5.

POLYMERS

5.1 INTRODUCTION
The term "polymer" is derived from the ancient Greek word “polus” which means "many
or much" and “meros” means "parts". The term was coined in 1833 by Jöns Jacob Berzelius.
A polymer is a large molecule, with many repeated subunits called as monomers. The units
composing polymers (monomers) posses low relative molecular mass. The broad range of
properties of polymers plays an essential role in everyday life. Polymers range from familiar
synthetic plastics such as polystyrene to natural biopolymers such as DNA and proteins that are
the fundamentals of structure and functions of biology. Polymers have unique properties like
toughness, elasticity, glassiness and semicrystalline structures rather than crystals. They are
widely used in house hold items, construction, automobiles, defence, electrical and electronic
goods and computer components etc.
5.2. Definitions
1. Polymers
A polymer is a large macromolecule that posses a high molecular weight, with many
repeated linkages or subunits called as monomers.
Example
Polyethylene and Polyvinyl chloride are polymers formed by the repeated linking of large
number of ethylene and vinyl chloride molecules respectively.
nCH2 = CH2 (CH2 – CH2)n
Ethylene (monomer) Polyethylene (polymer)

nCH2 = CHCl (CH2 – CHCl)n

Vinyl chloride (monomer) Polyvinyl chloride (polymer)

2. Monomer
A polymer is a small micromolecule that posses a low molecular weight, which combines
with each other to form a macro molecule or polymer.

3. Polymerization
Polymerization is the transition of low molecular weight constituent (monomers) into a
high molecular weight constituent (polymers) by a chemical reaction. It is the process in which a
large number of small molecules (monomers) combine to form a big molecule (polymer) with or
without the elimination of a product.
nCH2 = CH2 (CH2 – CH2)n
Ethylene (monomer) Polyethylene (polymer)

4. Degree of Polymerization (DP)

 Degree of Polymerization is the number of monomeric units in
a macromolecule or polymer. It is also defined as the number of repeating units (n) in a polymer
chain.
It is represented by the following relationship
Degree of Polymerization = Molecular weight of the polymeric unit
Molecular weight of the monomer

5CH2 = CH2 (CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2)

In this example, five repeating units are present in the polymer chain. So, the degree of
polymerization is 5.

(i) Oligo Polymers

Polymers with low degree of polymerization are known as oligo polymers, their molecular
weight ranges from 500 – 5000.

(ii) High Polymers

Polymers with high degree of polymerization are known as high polymers, and their
molecular weight ranges from 10,000 – 2,00,000.

5. Nomenclature of Polymers

(i) Homopolymer
A polymer containing same type of monomers is known as Homopolymer.

Example Polyethylene, Polypropylene.

–––M–M–M–M–M–––
(ii) Copolymer (or) Heteropolymer
A polymer containing more than one type of monomers is known as Copolymer.

Example Nylon, Terylene.

. . . – M1 – M2 – M1 – M2 – M1 – . . .

(iii) Homochain polymer

If the main chain of a polymer is made up of same species of atoms, it is called Homochain
polymer.

Example Polyethylene, Polyvinyl chloride

...–C–C–C–C–C–C–...

(iv) Heterochain Polymer

If the main chain of a polymer is made up of different atoms, it is called Heterochain
polymer.

Example Terylene, Nylon 6:6.

 ...–C–C–O–C–C–O–C–C–...

6. FUNCTIONALITY AND ITS SIGNIFICANCE

The functionality of a monomer determines the final polymer that will be formed due to
the combination of the monomers. The number of bonding sites or reactive sites or functional
groups present in a monomer that are available for coupling will determine whether the monomer
will be mono-, bi-, tri-, or polyfunctional.
Significance
a. Monofunctional or unifunctional : When a single reactive group is present in the monomer
molecule, then it is termed as monofunctional or unifunctional. However a monofunctional group
cannot lead to the propagation of a polymer chain. For example, in carboxylic acid, CH 3COOH,
the –COOH group is the monofunctional group.

b. Bifunctional: When two reactive groups are present in the monomer molecule, then it is termed
as bifunctional. More often than not, polymerization reaction with bifunctinal groups occurs when
a double bond splits to couple with another double bonded monomer. If a double bonded molecule
is present, then the polymer would be –
CH2 = CH2
Ethylene 2 – functionality
(Two bonding sites are due to the presence of one double bond in the monomer. Therefore
ethylene is a bifunctional monomer).

c. Trifunctional: When a monomer contains three groups that are reactive, then it is termed as
trifunctional.It is important to note that a trifunctional polymer may be a mixture of
monofunctional and bifunctional monomer structures.

H2N –(--CH2--)6—NH2
Hexa methylene diamine 3 - funionality
(This monomer contains three functional groups, hence it is a trifunctional monomer).
d. Poly functional: If forms cross – linked polymer (three-dimensional network polymer). All the
monomers in the polymer are connected to each other by strong covalent bonds.

