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Unit – 1 – HIGH POLYMERS

Introduction
LEARNING CONCEPT – 1 Polymers are macromolecules built up by the linking together of a large number
Polymers - Introduction– Types of
of small molecules or units. For example, polythene is a polymer formed by
Polymers – Degree of Polymerization
linking together of a large number of ethene (C2H4) molecules. Similarly,
– Functionality- Tacticity,
Stereospecific Polymers. polystyrene is formed by the linking of styrene monomer molecules.

The small molecules that combine to form polymer molecules are termed monomers; and the “repeat unit” in a polymer is
called as -mer.

No. of repeating units Name of the Mer

1 Monomer
2 Dimer
3 Trimer
- -
- -
n Polymer

Degree of Polymerization
The number of repeating units (n) in chain formed in a polymer, is known as degree of polymerization.

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Functionality
For a substance to act as a monomer, it must have at least two bonding sites or reactive sites. “The number of bonding sites
in a monomer is referred to as functionality”.
In an olefin, the double bond can be considered as a site for two valencies. When the double bond is broken, two single
bonds can be available for combination. Thus,

No. of Bonding sites Functionality

2 Bifunctional
3 Trifunctional
- -
- -
n Polyfunctional

Classification of Polymers

1. Based on Origin / Source

Natural Polymers – These are found in nature. Examples – Starch, Cellulose, Proteins, Nucleic acid, Natural Rubber etc.,
Synthetic Polymers – These are manmade polymers. Examples – Polyethylene, Polyvinyl chloride, Polystyrene, Nylon etc.,

2. Based on the nature of monomer

Homopolymer – The polymer is made up of same monomer. Example -

Polyethylene

Heteropolymer – The polymer is made up of two or more types of monomers.

Example – BUNA - S

3. Based on Structure

Linear polymers – The monomeric units are joined in the form of a long straight chain.
Example – High density Polyethylene (HDPE), Nylons etc.,

Branched chain polymers – They are mainly linear in nature, but also possess some
branches along the main chain. Example – Low density polyethylene (LDPE),
Glycogen, Amylopectin etc.,

Three – dimensional polymers – They contain monomer molecules connected to each

other by only covalent bonds. They contain three – dimensional cross linkages.
Examples – Bakelite, Urea – formaldehyde resin, etc.,

4. Based on arrangement of monomers in a heteropolymer

These polymers are also known copolymers.

Alternating Copolymers – The monomeric arrangement follow an alternating arrangement of monomers.

Statistical Copolymers – The monomeric arrangement follow a statistical rule.

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Block Copolymers – The monomers are arranged in blocks.

Tacticity
The word tacticity is derived from the Greek word called ‘Taktikos’ – which means “related to rearrangement.
“It is the stereochemical placement of atoms or molecules in a chiral carbon center on the backbone of the polymeric
chain”.
The arrangement of monomeric units in a polymer molecule can take place in an orderly or disorderly fashion with respect
to the main chain. The difference in configuration do affect the physical properties of the polymers.

Stereospecific Polymers

Based on the stereochemical orientation of atoms or molecules on the backbone of the polymeric chain, the polymers are
classified into three types.

• Isotactic Polymers
• Syndiotactic Polymers
• Atactic polymers

Isotactic Polymers
In the head-to-tail configuration of the polymeric chain, if the functional groups
are on the same side of the polymeric chain, the polymers are isotactic in nature.
Example - Polypropylene
Syndiotactic Polymers
In the head-to-tail configuration of the polymeric chain, if the functional groups
are arranged in an alternating manner, the polymers are syndiotactic in nature.
Example – Gutta Percha
Atactic Polymers
In the head-to-tail configuration of the polymeric chain, if the functional groups
are arranged at random, the polymers are atactic in nature.
Example – Polystyrene

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Types of Polymerization
LEARNING CONCEPT – 2 The process of polymerization reaction involves the union of two or more
• Types of Polymerizations
small, same or different monomer molecules to form a single large macro-
• Addition –
molecule, called Polymer.
• Condensation
• Copolymerization
• Co-ordination polymerization The three different types of polymerization reactions are
• Ziegler – Natta Catalysis • Addition polymerization
– Mechanism. • Condensation Polymerization
• Copolymerization.

