveyor belts, etc.

PTFE (POLY TETRA FLUORO ETHYLENE): It is commercially called teflon and fluon.

Preparation: Teflon is obtained by polymerization of water-emulsion of Tetrafluoro ethylene,

in presence of small amount of benzoyl peroxide under high pressure.

Properties:
1. It has excellent resistance to heat, electricity and chemicals (except hot alkali/hot F2).
2. It has high density, 2.1 – 2.3 g/cc and low co-efficient of friction.
3. It can be machined, punched and drilled.
4. It has high softening point (350oC) due to the presence of Fluorine atoms.

Applications:
1. It is used as an insulation material for motors, transformers, cables, wires, fittings, etc.
2. It is used for making gaskets, pump parts, tank linings, chemical carrying pipes,
tubings and tank, etc.
3. It is used for coating and impregnating glass fibres, asbestos fibres and cloths, etc.
4. It is used in the making of non-lubricated bearings and non-sticking stop-cocks for
burette, etc.
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POLY CARBONATES (PC):

Preparation: It is commercially called lexan and merlon. It is prepared by interaction of

diphenyl carbonate with bisphenol-A [2,2-bis(4-oxyphenyl)propane].

Properties:
1. It has high impact and tensile strength over a wide range of temperature.
2. It is soluble in organic solvents and alkalis.
3. It has good dimensional stability, stiffness and transparency, etc.
4. It has an excellent electrical insulation property.

Applications: It is used for making moulded domestic ware and electrical and electronics
materials like plugs, switches, etc.

POLY URETHANE (PERLON – U):

Preparation: It is obtained by treating 1, 6 - hexane diisocyanate with 1, 4 - butane diol.

Properties:
1. It is less stable than polyamides.
2. It has an excellent resistance to abrasion and solvents.

Applications:
1. It is used as coatings, films, foams, adhesives and elastomers, etc.
2. Resilient polyurethane fibres are used for formulating garments and swim suits, etc.
3. It is used to cast to produce gaskets, seal and printing rolls, etc.

NYLON 6, 6:

Preparation: It is obtained by the condensation polymerization of hexamethylene diamine

and adipic acid in 1:1 molar ratio.

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It is also prepared from 1, 3 – butadiene.

Properties:
1. It is translucent, whitish and horny, etc.
2. It has high melting point, 160 – 240oC.
3. It has an excellent resistance to high temperature and abrasion.
4. It is insoluble in solvents like C6H6 & acetone, but soluble in phenol & HCOOH.
5. It has good moulding and extrusion properties.

Properties of nylon fibres:

1. They are light, horny and have high melting.
2. They are insoluble in common solvents and absorb little moisture.
3. They have good strength and resistant to abrasion.
4. They are very flexible and retain to original shape after use.
5. On blending with wool, the strength and abrasion resistance of later increases.

Applications:
1. Nylon 6, 6 is primarily used for fibres in making socks, carpets and dresses, etc.
2. It is used to make filaments for ropes, bristles for tooth-brushes and tyre-cords, etc.

POLY ETHYLENE TEREPHTHALATE (PET): It is commercially called terylene / dacron.

Preparation: It is prepared by condensation polymerization of terephthalic acid and ethylene

glycol in basic medium.

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Properties:
1. It is a good fibre-forming material due to the presence of polar group and symmetrical
structure.
2. It’s fibre has high stretch resistance, high-crease and wrinkle resistance, etc.
3. It has high resistance to mineral and organic acids, but is less resistance to alkalis.
4. It has good mechanical properties like high modulus, tensile strength, tear strength
and impact strength, etc which are retained up to 150 – 175oC.
5. Blends of PET fibre with cotton and other cellulosic fibres have better feel and
moisture permeation.

Applications:
1. It is mostly used for making synthetic fibres like terylene, dacron, etc
2. It is used for blending with wool to provide better crease and wrinkle resistance.
3. As glass reinforcing material in safety helmets, aircrafts battery boxes, etc.
4. To make magnetic recording tape.
5. Glass filled PET mouldings are used for the houses of toasters, coffee makers, car
heater and water meter, etc.
6. Fibre applications like wearing apparel, curtain, thread, tire cord and fabrics for
industrial filtration.

RUBBERS (ELASTOMERS): Rubbers are high polymers, which have elastic properties in
excess of 300 percent. An elastomer molecule is not straight chained as in the case of
poly ethylene, but in the form of a coil and consequently it can be stretched like a spring. The
unstretched rubber is amorphous. As stretching is done, the macro molecules get partially
aligned with respect to another, thereby causing crystallization and consequently, stiffening
of material occurs. On releasing the deforming stress, the chains get reverted back to their
original coiled state and the material again becomes amorphous.

Coiled structure of natural rubber.

Natural rubber consists of basic material latex, which is a dispersion of isoprene. During the
treatment, these isoprene molecules polymerize to form, long-coiled chains of cis-poly
isoprene.
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The molecular weight of raw rubber is about 100,000 – 150,000 gram. Natural rubber is
made from the plants like havea brasillians and guayule, and the rubber latex is obtained by
making incisions in the bark of the rubber trees. The latex is transferred to a factory for
treatment.