5.3. Classification of polymers

5.3.1. Classification based on source of availability
1. Naturally occurring polymers
These occur in plants and animals and are very essential for life. These include starch
cellulose, proteins, nucleic acids and natural rubber. Starch is a polymer of glucose, cellulose is
also a polymer of glucose and proteins are polymers of amino acids. Natural rubber consists of
repeat units of isoprene (2-Methyl-1,3-Butadiene).
2. Semi synthetic polymers
These are mostly derived from naturally occurring polymers by chemical modifications. Cellulose
on acetylation with acetic anhydride in presence of sulphuric acid forms cellulose diacetate used
in making threads and materials like films, glasses etc. Vulcanised rubber has much improved
properties and is used in making tyres etc. Gun-cotton, which is cellulose nitrate, is used in making
explosives.
3. Synthetic polymers
The polymers which are prepared in the laboratory are called synthetic polymers. These
are also called man made polymers. These include fibres, plastics and synthetic rubbers and find
diverse uses as clothing, electric fittings, eye lenses, substitute for wood and metals.
5.3.2. Classification based on Mode of polymerization
1. Addition polymers
A polymer formed by the direct repeated addition of monomer is called addition polymerisation.
In this type of polymers, the monomers are unsaturated compounds and are generally derivatives
of ethene. It is a reaction that yields a polymer, which is an exact multiple of the original
monomeric molecule. The original monomeric molecule, usually, contains one or more double
bonds. In addition polymerization there is no elimination of any molecule.

Example 1 Polyethylene is produced from ethylene.

nCH2 = CH2 (CH2 – CH2)n
Ethylene (monomer) Polyethylene (polymer)

Example 2 PVC is produced from vinyl chloride.

nCH2 = CHCl (CH2 – CHCl)n

Vinyl chloride (monomer) Polyvinyl chloride (polymer)
2. Condensation polymers (or) step wise polymerization
Condensation polymerisation involves a series of condensation reactions generally
involving two different monomers. It is a reaction between simple polar groups containing
monomers. Each monomer normally contains two functional groups. During these reactions, there
is a loss of small molecules usually water and HCl. Some of the condensation polymers are; nylon,
terelene, alkyd resins, bakelite. The formation of nylon 66 is shown.
Example 1 Hexamethylene diamine and adipic acid condense to form a polymer, Nylon 66
(polyamide).
nHO2C(CH2)4CO2H + nNH2(CH2)6NH2 (OC(CH2)4CO-NH(CH2)6NH)n + 2n H2O
Adipic acid Hexamethylene diamine Nylon 66

In some cases condensation polymerization takes place without the elimination of small
molecules like H2O, HCl etc, but by just the opening of cyclic compounds.

Caprolactum Nylon 6

Example 2 Polymerisation of caprolactum to form Nylon 6.

3. Copolymers
When the polymers are synthesized by polymerization of two or more than two different
monomers, they are called copolymers. High molecular weight polymers, obtained by
copolymerization, are called copolymers. Copolymerization is mainly carried out to vary the
properties of polymers such as hardness, strength, rigidity, heat resistance etc. When styrene and
butadiene are polymerized, it gives the copolymer called styrene-butadiene rubber.

Example 1 Butadiene and styrene copolymerize to give GR-S rubber.

5.3.3. Classification according to its growth
In many polymerisation processes, it is difficult to find out whether the polymerisation has
occurred through addition or condensation. Therefore the polymers has been classified according
to the mode of addition of monomers. The polymerisation has been divided into two types.
(i) Chain growth polymerisation.
(ii) Step growth polymerisation.
(i) Chain growth polymerisation
Chain growth polymerisation involves a chain reaction. Therefore it requires an initiator like
organic peroxide to form free radical. These free radicals are added to another monomer forming
another free radical. The process results in the formation of chain and ultimately a polymer is
formed. This is known as chain growth polymerisation. The initiators are added in small quantities.
Examples :
Monomer Polymer
Ethylene Polyethylene
Butadiene Polybutadiene
Tetrafluoroethylene Teflon (PTFE)
Vinyl chloride Polyvinyl chloride (PVC)
ii) Step growth polymerisation
This type of polymerisation is due to the condensation process which takes place in several
steps. The condensation process may or may not be accompanied by elimination of smaller
molecules such as water etc.
Examples,
Monomer Polymer
Adipic acid and Hexamethylene diamine Nylon 66
Terephthalic acid and ethylene glycol Terelene or Dacron
Phenol and formaldehyde Bakelite
5.3.4. Classification based on structure
On the basis of structure of polymers, these can be classified as :
(i) Linear chain polymers
(ii) Branched chain polymers
(iii) Crossed linked polymers.
(i) Linear chain polymers
These are polymers in which monomeric units are linked to form linear chains. These
linear polymers are well packed and therefore have high densities, high tensile strength and high
melting points. For example, polythene, nylon and polyesters are linear chain polymers.
(ii) Branched chain polymers
 These are polymers in which monomers are joined to form long chains with branches of
different lengths. Fig (b) These branched chain polymers irregularly packed and therefore, they
have low tensile strength and melting points than linear polymers. For example, low density
polyethene , glycogens etc.
(iii) Cross-linked polymers
These are polymers in which monomer units are cross- linked together to form a three-
dimensional net work. These polymers are hard, rigid and brittle because of network structure.
These are shown in Fig (c). For example melamine formaldehyde resin bakelite etc.