Addition Polymerization

This reaction is also known as CHAIN POLYMERIZATION

It is the reaction in which the monomers containing unsaturation (i.e., double bond or triple bond) react together in the
presence of heat, light or catalyst and form a large molecule without any loss in molecular weight.

Salient features
• It is the reaction that yields a product, which is an exact multiple of the original monomeric molecule.
• The molecular weight of the polymer is equal to the total weight of the monomers.
• The molecular weight will be integral multiple to the weight of the monomer.
• The reaction must be instigated by the application of heat, light or a catalyst for breaking the double bond present
in the monomer.

Condensation Polymerization

This reaction is also known as STEP POLYMERIZATION

It is defined as the reaction occurring between simple polar groups containing monomers with formation of polymer and
elimination of small molecules like H2O, HCl, etc.,

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The reaction occurs between the monomers containing simple polar groups to form a polymer by the elimination of small
molecules like water, HCl, ammonia, etc.

Salient Features
• The molecular weight of the polymer is not equal to the total weight of the monomers reacted.
• The reaction takes place in steps.
• The rate of reaction is slow.

Differences between Addition Polymerization and Condensation Polymerization

Addition Polymerization Condensation Polymerization

1. This is also known as Chain Polymerization 1. This is also known as Step polymerization
2. The monomers containing unsaturation will react 2. The monomers containing simple polar groups will
react
3. The molecular weight of the polymer formed is 3. The molecular weight of the polymer formed is
equal to the total weight of the monomers less than the total weight of the monomers
reacted. reacted.
4. No small molecules are lost. 4. Small molecules like H2O, HCl or NH3 will be
lost.
5. The repeating units are added one at a time to the 5. Any two monomeric species present can react.
growth chain.
6. The number of units decreases steadily throughout 6. Monomers disappear early in the reaction.
the reaction.
7. High molecular weight polymers are formed at 7. The degree of polymerization rises steadily
once. throughout the reaction
8. Longer reaction time affects the molecular weight, 8. To obtain higher molecular weight, longer
but yield is high. reaction times are essential.

Copolymerization

It is the joint polymerization of two or more monomeric species. The polymers obtained are known as copolymers.
Example – Copolymerization of styrene and butadiene yield Styrene Butadiene rubber (SB – R).

Coordination Polymerization

It is also known as Ziegler – Natta Catalysis or stereospecific polymerization.

Carl Ziegler and Giulio Natta discovered that a combination of transition metal halides (TiCl4 or TiCl3, ZrBr3, TiCl2, halides
of V, Mo, Zr, Cr and W) with an organometallic compound like triethyl aluminium, triethyl aluminium were used to
synthesize stereospecific polymers.

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Mechanism of Stereospecific Polymerization

Step – 1 – Chain initiation reaction

Step – 2 – Chain propagation reaction

Step – 3 – Chain termination reaction

The method is important because it is used to synthesize stereospecific polymers. This is used in the synthesis of
polypropylene, polydiene, etc. During polypropylene synthesis, if conventional catalysts are employed,
random or atactic polymers are obtained. By using a suitable catalyst, solvent and temperature, it is possible to
synthesize stereospecific polymers.

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Plastics:
LEARNING CONCEPT – 3 The word plastic is derived from a Greek word called PLASTIKOS.
• Plastics – Properties – PLASTIKOS means it can be easily moulded.
• Types - Thermoplastics –
Thermosets – with examples – Plastics are “organic materials of high molecular – weight, which can be
• Differences. easily moulded into any desired form when subjected to heat and pressure
in the presence of a catalyst”.

Nowadays, plastics are synonymously considered as RESIN. However, Plastics are not resin and Resin is a part of plastic.

Characteristics of Plastics

• Light in weight – They have a specific gravity of 1 to 2.4

• Good thermal and Electrical Insulation – They possess very low thermal and electrical conductance.
• Corrosion resistance – Plastics are highly corrosion resistant.
• Easy workability – Casting, moulding, drilling, sawing, machining, etc. of plastic can be easily done.
• Easy moulding – Can be easily moulded into typical shapes and forms.
• Chemical Resistance – Have resistance to the action of light, oils, acids and dampness. They do not absorb water.
• Mechanical Stability – they have good dimensional stability, abrasion resistance, and tensile strength (up to
5500 kg/cm2).