Structure of natural rubber.

Drawbacks of rubber:
1. It becomes soft at high temperature and is too brittle at low temperature. So it can be
used in the temperature range of 10 – 60oC only.
2. It is weak, because of its low tensile strength, 200 kg per sq.cm.
3. It has large water – absorption capacity.
4. It is non-resistant to non-polar solvents like benzene and CCl4, etc.
5. In organic solvents, it undergoes swelling and gradual disintegration.
6. Due to it’s oxidation in air, it is not durable.
7. It is attacked by oxidizing agents like HNO3, H2SO4, Chromic acid, Sodium
hypochlorite, Chlorine dioxide, etc.
8. It possesses marked tackiness, which means that under pressure two fresh raw
rubber surfaces coalesce together to form a single piece.
9. When stretched to a great extent, some molecular chains undergo, sliding or slippage
over each other, hence it suffers from permanent deformation.

VULCANIZATION:
To improve the properties of rubber, it is compounded with various chemicals like S,
H2S, benzoyl chloride, etc. The process of heating the raw rubber at 100 – 140oC with
sulphur is called vulcanization. The added sulphur combines chemically at the double bonds
of different rubber molecules and provides cross-linking between the chains. This cross-
linking during vulcanization brings about a stiffening of the rubber by anchoring and
consequently preventing intermolecular movement of rubber springs. The amount of S added
determines the extent of stiffness of vulcanized rubber. For example, a tyre rubber contains 3
- 5% S, but a battery case rubber may contain as much as 30% S.

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 Vulcanization of raw rubber with S.

Advantages of Vulcanized rubber:

1. Good tensile strength, extensibility, slight tackiness and excellent resilience.
2. High resistance to moisture, oxidation and abrasion, etc.
3. Possess low water-absorption tendency and low elasticity.
4. Better resistance to organic solvents like CCl4, benzene, petrol, etc.
5. Operational temperature range, – 40 to 100oC.

SYNTHETIC RUBBERS (ELASTOMERS): A synthetic rubber is a vulcanisable man-made

rubber like polymer, which can be stretched to at least twice its length, but it returns to its
original shape and dimensions as soon as stretching force is released. Example: Styrene-
butadiene rubber (SBR), nitrile rubber, neoprene, butyl rubber, thiokol, hypalon and
polyurethane rubber, etc.

BUTYL RUBBER (GR-I):

Preparation: It is prepared by the co-polymerization of isobutene with isoprene.

Properties:
1. It has an excellent resistance to heat, abrasion, ageing, chemicals like HNO3, H2SO4,
HCl and HF, polar solvents like alcohol and acetone, etc.
2. It is soluble in hydrocarbon solvents like benzene, toluene, etc.
3. It has good electrical insulating property and high resistance to ozone.

Applications: It is used to make cycle and automobile tubes, hoses, conveyor belts,
tank-linings, insulation for high voltage wires and cables, etc.

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STYRENE BUTADIENE RUBBER (SBR / GR – S or Buna – S):

Preparation: It is obtained by co-polymerization of 1,3 – butadiene and styrene by weight in

the ratio 3:1.

Properties:
1. It has high abrasion resistance, high load – bearing capacity and resilience.
2. It oxidizes in presence of ozone.
3. It swells in oils and solvents.
4. It can be vulcanized like natural rubber using S / Sulphur monochloride (S2Cl2).

Applications: It is used for the manufacture of motor cycle tyres, floor tiles, shoe soles,
gaskets, foot-wear components, wire and cable insulations, carpet backing, adhesives and
tank-lining, etc.

COMPOSITES:

Introduction: Each class of basic engineering materials (metals/high polymers /ceramics)

has its own outstanding and unique properties along with certain limitations. Any of these
cannot be properly used where very stringent and specific requirements are needed. For
example, structural materials required for gas turbines, high temperature retort, supersonic
aircrafts, missiles, space crafts, etc must have high specific strength, stiffness and excellent
resistance to corrosion, abrasion, impact and heat. In order to meet the above requirements,
technologists and scientists have developed a new class of materials called “composites”. A
composite material may be defined as “any multiphase material which consists of two or
more physically and/or chemically distinct phases with an interface separating them”. These
materials possess combination of properties. Generally they are dense and also increase in
strength and stiffness without the disadvantage of brittleness. Example: Wood, bone and
rein force concrete, etc

Advantages: They have higher specific strength, stiffiness and fabrication and lower specific
gravity, electrical conductivity and thermal expansion. They show better resistant to
mechanical shock, corrosion, oxidation and deformation at higher temperature.

Applications:
1. In automobile industries, transportation industries, turbine engines, wire drawing dies,
valves, pump parts, spray nozzles, storage tanks, etc.
2. In fabrication of roof and floors, furniture, sports goods, high speed machinery, etc
3. Marine applications like propellers, shafts, hulls, spars and other ship parts, etc.
4. Aeronautical applications like components of rockets, aircrafts, missiles, and
helicopters, etc.
5. Communication antennae, electronic circuit boards (eg. PCB) , etc
6. Safety equipments like ballistic protection.