Linear

Branched

Cross linked

5.3.5. Classification based on molecular forces

The intermolecular forces present in polymers are vanderwaal’s forces and hydrogen
bonding. Although these are weak forces but in macromolecules (polymers), these forces have
accumulative effect all along the chain of polymers. Polymers are thus classified into four
categories on the basis of magnitude of these intermolecular forces in them.
(i) Elastomers
In these polymers, the chains are held together by weakest intermolecular forces which permit the
polymers to be stretched. A few ‘cross-links’ are introduced between the chains which help the
polymers to regain its original position, when the force is released. e.g., vulcanised rubber.
(ii) Fibres
These polymers possess high tensile strength and are used in making fibres. This is due to the
strong inter nuclear forces like hydrogen bonding which operate, for example in nylon-66 (a
polyamide) These forces also lead to close packing of chains and thus give crystalline nature.
Because of that, these polymers show sharp melting points.
(iii) Thermoplastics
These are polymers in which the intermolecular forces of attraction are mid-way between those
of elastomers and fibres. Due to that, these can be easily moulded by heating. In thermoplastic
polymers, there exists no cross-linking between chains. Examples of these polymers are
polyethylene, polystyrene etc.
(iv) Thermosetting polymers
These are prepared from low molecular mass semifluid substances. When heated in a mould,
they get highly cross-linked to form hard infusible and insoluble products. The common example
is bakelite.

Classification based on Thermal Behavior

There are two types.
1. Thermoplastics
2. Thermosetting Plastics
1. Thermoplastics
Thermoplastic polymer is one, which softens on heating and becomes rigid on cooling.
This is due to the disruption of weak attractive forces between the long polymer molecule on
heating. Most addition polymers and some condensation polymers are thermoplastics; they are
generally soluble in organic solvents.
Examples: Nylon, Polyethylene, Polystyrene and Polyvinyl chloride
2. Thermosetting plastics
Thermosetting plastics are one, which becomes hard on heating and they cannot be
softened again. Various polymer chains are held together by strong covalent bonds called
crosslinks.
Examples: Polyurethanes, Bakelite, Polyester.
Difference between Thermoplastic and Thermosetting Resins
THERMOPLASTIC RESINS THERMOSETTING RESINS

They are formed by addition They are formed by condensation

polymerization polymerisation
They consist of linear long chain They consist of three dimensional
polymers. network structures.
All the polymer chains are held All the polymer chains are linked by
together by weak vander waals forces. strong covalent bonds.

They are weak, soft and less brittle. They are strong, hard and more brittle.
They soften on heating and harden on They do not soften on heating.
cooling.
They can be remoulded. They cannot be remoulded.
They have low molecular weights. They have high molecular weights.
They are soluble in organic solvents. They are insoluble in organic solvents.
Example: PVC, polyethylene. Example: Backelite, polyester.

5.4 Glass transition temperature (Tg)

Glass transition temperature (Tg) is the temperature below which amorphous domains lose
the structural mobility of the polymer chains and become rigid glasses. Glass transition
temperature is the reversible transition in amorphous materials from a hard and relatively brittle
state into a molten or rubber-like state. An amorphous solid that exhibits a glass transition is called
a glass.
Tm is the temperature at which crystalline domains lose their structure, or melt. As
crystallinity increases, so does Tm .
Thermal Behavior of Polymers at Glass Transition Temperature (Tg)
• At low temperatures, all amorphous polymers are stiff and glassy, sometimes called as the
Vitreous State, especially for inorganic polymers.
• On Warming, polymers soften in a characteristic temperature range known as the glass-rubber
transition region.
• The glass transition temperature (Tg), is the temperature at which the amorphous phase of the
polymer is converted between rubbery and glassy states.
• Tg constitutes the most important mechanical property for all polymers. In fact, upon synthesis
of a new polymer, the glass transition temperature is among the first properties measured.
The following physical properties undergo a drastic change at the glass transition temperature of
any polymer:
a) hardness
b) volume
c) modulus (Young’s module)
d) percent elongation-to-break

A: liquid region
B: liquid with some elastic response
C: Rubbery region
D: glassy region
E: crystallites in a rubbery matrix
F: crystallites in a glassy matrix

5.7. General Purpose Plastics

 They have low mechanical properties. They are used for the manufacture of commodity
items. They account for about 80 – 85% of total polymer production

Example: Polystyrene, Polyethylene, Polypropylene.

Properties:
 They have low mechanical properties.
 They have low abrasion resistance and poor dimensional stability.
 They are mostly crystalline with low glass transition temperature.
 They cannot be used at high temperature since they have low use temperature.
2. Engineering plastics
Engineering plastics are obtained from high polymer resins. They have high mechanical
strength and toughness. They are mainly used in load bearing application and also used to replace
conventional materials like metal, wood, glass and ceramics.