Types of Plastics

Based on the nature of intermolecular forces, the plastics are classified into two types.
• Thermoplastic materials.
• Thermosetting materials.

Thermoplastic Materials
• These are also known as Thermoplasts.
• They are linear long-chain polymers.
• They are formed during addition polymerization.
• They can be softened on heating and hardened on cooling reversibly.
• Hardness is a temporary property subjected to the rise and fall of temperature.
• They can be recycled, reshaped and reused.
• They are soluble in organic solvents
• Examples – Polyethylene (PE), Polypropylene (PP), Polystyrene (PS), Polyvinyl Chloride (PVC),
Polytetrafluoroethylene (PTFE).

Thermosetting Materials
• These are also known as Thermosets.
• These polymers during moulding (by heating) get hardened and once they are solidified, they cannot be softened.
• They are permanently setting polymers.
• During moulding, they acquire a three-dimensional structure with strong covalent bonds.
• Once moulded, they cannot be recycled, reshaped and reused.
• They are not soluble in all organic solvents.
• Examples – Bakelite, Polyester (terylene), Epoxy resins (Araldite), Urea – formaldehyde, etc.

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Differences between thermoplastics and thermosets

Thermoplastics Thermosets
1. They are softened on heating readily. 1. They do not soften on heating. On prolonged heating, they get
charred.
2. They consist of linear long-chain molecules. 2. They have three-dimensional structures with strong covalent
bonds.
3. They are mostly formed by addition polymerization. 3. They are mostly formed by condensation polymerization.
4. They can be softened, recycled, reshaped and reused on 4. They cannot be softened, recycled, reshaped and reused.
heating.
5. They are usually soft, weak and less brittle 5. They are usually hard, strong and brittle.
6. They can be reclaimed from wastes. 6. They cannot be reclaimed from wastes.
7. They are usually soluble in some organic solvents 7. They are insoluble in almost all organic solvents.

Uses of Plastics

Plastics have assumed a very important position as engineering materials. Some of the important applications/uses of
plastics are

• For making electrical goods.

• For making handles for tools and covers of machines.
• For making electrical appliances such as plugs, switches, holders radio and TV cabinets.
• For making hoses, water tubes, electrical cables, gramophone records, machine parts, telephone parts, packing
bags, seat covers, light fixtures, tank linings, etc.
• For making household articles like toys, combs, trays, toilet goods, toothbrush bristles, lenses, racket strings, etc.
• For making synthetic fibers like Terylene, nylon, etc.
• For preparing decorative laminates and mouldings.

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INDIVIDUAL POLYMERS
LEARNING CONCEPT – 4 1. Polyvinyl Chloride
• Preparation, Properties and It is a thermoplastic polymer. In PVC the mass of chlorine is 57% of the total
Applications of – mass of the polymer.
o Polyvinyl Chloride
o Teflon
o Bakelite Method of Preparation:
o Nylon It is obtained by the free radical addition polymerization of vinyl chloride in
the presence of benzyl peroxide or hydrogen peroxide.

Vinyl chloride is obtained by treating acetylene with HCl at 60-80° C in the presence of a metal oxide catalyst.

Properties
• PVC is colorless, non – inflammable and chemically inert powder. It is strong but brittle.
• It is resistant to ordinary light, atmospheric gases, moisture, inorganic acids and alkalis, but undergoes
degradation in heat or UV light.
• It is soluble in hot chlorinated hydrocarbons like ethyl chloride
• Pure resin possesses a high softening point.
• It has greater stiffness and rigidity compared to polyethylene.

Engineering Applications
• It is widely used as a synthetic plastic.
• Rigid PVC is used for making sheets, light fittings, safety helmets, refrigerator components, tires, and cycle and
motorcycle mudguards.
• Plasticized PVC is used in making continuous sheets viz., tablecloths, raincoats, curtains, etc.,
• Used in injection moulding of articles like toys, tool – handles, radio – components, chemical containers,
conveyor belts, etc.,

2. Poly Tetrafluoro Ethylene (PTFE)

It is also known as the Teflon of FLUON. It is an addition polymer.