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FIBRE REINFORCED COMPOSITES:
It involves three components; filament, polymer matrix and bonding agent. They have high
specific strength, fracture strength, stiffiness and modulus, excellent shock resistance and
wear resistance and greater stability at high temperature.

FIBRE REINFORCED POLYMER COMPOSITES

Glass FRPC Carbon FRPC Armid FRPC Alumina &/or carbon

FR metal composites

Glass FRPC: They have lower density, higher tensile strength, impact resistance and
excellent resistance to corrosion and chemicals. They used to make automobile parts,
storage tanks, transportation industries and plastic pipes, etc.

Carbon FRPC: They have excellent resistance to corrosion, lower density & greater stability
at high temperature. They used to make structural components of aircraft & helicopters and
to make sports goods, fishing rods, etc.

Armid FRPC:

Type: 1. Short FRPC: They have high aspect ratio, high surface area & Inherent toughness,
high strength, heat stability & wear resistance. They used to make automobile brakes and
clutches.

Type: 2. Long FRPC: They have capability to absorb energy, high ductility and
compressibility. They used to make commercial aircrafts, helicopter parts (blades, motor
housing), and protective apparel (thermal and ballistics), etc.

Alumina &/or carbon FRPC: They have high specific strength, stiffness & abrasion resistance,
high creep resistance & dimensional stability, low density, wear resistance and resistant to
thermal distortion. Matrix-Al alloy used to make components of engine in automobile industry
and matrix-Ni & Co based alloy used to make components of turbine engines.

QUESTION BANK
PART – A

1. Define polymer with an example.

2. What is meant the degree of polymerization?
3. Write any two examples for homopolymer and heteropolymer.
4. What is meant by polymerization?
5. Distinguish addition and condensation polymerization.
6. Define monomer with any two examples.
7. Define thermoplastics. Give any one example.
8. Define thermosetting plastics. Give any one example.
9. Write down the repeating units of PET and Nylon 6, 6.
10. Write the monomers of Nylon 66.
11. Name any two synthetic polymers which are used for making textile fibres.
12. What is meant the term vulcanization of rubber? Mention its uses.
13. What is the main purpose of vulcanization?
14. What is an elastomer?
15. Why cannot thermosetting plastics be reused and reshaped?
16. Why are plastics indispensable in everyday life?

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17. What is addition polymerization? Give one example.
18. What is condensation polymerization? Give one example.
19. Write down the steps involved in the free radical polymerization.
20. What are plastics? Give any two examples.
21. What are the advantages of plastics?
22. Mention any four drawbacks of plastics.
23. Differentiate thermoplastics from thermosetting plastics.
24. Name the monomers of polycarbonate.
25. Why is Teflon used in the electric appliances?
26. Why is Teflon highly chemical resistant?
27. Give the preparation and uses of PVC.
28. Give the preparation and uses of PTFE.
29. What are the repeating units present in Nylon 66 and PET?
30. Differentiate between homo chain polymer and hetero chain polymers.
31. PVC is soft and flexible whereas bakelite is hard and brittle. Give reason.
32. Give the preparation of polycarbonate.
33. Give the preparation of Nylon 66.
34. How will you synthesize Dacron?
35. Write a note on Polyurethane.
36. State the monomers used in the following: a. Butyl rubber b. Terylene c. PVC d. Merlon e. SBR
37. Distinguish elastomers from plastics.
38. What is meant by FRP?
39. Write a note on natural rubber. Give two examples.
40. What are composite materials? Give two examples.
41. What are synthetic rubbers? Give two examples.
42. Give the preparation of butyl rubber.
43. Give the preparation of SB rubber.
44. Mention any four advantages of vulcanization.
45. Write any four drawbacks of natural rubber.
46. Mention any four applications of rubber
47. List the characteristics of composite materials.
48. Mention any four applications of composite materials.
49. Write down the types of FRC.

PART – B

1. Distinguish between thermoplastics and thermosetting plastics.

2. Differentiate addition and condensation polymerizations.
3. Discuss the free radical mechanism of addition polymerization.
4. Explain addition and condensation polymerization with suitable examples.
5. a) What is meant by vulcanization of rubbers. Mention its uses.
b) Explain why natural rubber needs vulcanization. How is it carried out?
6. Discuss briefly the process of vulcanization of rubber.
7. What are elastomers? Give preparation and applications of butyl rubber and SBR.
8. Describe the method of preparation, properties and applications of the following polymers.
a) PVC b) PC c) PTFE d) PU e) Nylon-66 f) PET
9. Discuss the potential applications of polymer reinforced concretes in any three of the following fields:
Transportation, aircraft & aero plane, construction, corrosion resistance material and electric industries.
10. What are composite materials? Discuss the type of polymer matrix composites.

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