Example: PVC, Polyethylene, Polycarbonates, polyurethanes, Nylon and PET

(Polyethylene Terepthalate).
Properties:
Engineering plastics have
 high mechanical strength and abrasion resistance.
 very good rigidity and high load bearing capacity.
 good thermal stability,
 high dielectric constants and good dimensional stability.
 They are light weight and readily moldable into complicated shapes
 They can be used in the same manner as metals, alloys and ceramics.

5.5 IMPORTANT ENGINEERING PLASTICS

1 POLYVINYL CHLORIDE (PVC)
Monomer Preparation: Vinyl chloride is prepared by treating acetylene with hydrogen
chloride at 60-80C in the presence of metal chloride as catalyst.

CH CH + HCl CH2 CH

Cl
Acetylene Vinylchloride

PVC Preparation: Polyvinyl chloride is obtained by emulsion polymerization of vinyl chloride in

presence of benzoyl peroxide (BPO) (or) hydrogen peroxide under pressure.
 BPO
n CH2 CHCl + HCl [ CH2 CH ] n
Polymerisation
Vinylchloride Cl
PVC

Properties
 PVC is colorless, odourless non-inflammable and chemically inert.
 It is insoluble in inorganic acids and alkalis, but soluble in hot chlorinated hydrocarbons
such as ethylchloride.
 It undergoes degradation in presence of heat (or) light.
Uses
 It is the most widely used synthetic plastic.
 It is used in the production of pipes, cable insulations, table covers and rain – coats, etc.,
 It is also used for making sheets, which are employed for tank-linings, light fittings,
refrigerator components, etc.,

2 TEFLON (OR) POLYTETRAFLUOROETHYLENE (PTFE)

Monomer Preparation

CaF2 + H2SO4 CaSO4 + 2HF

CH4 + 3Cl2 CHCl3 + 3HCl

CHCl3 + 2HF CHClF2 + 2HCl

2CHClF2 CF2 CF2 + 2HCl

Tetrafluoroethylene

Teflon Preparation: Teflon is obtained by polymerization of tetrafluoroethylene at elevated

pressure in presence of benzoyl peroxide as Initiator.

(C6H5CO)2O2
nCF2 CF2 [ CF2 CF2 ]n
Polymerisation Teflon

Properties
 It has high melting point due to the presence of fluorine atoms.
  It has an excellent thermal stability.
 It is extremely tough, flexible material having high softening point (about 350C).
 It has extremely good electrical and mechanical properties.
 It is corrosive resistant towards acid and alkali.
Uses
 It is used for making non-lubricating bearings, chemical carrying pipe, etc.
 It is used as a electrical insulating material in motors, cables, transformers, electrical
fittings.
 It is also used for making gaskets, packings, pump parts, tank linings, etc.
 It is used in making non-sticking stop cocks for burettes and kitchen appliances.
3. Bakelite
Reaction:

Step I:
Formation of ortho and para hydroxy benzyl alcohols from phenol and formaldehyde:

Step II:
Formation of Novalac from ortho-hydroxy,benzyl alcohol

Ortho-Hydroxy Benzyl Alcohol Novolac

Step III:
Formation of Bakelite from Novalac
Properties of bakelite
Some important properties of bakelite are listed below.
 It can be quickly molded.
 Very smooth molding can be obtained from this polymer.
 Bakelite moldings are heat-resistant and scratch-resistant.
 They are also resistant to several destructive solvents.
 Owing to its low electrical conductivity, bakelite is resistant to electric current.

Uses of Bakelite
 Since this element has a low electrical conductivity and high heat resistance it can be used
in manufacturing electrical switches and machine parts of electrical systems.
 Used in molding.
 Phenolic resins are also extensively used as adhesives and binding agents.
 They are further used for protective purposes as well as in the coating industry.
 Bakelite has been used for making the handles of a variety of utensils.
 It is one of the most common and important polymers that are used to make different parts
of many objects.

4. Acrylonitrile butadiene styrene (ABS)

Acrylonitrile butadiene styrene (ABS) (chemical formula (C8H8)x·(C4H6)y·(C3H3N)z) is a

common thermoplastic polymer. Its glass transition temperature is approximately 104 °C). ABS is
amorphous and therefore has no true melting point.
ABS is a terpolymer made by polymerizing styrene and acrylonitrile in the presence of
polybutadiene. The proportions can vary from 15% to 35% acrylonitrile, 5% to 30% butadiene and
40% to 60% styrene. The result is a long chain of polybutadiene crisscrossed with shorter chains
of poly(styrene-co-acrylonitrile). The nitrile groups from neighbouring chains, being polar, attract
each other and bind the chains together, making ABS stronger than pure polystyrene. The
acrylonitrile also contributes chemical resistance, fatigue resistance, hardness, and rigidity, while
increasing the heat deflection temperature. The styrene gives the plastic a shiny, impervious
surface, as well as hardness, rigidity, and improved processing ease. The polybutadiene, a rubbery
substance, provides toughness and ductility at low temperatures, at the cost of heat resistance and
rigidity. For the majority of applications, ABS can be used between −20 and 80 °C, as its
mechanical properties vary with temperature. The properties are created by rubber toughening,
where fine particles of elastomer are distributed throughout the rigid matrix.