Method of preparation
It is prepared by polymerizing water emulsion of tetra fluoro ethylene under pressure in the presence of benzoyl peroxide
as catalyst.

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Properties
• Due to the presence of highly electronegative fluorine atoms, they have high intermolecular forces of attraction.
• They are tough and have a high softening temperature (up to 350° C).
• They are waxy to touch and have a high coefficient of friction.
• They are good electrical insulators.
• They have good mechanical properties.
• They have good chemical resistance, but soluble in hot chlorinated hydrocarbons.

Engineering Applications
• It is used as an insulator in motors, transformers, cable wires, fittings, etc.
• It is used for coating and impregnating glass fibers, asbestos, fibers and cloths.
• It is used for making gaskets, packings, pump parts, tank linings, chemical carrying pipes, tubing, etc.
• It is used in making non-lubricating bearings, non-sticking stop-cocks (for burettes), etc.

3. Bakelite
It is also known as phenol formaldehyde resin.
It is a condensed polymer.

Method of Preparation
It is prepared by condensing phenol with formaldehyde in the presence of an acidic/alkaline catalyst. The reaction takes
place in three steps.

Step – 1
Phenol and formaldehyde react together to form ortho and para hydroxy products, o-hydroxy methylol phenol and p-
hydroxy methylol phenol.

Step – 2
The formed ortho and para hydroxy products react with phenol to give a linear polymer NOVOLAC.

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Step – 3
NOVOLAC in the presence of hexamethylene tetramine gives Bakelite.

Properties
• Phenolic resins (like Bakelite) are set to rigid, hard, strong, scratch-resistant, infusible, water-resistant, insoluble
solids, which are resistant to non-oxidizing acids, salts and many organic solvents.
• They can be attacked by alkalis, because of the presence of free hydroxyl groups in their structures.
• They possess excellent electrical insulating characteristics.
• They are good anion exchange resins capable of replacing anions with –OH groups.
• They are good adhesives, corrosion resistant and resistant to atmospheric gases, moisture and UV light.

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Engineering Applications
1. For making electric insulator parts like switches, plugs, switch-boards, heater handles, etc.
2. For making moulded articles like telephone accessories, and cabinets for radio and television.
3. For impregnating fabrics, wood and paper.
4. As adhesives (e.g., binder) for grinding wheels.
5. In paints and varnishes.
6. As hydroxyl group exchanger resins in water softening
7. For making bearings, used in propeller shafts for the paper industry and rolling mills.

4. Nylon – 6:6
These belong to the class of polyamides. They are condensing polymers.

Method of preparation
It is obtained by polymerizing hexamethylene diamine and adipic acid.

Properties
• High mechanical strength, stiffness, hardness and toughness.
• Good fatigue resistance.
• High mechanical damping ability.
• Good sliding properties.
• Excellent wear resistance.

Engineering Applications
• Used as a thread in bristles for toothbrushes.
• As gears, fittings and bearings.
• Threads, ropes, nets, parachutes.
• Air bags, swimwear, machine parts.

• Thermoplastic materials can be melted and reshaped multiple times, making them
recyclable, while thermosetting materials, once hardened, cannot be remelted due to
their permanent cross-linked structure, making them heat-resistant but non-recyclable.
• Polyvinyl chloride (PVC) is soft because it is a thermoplastic, meaning its polymer chains
are loosely held together, allowing flexibility and easy reshaping when heated. Bakelite,
on the other hand, is a thermosetting polymer with a rigid, cross-linked structure formed
during curing, making it hard, heat-resistant, and inflexible. This cross-linking gives
Bakelite its high durability and strength.

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RUBBERS
LEARNING CONCEPT – 5 These are also known as elastomers. These are high molecular weight
• Rubbers – Natural - Synthetic – compounds that exhibit elastic properties. On application of deformation
Properties of natural rubber – force, they stretch out and regain their original shape on the removal of the
Vulcanization. deformation force. They can be stretched up to 4 to 10 times of their initial
length.
Their elastic nature is due to their curly structure. Elastomers are expected to have the following characteristics.

• They have elasticity i.e.; it can be stretched by applying stress and can regain their original shape and dimension
by releasing the stress.
• They have very low inter-chain attraction forces.
• They have a coiled structure.
• They can absorb water.
• They have low chemical sensitivity
• At high temperatures they become sticky.

Elastomers are of two types

• Natural rubber
• Synthetic rubber

Natural Rubber
• It is also known as cis-polyisoprene.
• It is obtained from the latex of natural rubber plant Hevea brasilensis i.e., natural rubber plant.
• Natural rubber consists of the basic material latex, which is a dispersion of isoprene.
• During treatment, these isoprene molecules polymerize to form, long-coiled chains of cis-polyisoprene.

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Gutta – Percha
• It is trans-polyisoprene.
• It is prepared from the matured leaves of Dichopsis Gutta and Palagam Percha.
• Matured leaves are grounded well, treated well with water at 70°C and the
dispersion is poured into cold water. The resin floats on the water and is collected.
Properties
• At room temperature, they are horny and tough. They soften at 100°C.
• They are insoluble in aliphatic hydrocarbons, but insoluble in aromatic and chlorinated hydrocarbons.
Engineering Applications
• They are used in the manufacturing of golf ball covers, submarine cables, adhesives and tissues for surgical
purposes.
Disadvantages of Natural Rubber
• It is soft at high temperature, brittle at low temperatures. Its working temperature is in the range of 10 to 60°C
only.
• It is weak and has poor tensile strength, 200kg/cm2.
• It has a high-water absorption capacity, swells in water.
• It dissolves in mineral oils, acids, bases and non-polar organic solvents like benzene.
• It is attacked by oxidizing agents including atmospheric oxygen and becomes sticky.
• It undergoes permanent deformation when stretched.
These properties make rubber limited in use and compounding of rubber solves the problems.

Vulcanization of Rubber
• To improve the properties of natural rubber, it is compounded with some chemicals like Sulphur, hydrogen
sulphide, benzoyl chloride, etc. This process is known as vulcanization and the chemical compounded is known
as vulcanizing agent. The most commonly used vulcanizing agent is Sulphur.
• The natural rubber and Sulphur is heated to 100 - 140°C, Sulphur combines chemically at the double bonds of
the different chains of rubber and produces three dimensional crossed linked rubber, which over comes all the
drawbacks of natural rubber.
• This vulcanized rubber does not melt on heating. The extent of stiffness of vulcanized rubber depends on the
amount of Sulphur added. For example, a tyre rubber may contain 3-5 % of sulphur, but a battery case rubber
may contain as much as 30% sulphur. Vulcanization provides cross-linking of sulphur atoms between the adjacent
chains of rubber.

• The curing time may vary. Over-curing temperature decreases stretch and tensile strength, under-curing makes it
too soft. So proper curing is required.
• The amount of Sulphur used for ordinary soft rubber is 1 to 5% whereas for hard rubber it is 40 to 45% of the
rubber. The other vulcanizing agents used include Se, Te, benzoyl chloride, tri nitro benzene, alkyl phenol
sulphides, H2S, MgO, benzoyl peroxide, etc.

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Advantages of Vulcanization
Vulcanization transforms the weak, thermoplastic rubber into a strong and tough rubber.
• The working temperature range is – 10 °C to 100 °C.
• The tensile strength increases. (2000kg/cm3)
• The water absorptivity decreases.
• The article made from vulcanized rubber returns to the original shape when the deforming load is removed, i.e.,
the resilience power is increased.
• The vulcanized rubber becomes resistant to organic solvents like CCl4, benzene, fats and oils; however, it swells in
these solvents
• It becomes resistant to abrasion, ageing and reactivity with oxygen & ozone.
• It becomes better electrical insulator.
• It can be easily manipulated into desired shape.

Synthetic rubber
The natural rubber sources are not sufficient and could not supplement the needs of automobile industry. An attempt was
made to synthesize rubber, but rubber like materials were synthesized to supplement the needs of various industries. These
materials synthesized by various processes are called elastomers. The artificially prepared polymer, which has elastomeric
property, is known as synthetic rubber. There are several types of synthetic rubbers available and used on commercial
grade.