Preparation
ABS is made by dissolving polybutadiene in liquid acrylonitrile and styrene monomers and then
polymerizing the monomers by the introduction of free-radical initiators

ABS is derived from acrylonitrile, butadiene, and styrene. Acrylonitrile is a synthetic monomer
produced from propylene and ammonia; butadiene is a petroleum hydrocarbon obtained from the
C4 fraction of steam cracking; styrene monomer is made by dehydrogenation of ethyl benzene —
a hydrocarbon obtained in the reaction of ethylene and benzene.

ABS

Properties

 ABS provides favourable mechanical properties such as impact resistance, toughness, and
rigidity when compared with other common polymers.
 A variety of modifications can be made to improve impact resistance, toughness, and heat
resistance.
  The impact resistance can be amplified by increasing the proportions of polybutadiene in
relation to styrene and also acrylonitrile, although this causes changes in other properties.
 Impact resistance does not fall off rapidly at lower temperatures.
 Stability under load is excellent with limited loads. Thus, by changing the proportions of
its components, ABS can be prepared in different grades.
 Two major categories could be ABS for extrusion and ABS for injection moulding, then
high and medium impact resistance.
 ABS would have useful characteristics within a temperature range from −20 to 80 °C

Applications

 ABS's light weight and ability to be injection molded and extruded make it useful in
manufacturing products such as drain-waste-vent (DWV) pipe systems.
 Musical instruments such as recorders, plastic oboes and clarinets, piano movements, and
keyboard keycaps are commonly made out of ABS
 Other uses include golf club heads (because of its good shock absorbance), automotive trim
components, automotive bumper bars, binoculars, inhalers, monoculars, nebulizers.
 Enclosures for electrical and electronic assemblies (such as computer cases), protective
headgear, whitewater canoes, buffer edging for furniture and joinery panels, luggage and
protective carrying cases, pen housing, and small kitchen appliances.
 Toys, including LEGO and Kre-O bricks, are a common application
 In the field of medicine ABS is used in non-absorbable sutures, tendon prostheses, drug-
delivery systems tracheal tubes,

5.6 Types of compounding of plastics

Molding
Molding is the process of manufacturing by shaping liquid or pliable raw material using a rigid
frame called a mold or matrix. This itself may have been made using a pattern or model of the final
object.
A mold or mould is a hollowed-out block that is filled with a liquid or pliable material such as
plastic, glass, metal, or ceramic raw material. The liquid hardens or sets inside the mold, adopting
its shape. A mold is a counterpart to a cast. The very common bi-valve molding process uses two
molds, one for each half of the object.

Articulated molds have multiple pieces that come together to form the complete mold, and then
disassemble to release the finished casting; they are expensive, but necessary when the casting
shape has complex overhangs.

Piece-molding uses a number of different molds, each creating a section of a complicated object.
This is generally only used for larger and more valuable objects.

Blow molding is a manufacturing process for forming and joining together hollow plastic or glass
parts.

Injection molding
Injection molding is a manufacturing process for producing parts by injecting molten material into
a mould, or mold. Injection moulding can be performed with a host of materials mainly including
metals (for which the process is called die-casting), glasses, elastomers, confections, and most
commonly thermoplastic and thermosetting polymers. Material for the part is fed into a heated
barrel, mixed (using a helical screw), and injected into a mould cavity, where it cools and hardens
to the configuration of the cavity. After a product is designed, usually by an industrial designer or
an engineer, moulds are made by a mould-maker (or toolmaker) from metal, usually either steel or
aluminium, and precision-machined to form the features of the desired part. Injection moulding is
widely used for manufacturing a variety of parts, from the smallest components to entire body
panels of cars. Advances in 3D printing technology, using photopolymers that do not melt during
the injection moulding of some lower-temperature thermoplastics, can be used for some simple
injection moulds.
Injection moulding uses a special-purpose machine that has three parts: the injection unit, the
mould and the clamp. Parts to be injection-moulded must be very carefully designed to facilitate
the moulding process; the material used for the part, the desired shape and features of the part, the
material of the mould, and the properties of the moulding machine must all be taken into account.
The versatility of injection moulding is facilitated by this breadth of design considerations and
possibilities.

Applications
Injection moulding is used to create many things such as wire spools, packaging, bottle caps,
automotive parts and components, toys, pocket combs, some musical instruments (and parts of
them), one-piece chairs and small tables, storage containers, mechanical parts (including gears),
and most other plastic products available today. Injection moulding is the most common modern
method of manufacturing plastic parts; it is ideal for producing high volumes of the same object.