Examples – BUNA – S, BUNA – N, Thiokol Rubber

Important differences between natural rubber and vulcanized rubber

• Elasticity and Strength: Natural rubber is soft and less durable, while vulcanized rubber
undergoes a curing process with sulfur, increasing its elasticity, strength, and resistance to wear.
• Temperature Resistance: Natural rubber becomes sticky in heat and brittle in cold, whereas
vulcanized rubber maintains its flexibility and durability over a wide range of temperatures.
• Chemical Resistance: Vulcanized rubber is more resistant to chemicals, oils, and solvents
compared to natural rubber, making it more suitable for industrial applications

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Synthetic Polymers
LEARNING CONCEPT – 6 1. Buna – S
• Preparation, properties and • It is the most important type of synthetic rubber.
applications of – • It is also known as Styrene – Butadiene rubber or GR - S
o BUNA – S, Method of Preparation
o Thiokol rubber. It is obtained by copolymerizing butadiene (75% by weight) and styrene
(25% by weight) in the presence of sodium metal as catalyst.

Properties
• It possesses high abrasion resistance, high load bearing capacity and resilience.
• It can be oxidized easily in the presence of even trace amount of ozone in the atmosphere.
• It swells in oils and solvents.
• It is also a good electrical insulator.

Engineering applications
• It is mainly used in the manufacturing of motor tyres.
• It is also used in the manufacturing of floor tiles, shoe soles, gaskets, foot – wear components, wire and cable
insulations, carpet backings, adhesives, tank linings, etc.

2. Thiokol Rubber
• It is also known as polysulphide rubber or GR – P

Method of Preparation
It is prepared by condensing sodium polysulphide and ethylene dichloride.

Properties
• It possesses extremely good resistance to mineral oils, fuels, solvents, oxygen, ozone and sunlight.
• It is also impermeable to gases.
• It also possesses good strength and abrasion resistance.

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Applications
1. It is used for coating fabrics, for making life rafts and jackets.
2. It is used for making gaskets, diaphragms and seals in contact with solvent and for printing rolls.
3. It is used for lining hoses for gasoline and other transport pipes
4. Liquid Thiokol can be used to make tough solvent resistant temperature liquid compounds which are used as liners for
aircraft.

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Introduction
LEARNING CONCEPT – 7
• Fiber Reinforced Plastics - Fiber – Reinforced plastic (FRP) is a composite material. An FRP
Introduction – composite is defined as a polymer that is reinforced with a fiber.
o Need for reinforcement –
o Types of FRP – Aramids – FRP consists of two phases,
Kevlar and Nomex – i. Continuous Phase or matrix phase
Preparation and ii. Dispersed phase or reinforcement phase.
applications.
Matrix is a polymer usually an epoxy, vinyl ester or polyester thermosetting plastic.
Fiber or dispersed phase with a high strength such as glass, graphite, alumina, carbon, boron, beryllium and aromatic
polyamides.

Need for Reinforcement

Polymer composites are required to withstand the intense conditions in many applications and are favored over many
traditional metals and materials due to their advantageous characteristics which include:
1. They are light in weight
2. They have a high strength-to-weight ratio
3. They are much stronger and more durable than conventional metals like steel, aluminum
4. They are most suitable for aerospace applications due to their inherent characteristic properties.
5. They have good corrosion resistance
6. They have high fatigue strength
7. They have high-temperature resistance.

Constituents of Composites

i) Fibers: Three types of fibers viz. carbon, glass and aramid fibers are used
ii) Matrix: The matrix should transfer the forces between the fibers and protect the fibers from the environment. Commonly
used matrices are thermo-sets viz. vinyl ester or epoxy.

Types of Fiber-Reinforced Composites

1. Glass Fiber Reinforced Plastics (GFRP)

• Glass fibers are made by mixing silica, sand, limestone, folic acid and other minor ingredients.
• The mix is heated up to 1260 °C and allowed through fine holes in a platinum plate.
• The glass strands are cooled, gathered and wound.
• For example, aluminium lime borosilicate glass fibers have high electrical insulating properties, low
susceptibility to moisture and high mechanical properties.
• Glass fibers have excellent characteristics equal to or better than steel in certain forms.