Extrusion molding
Extrusion is a process used to create objects of a fixed cross-sectional profile by pushing material
through a die of the desired cross-section. Its two main advantages over other manufacturing
processes are its ability to create very complex cross-sections; and to work materials that are brittle,
because the material encounters only compressive and shear stresses. It also creates excellent
surface finish and gives considerable freedom of form in the design process.
Drawing is a similar process, using the tensile strength of the material to pull it through the die. It
limits the amount of change that can be performed in one step, so it is limited to simpler shapes,
and multiple stages are usually needed. Drawing is the main way to produce wire. Metal bars and
tubes are also often drawn.
Extrusion may be continuous (theoretically producing indefinitely long material) or semi-
continuous (producing many pieces). It can be done with hot or cold material. Commonly extruded
materials include metals, polymers, ceramics, concrete, modelling clay, and foodstuffs. Products
of extrusion are generally called extrudates.
Process
The process begins by heating the stock material (for hot or warm extrusion). It is then loaded into
the container in the press. A dummy block is placed behind it where the ram then presses on the
material to push it out of the die. Afterward the extrusion is stretched in order to straighten it. If
better properties are required then it may be heat treated or cold worked.
Applications

 In the food industry with the advent of industrial manufacturing, extrusion found
application in food processing of instant foods and snacks
 For use in pharmaceutical products, extrusion through nano-porous, polymeric filters is
being used to produce suspensions of lipid vesicles liposomes or transfersomes with a
particular size of a narrow size distribution.
 The extrusion production technology of fuel briquettes is the process of extrusion screw
wastes (straw, sunflower husks, buckwheat, etc.) or finely shredded wood waste (sawdust)
under high pressure when heated from 160 to 350 °C
 The majority of synthetic materials in textiles are manufactured with extrusion only. Fiber
forming substances are used in extrusion to form various synthetic filaments. The molten
materials are passed through a spinneret that helps in forming fibers.

Compression moulding
Compression molding is a method of molding in which the molding material, generally preheated,
is first placed in an open, heated mold cavity. The mold is closed with a top force or plug member,
pressure is applied to force the material into contact with all mold areas, while heat and pressure
are maintained until the molding material has cured; this process is known as compression molding
method and in case of rubber it is also known as 'Vulcanisation'. The process employs
thermosetting resins in a partially cured stage, either in the form of granules, putty-like masses, or
preforms.

Compression molding is a high-volume, high-pressure method suitable for molding complex,

high-strength fiberglass reinforcements. Advanced composite thermoplastics can also be
compression molded with unidirectional tapes, woven fabrics, randomly oriented fiber mat or
chopped strand. The advantage of compression molding is its ability to mold large, fairly intricate
parts. Also, it is one of the lowest cost molding methods compared with other methods such as
transfer molding and injection molding; moreover it wastes relatively little material, giving it an
advantage when working with expensive compounds.

Process

Compression molding is a forming process in which a plastic material is placed directly into a
heated metal mold then is softened by the heat and therefore forced to conform to the shape of
the mold, as the mold closes. Once molding is completed excess Flash may be removed.
Typically, compression molding machines open along a vertical axis.

Applications
 Car tyres / rubber tyres
 Rubber gaskets or seals
 Handles
 Electrical components
 Automotive parts
 Other various polymer matrix composite parts

5.7 Conducting polymers

Polypyrrole (PPy)
Polypyrrole (PPy) is an organic polymer obtained by oxidative polymerization of pyrrole. It is a
solid with the formula H(C4H2NH)nH. It is an intrinsically conducting polymer, used in
electronics, optical, biological and medical fields.
Structure

Preparation
Different methods can be used to synthesize PPy, but the most common are electrochemical
synthesis and chemical oxidation.

Chemical oxidation of pyrrole:

n C4H4NH + 2n FeCl3 → (C4H2NH)n + 2n FeCl2 + 2n HCl

The process is thought to occur via the formation of the pi-radical cation C4H4NH+. This
electrophile attacks the C-2 carbon of an unoxidized molecule of pyrrole to give a dimeric cation
[(C4H4NH)2]++. The process repeats itself many times.

Properties

 Films of PPy are yellow but darken in the air due to some oxidation.
 Doped films are blue or black depending on the degree of polymerization and film
thickness.
 Doping makes the materials brittle
 They are stable in the air up to 150 °C at which temperature the dopant starts to evolve.
 PPy is an insulator, but its oxidized derivatives are good electrical conductors.

Applications
PPy and related conductive polymers have two main application in electronic devices and for
chemical sensors.

Polyacetylene
Polyacetylene (IUPAC name: polyethyne) usually refers to an organic polymer with the repeating
unit (C2H2)n. The name refers to its conceptual construction from polymerization of acetylene to
give a chain with repeating olefin groups. This compound is conceptually important, as the
discovery of polyacetylene and its high conductivity upon doping helped to launch the field of
organic conductive polymers. The high electrical conductivity discovered by Hideki Shirakawa,
Alan Heeger, and Alan MacDiarmid for this polymer led to intense interest in the use of organic
compounds in microelectronics (organic semiconductors). This discovery was recognized by the
Nobel Prize in Chemistry in 2000. Early work in the field of polyacetylene research was aimed at
using doped polymers as easily processable and lightweight "plastic metals". Despite the promise
of this polymer in the field of conductive polymers, many of its properties such as instability to air
and difficulty with processing have led to avoidance in commercial applications.

Structure

Preparation
From acetylene
A variety of methods have been developed to synthesize polyacetylene, from pure acetylene and
other monomers. One of the most common methods uses a Ziegler–Natta catalyst, such as
Ti(OPr)4/Al(C2H5)3, with gaseous acetylene. This method allows control over the structure and
properties of the final polymer by varying temperature and catalyst loading.

From precursor polymers

Polyacetylene can also be synthesized from precursor polymers. This method enables processing
of the polymer before conversion to insoluble polyacetylene. Short, irregular segments of
polyacetylene can be obtained by dehydrohalogenation of poly(vinyl chloride).

Properties

 They are insoluble in solvents,

 While both cis and trans-polyacetylene show high thermal stability
 exposure to air causes a large decrease in the flexibility and conductivity
 When polyacetylene is exposed to air, oxidation of the backbone by O2 occurs.
 Coating with polyethylene or wax can slow the oxidation temporarily, while coating with
glass increases stability indefinitely

Applications
  Polyacetylene has no commercial applications, although the discovery of polyacetylene as
a conductive organic polymer led to many developments in materials science.
 Conducting polymers are of interest for solution-processing for film-forming conductive
polymers. Therefore, attention has shifted to other conductive polymers for application
purposes including polythiophene and polyaniline.
 Molecular electronics could also be a potential application of conductive polyacetylene.

Polyaniline

Polyaniline (PANI) is a conducting polymer and organic semiconductor of the semi-flexible rod
polymer family. The compound has been of interest since the 1980s because of its electrical
conductivity and mechanical properties. Polyaniline is one of the most studied conducting
polymers.
Structure

Preparation
Although the synthetic methods to produce polyaniline are quite simple, the mechanism of
polymerization is probably complex. The formation of leucoemeraldine can be described as
follows, where [O] is a generic oxidant:
n C6H5NH2 + [O] → [C6H4NH]n + H2O
A common oxidant is ammonium persulfate in 1 M hydrochloric acid.

Properties

 Polyaniline is typically produced in the form of long-chain polymer aggregates.

 Polyaniline has high stability at room temperature.
 Polyaniline is highly electrically conducting.
 Polyaniline sensors typically exploit changes in electrical conductivity between the
different oxidation states or doping levels.
Applications

 The major applications are printed circuit board manufacturing: final finishes, used in
millions of m2 every year, antistatic and ESD coatings, and corrosion protection.
 Polyaniline and its derivatives are also used as the precursor for the production of N-doped
carbon materials through high-temperature heat treatment.
 Printed emeraldine polyaniline-based sensors have also gained much attention for
widespread applications where devices are typically fabricated via screen, inkjet

5.8 Composites
Polymer Matrix Composites (or) FRP (Fiber Reinforced Polymer Composites)
Preparation:
Fiber–reinforced plastics are obtained by bonding a fiber material with a resin matrix and curing
them under heat and pressure. The resin matrixes commonly used in FRP are polyesters, epoxy,
phenolic, silicone, and polyamide polymer resins. The main reinforcing agents used in FRP
composites are glass, graphite, alumina, carbon, boron, etc. The properties of FRP mainly depend
on nature of the resin matrix.
Properties of FRP:
It has good mechanical properties, since the fiber prevents slip and crack propagation.
It possesses high corrosion resistance and heat resistance property.
It possesses higher yield strength, fracture strength.
Examples of Resin Matrix
RESIN
REASON
Polyester resin : To provide very good strength and mechanical properties.
Epoxy resin : To impart good mechanical properties
Silicone resins : To impart excellent thermal and electrical properties
Phenolic resins : To withstand high temperatures

Examples of FRP composite

Glass – FRP
Properties
(i) lower densities, dielectric constants,
(ii) Higher tensile strength and impact resistance.
(iii) Excellent corrosion resistance, chemical resistance,
Uses
Non-flammability Automobile parts, storage tanks, plastic pipes, flouring, transportation
industries, etc.,
Boron – FRP
Properties
(i) Excellent stiffness and compressive strength.
(ii) Manufacturing of B-FRP is difficult.
Uses
Horizontal and vertical tail in aeroplane, stiffening spares, ribs, etc.
Carbon – FRP
Properties
(i) Lighter density.
(ii) Excellent resistance to corrosion.
(iii) Retention of desired properties even at elevated temperatures.
Uses
Structural components of air craft and helicopters, recreational equipments, sports material,
antenna disc, solar panel etc.,
Alumina – FRP
Properties
Good abrasion resistance, creep resistance and dimensional stability.
Uses
Components of engine parts in automobile industry, and components of turbine engine.