Properties
• They have a high ratio of surface area to weight. As a result, they are more useful and also, they are vulnerable to
chemical attacks.
• Blocks of fibers trap the air, which makes them good thermal insulators. Their thermal resistance is 0.04W/mk.
• The fresh and thin fibers are the strongest. If the surface of the FRP is more, its strength is less. Moisture is easily
adsorbed and worsens the microscopic cracks, surface defects, etc.

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• It can undergo more elongation before it breaks.

• The viscosity of molten glass is very important. If the viscosity is higher, the FRP breaks during drawing, or if the
viscosity is too low, the glass will form droplets.

Applications
• Fiberglass possesses low density, high tensile strength, high impact resistance, excellent chemical and corrosion
resistance and is stiff and rigid.
• They are used in making automotive parts, storage tanks, plastic pipes, industrial floorings and transport vehicles
to boost fuel efficiency.

2. Carbon Fiber Reinforced Plastics (CFRP):

• Carbon fibers have a high modulus of elasticity and a low elongation coefficient.
• These are highly stiff, do not absorb water and are resistant to chemical attack.
• They do not undergo stress corrosion, do not show any creep and withstand fatigue.
• They are electrically conductive and might be corrected in a galvanic way when they are in contact with steel.

Properties
• They are alkali-resistant and are resistant to corrosion. Hence, they are used for corrosion control and
rehabilitation of concrete structures.
• They have low thermal conductivity.
• These have a high strength-to-weight ratio, which eliminates the requirement for heavy construction equipment
and supporting structures.
• These are available in rolls of very long length. Therefore, they need very few joints to avoid laps and their
transportation is easy.
• CFRP has a short curing time. So, they reduce the project duration and downtime of the structure to a great extent.
• CFRP is a bad conductor of electricity and is non-magnetic.

3. Aramid Fiber Reinforced Polymers (Bullet Proof Plastic)

• Aramids (Aromatic polyamides) belong to the family of nylons (for example, Nomex, Kevlar) which are being
used to make bulletproof vests and puncture-resistant tyres.
• They are also used in the manufacture of helmets.
• They are sensitive to elevated temperatures, moisture and ultraviolet radiation.
• But they have problems with relaxation and stress corrosion.

i) Kevlar:
It is a p-polyphenylene tere-phthalamide. It has recurring units joined by amide links, which have a carbonyl group and
an amine group. The repeating units consist of benzene rings as shown

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ii) Nomex:
This is produced by a condensation reaction between m-phenylenediamine and iso-phthaloyl chloride. It has meta-
phenylene groups which are attached to the phenyl ring at 1 and 3 positions as shown below.

Properties
• They appear yellow, have low density and high strength.
• These have good impact resistance, abrasion and chemical resistance and resistance to thermal degradation.
• However, some grades of aramids undergo degradation when exposed to UV light.

Applications
• They are used in the manufacture of protective apparel such as gloves, bulletproof vests, motorcycle protective
clothing, etc.
• Belts and hosing for industrial and automotive parts, aircraft body parts, fiber optic and electro-mechanical
cables are also made with them.

General advantages of FRP

• They can provide a maximum stiffness-to-density ratio of 3.5 to 5 times that of aluminium or steel.
• They can absorb impact stress and have high fatigue endurance limits.
• They strengthen the material properties and reduce corrosion potential.

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INTRODUCTION
LEARNING CONCEPT – 8
Conducting polymers – Most polymeric materials are poor conductors (insulators) of
• Introduction – electricity because of the non-availability of many free electrons for
• Classification – Intrinsic and extrinsic – the conduction process.
• Applications. However, some polymers have electrical conductivity on par with
the metallic conductors are called conducting polymers. Special
polymers with conductivities as high as 1.5 x 10 ohm m have been made.
7 -1 -1

Their conductivity may be due to unsaturation or due to the presence of externally added ingredients to polymers.
Electrical conductivity of a few polymers

Polymer Electrical Conductivity

Phenol-Formaldehyde 10-9 – 10-10
Nylon – 6:6 10-12 – 10-13
Polystyrene < 10-14
Polyethylene 10-15 – 10-17
Poly tetra fluoro ethylene < 10-17

Types of Conducting Polymers

Conducting polymers can be classified as

1. Intrinsically conducting polymers (ICP)
2. Doped conducting polymers (DCP)
✓ P-doping
✓ N-doping
3. Extrinsically conducting polymers (ECP)
✓ Conductive element-filled polymer
✓ Blended conducting polymer