Types of Fibre Reinforced Polymer (FRP)

1. Glass Fibre Reinforced Polymer (GFRP)
Glass fibres are basically made by mixing silica sand, limestone, folic acid and other minor
ingredients. The mix is heated until it melts at about 1260°C.
The molten glass is then allowed to flow through fine holes in a platinum plate. The glass strands
are cooled, gathered and wound. The fibres are drawn to increase directional strength. The fibres
are then woven into various forms for use in composites.
Based on an aluminium lime borosilicate composition, glass produced fibres are considered as the
predominant reinforcement for polymer matrix composites due to their high electrical insulating
properties, low susceptibility to moisture and high mechanical properties.
Glass is generally a good impact resistant fibre but weighs more than carbon or aramid. Glass
fibres have excellent characteristics equal to or better than steel in certain forms.
2. Carbon Fibre Reinforced Polymer (CFRP)
Carbon fibres have a high modulus of elasticity, 200-800 GPa. The ultimate elongation is 0.3-2.5
% where the lower elongation corresponds to the higher stiffness and vice versa.
Carbon fibres do not absorb water and are resistant to many chemical solutions. They withstand
fatigue excellently and neither corrode nor show any creep or relaxation.
3. Aramid Fibre Reinforced Polymer (AFRP)
Aramid is the short form for aromatic polyamide. A well-known trademark of aramid fibres is
Kevlar but there does exist other brands as well such as Twaron, Technora and SVM.
The modulii of the fibres are 70-200 GPa with an ultimate elongation of 1.5-5% depending on the
quality. Aramid has a high fracture energy and is therefore used for helmets and bullet-proof
garments.
They are sensitive to elevated temperatures, moisture and ultraviolet radiation and therefore not
widely used in civil engineering applications. Finally, Aramid fibres do have problems with
relaxation and stress corrosion.
Applications of FRP
Aerospace applications:
This area uses only about 0.6% of FRPs at present, but with further development and lower
environmental costs it will require much more.Carbon fibers in FRPs reduce the weight by 25%
but ensure equal or greater strength when compared to aluminum sheets. They offer excellent
tensile strength and tolerate harsh environments and extremes of temperatures. They expand little
with heat and possess high stiffness. Though initially expensive, they save money for the aerospace
industry where every gram of additional weight is grudged because of the effect on the fuel
consumption, journey length and costs, and aerodynamic safety.
Carbon-FRP also allows for complex molded part production, reducing the number of parts by an
astonishing 95%. This makes production simpler, faster and cheaper compared to other materials
like steel or cast aluminum. Many giant modern aircraft are made of more than 50% carbon-FRP.
Helicopter rotor blades on high-end drones are also increasingly being made using FRPs.
Consumer goods:
Many sportspeople are finding it easier to heft their equipment nowadays, thanks to the use of
carbon and other FRPs in all kinds of sporting goods. Musical instruments or their components,
firearms, camping tents and camera tripods have all benefited from these versatile materials, with
6% of FRPs being used in this area.
Protective equipment:
When compounds called aramids are used in FRPs, they produce materials with extremely high
thermal and impact resistance, and exceptional mechanical strength, ideal for use in bullet-proof
and fire-resistant suits, as well as blast protection vehicles and structures.
Marine infrastructure:
FRPs are ideal replacements for wood, in marine waterfront environments, or on ships, where they
reduce the structural weight and enhance corrosion resistance. Rolling bridges, floating causeways
and platforms for sea bases are other applications.
Power industry:
FRP demand is expected to grow by over 300% in industry and energy applications over the
coming decade, mostly in electronic and electrical components.
Most FRPs are electrically insulative, tolerate rugged environmental chemicals (even corrosive
ones), resist degradation due to heat, are relatively non-flammable, have excellent structural
integrity, and can tolerate ultraviolet radiation. Glass-FRPs are non-magnetic and also resist
sparking, making them useful in power components. Reinforced plastics are also used to construct
wind turbine blades and for the storage modules of gas tanks.
Other applications of FRP
1. Carbon FRPs are used in prestressed concrete for applications where high resistance to
corrosion and electromagnetic transparency of CFRP are important.
2. CFRP composites are employed for underwater piping and structural parts of offshore
platform. Added to that, FRP declines the risk of fire.
3. Carbon fibre reinforced polymers are used to manufacture underwater pipes for great depth
because it provides a significantly increased buoyancy (due to its low density) compared to steel.
4. The stairways and walkways are also made of composites for weight saving and corrosion
resistance.
5. It is used in high-performance hybrid structures.
6. FRP bars are used as internal reinforcement for concrete structures.
7. FRP bars, sheets, and strips are used for strengthening of various structures constructed from
concrete, masonry, timber, and even steel.
8. FRPs are employed for seismic retrofitting.
9. Fibre reinforced polymers are used in the construction of special structures requiring electrical
neutrality.
10. The high energy absorption of aramid fibre reinforced polymer (AFRP) composites makes
them suitable for strengthening engineering structures subjected to dynamic and impact loading.