Intrinsically conducting polymers

• These have conjugation of π bonds in their structure.
• The conduction process is due to the overlapping of orbitals containing conjugated π-electrons, resulting in the
formation of valence bands as well as conduction bands separated by a significant Fermi energy gap.
• The electrical conductivity is due to thermal or photolytic activation of the electrons, which gives them sufficient
energy to cross the Fermi gap and cause conduction.
• Conductivity of such polymers is of the order10-10 S.Cm-1
• Examples –
o Poly acetylene polymers e.g., poly – p-phenylene, polyquinoline etc.,
o Polymers with condensed aromatic rings e.g. poly aniline, polyanthralene, etc.,
o Polymers with aromatic, hetero aromatic and conjugated aliphatic units e.g. polypyrrole, polythiophene,
polybutadiene, etc.,

Doped Conducting Polymers

• These are obtained by exposing a polymer to a charge transfer agent either in the gas phase or in solution.
• These can be easily oxidized and reduced.
• The conductivity of such an ICP can be increased by creating either positive or negative charges on the polymer
backbone by oxidation or reduction.

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This technique is called doping, which is of two types.

1. p-doping polymers
• It involves treating an ICP with a Lewis acid, thereby the positive charges are created on the polymer backbone
by an oxidation process.
• This is also called oxidative doping. Polyacetylene is an example.
• Some of the common p-dopants are I2, Br2, FeCl3, PF6, Naphthyl amine, etc.

2. n-doping polymers
• This involves treating an intrinsically conducting polymer with a Lewis base, thereby reduction process takes place
and a negative charge on the polymer backbone is created.
• Some of the common n-dopants used are Li, Na, Ca, tetra butyl ammonium, etc.

Extrinsically conducting polymers:

These are the polymers whose conductivity is due to the presence of “externally” added ingredients to them. They are of
two types.
1. Conductive element-filled polymers:
• This is a resin or polymer filled with conducting elements such as carbon black, metallic fibers, metal oxides,
etc.
• The polymer acts as a binder to hold the conducting element together in the solid entity.
• They have reasonably good conductivity.
• These are low-cost polymers that are lightweight, have mechanical durability and have design compatibility.
• They are extensively used in the medical field.
• The disadvantage with them is that the addition of 10% carbon black will reduce the tensile, impact and
elongation strengths of the polymer.
2. Blended conducting polymers:
• They are obtained by blending a conventional polymer with a conducting polymer either by physical or
chemical change to improve the physical, chemical and mechanical properties of the polymer.
• They are used in electromagnetic shielding.
• They are also used in making rechargeable batteries, analytical sensors, ion exchangers, electronic displays,
optical fibers and photovoltaic devices.

Characteristics of Conducting Polymers

• The conjugation length of a polymer chain, doping level, temperature of operation and frequency of current are
some important factors that influence the conductivity of a conducting polymer.
• They have wide applications due to their low weight, easy process of manufacture and good mechanical
properties.
• They possess good conductivity and store charge.
• They are transparent to X-rays.
• They can be easily processed with product stability and efficient recycling.

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Applications of Conducting Polymers

1. In rechargeable lightweight batteries based on a perchlorate doped poly acetylene–lithium system, which is 10
times lighter than lead storage batteries.
2. In optical display devices based on polythiophene.
3. In wiring systems in aircraft and aerospace components.
4. In telecommunication systems.
5. In antistatic coatings for clothing.
6. In electromagnetic screening materials.
7. In electronic devices such as transistors and diodes.
8. In solar cells and drug delivery systems for the human body.
9. In molecular wires and molecular switches.
However, their conductivities are inferior to metals and hence have limited applications compared to metals.

Mechanism of conduction in Intrinsic Conducting polymers

• Intrinsic conducting polymers conduct electricity due to their conjugated structure, where
alternating single and double bonds create a pathway for delocalized π-electrons to move.
• The conduction mechanism involves thermally excited electrons that jump from the valence band
to the conduction band, leaving behind mobile holes.
• The conductivity increases with temperature as more charge carriers are generated.
• However, intrinsic conductivity is generally lower than that of doped polymers due to fewer
available carriers.

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