ENGINEERING CHEMISTRY CY3151

UNIT I : POLYMER CHEMISTRY

Introduction: Functionality-degree of polymerization.
Classification of polymers (Source, Structure,
Synthesis and Intermolecular forces). Mechanism of
free radical addition polymerization. Properties of
polymers: Tg, tacticity, molecular weight-number
average, weight average, viscosity average and
polydispersity index (Problems). Techniques of
polymerization: Bulk, emulsion, solution and
suspension.
Engineering Plastics: Polyamides, Polycarbonates
and Polyurethanes. Compounding and Fabrication
Techniques: Injection, Extrusion, Blow and
Calendaring
Polymer
Poly- mer = many – units
Units – monomer(s)
Polymer is a combination of large number of
small molecules called monomer(s)
Monomers are joined together by a
chemical bond to give a macromolecule, polymer
Molecular weight – 10,000 – 10,00,000
Examples of polymers : PE, PVC, PS, Nylon 66, etc.,
H H H H H H
C C C C C C
CH2=CH2 H H H H H H
Polyethylene (PE)

Polymer is a macromolecule but all macromolecules are not polymers

Naturally occurring polymers : Wood, Rubber, Cotton, Wool, Leather, Silk
Classified as Plastic, elastomer, fibers
Commonly used polymeric materials

Plastic

Elastomer
Fiber
Why Polymer?
Light weight
Strength
Size and shape flexibility
Visual aesthetic
Properties of polymers
High tensile strength (elasticity)
Non magnetic solids
Low electrical conductivity because of covalent bonds

Applications
Automobile
Electrical and electronic components
Computer components
History of polymers
Polymer examples
Nomenclature of polymers
Homopolymers – the repeating unit is
same Ex: PE
It can be Linear or branched chain

Heteropolymers – contains more than

one monomers Ex: Nylon 66, Terylene
It can be Linear, branched, cross linked
or network polymer (numerous cross link
between them)
Functionality of a monomer
It is the number of bonding sites (or) reactive sites or functional groups
present in the molecule
Ex: The double bond in vinyl monomers (CH2 = CHX) can be considered
as a site for two free valency's. When the double bond is broken, two
single bonds become available for combination

H2C=CHX → --- [--CH2 – CHX--]n ------

a)When the functionality of monomer is two (bifunctional), linear (or)

straight chain polymer is formed
Ex: (a)vinyl monomers (b)adipic acid (c) hexamethylene diamine

• -M-M-M-M-M-M-M or –M1-M2-M1-M2-M1-M2
b) When the functionality of monomer is three (tri- functional), three-
dimensional net work polymer is formed
Ex: glycerol, Phenol in Bakelite
Triglycerides are made up of monomers of glycerol molecules each
bonded to three fatty acid “tails.”
when a trifunctional monomer is mixed in small amounts with a
bifunctional monomer, a branched chain polymer is formed
Ex: Urea formaldehyde, phenol formaldehyde
High strength, hardness, heat resistance, insoluble in all organic solvents
Degree of polymerization (Dp)
It is a number, which indicates the number of repetitive units (monomers)
present in the polymer

It is the indirect way of expressing the molecular weight of a polymer

Oligomers – 2-40 monomers, formed due to incomplete polymn or thermal

degradation
Problems

i) Calculate the Dp for LDPE with a molecular weight of 20,000 amu

Dp = 20,000/28.05 = 713

ii) Calculate the molecular weight of a given PVC given that Dp is 338

Mol.Wt. of VC (-CH2=CHCl-)n is 2(12.011) + 3(1.008) + 1(35.45)

= 62.496 g/mol
Mol.Wt. of PVC = 62.496 x 338 = 21123.648 g
Classification of polymers
I Based on Source
Inorganic
Natural Ex: Sand and Clay

Organic
Ex: Isoprene, Cellulose,
Source Semi synthetic-derived
from natural polymer by Starch
chemical treatment
Ex:Rayon from wood

Inorganic
Ex: Ceramic, Fibre, Glass

Synthetic
Organic
Ex: PVC,PE,PS
II Based on structure
a)Linear structure - have repeat units joined end to end in single chains
-M-M-M-M-M-M-M- or –M1-M2-M1-M2-M1-M2-
Ex : Teflon, Nylon 66,HDPE – produced
at low P
Highly crystalline, high tensile strength,
more density, relatively opaque

b) Branched structure - branch chains have connected to main chains

Ex : LDPE – produced at high P
More branching, low crystaline,
less density
Used in packing foam and wash bottle
c) Cross linked structure
These are usually formed from bi- functional and tri- functional
monomers and contain strong covalent bonds between various linear
polymer chains
Ex: vulcanized rubber, urea-formaldehyde resins
Cross linked polymers are hard and do not melt, soften or dissolve in
most cases
III Based on preparation
The reaction by which monomers combine to give polymer
a) Addition or chain growth polymerization - formed by the repeated
addition of monomer molecules possessing double or triple bonds
Gives a product which is an exact multiple of the original monomeric
molecule Ex : CH2=CHX X = H, Cl, -CH3, C6H5(Ph)
b) Condensation or step growth polymerization
It is formed by repeated condensation reaction between two different
bi- functional or tri- functional monomeric units with polar groups
Here, elimination of small molecules such as water, alcohol, hydrogen
chloride, etc. take place
Ex : Nylon 66, polyester
c) Co polymerization
It is a hetero polymer formed by joint polymerization of two or more
monomers with no by product elimination
Ex : SBR (Buna-S Rubber)
It is further divided into –
IV Based on molecular forces
Based on magnitude of intermolecular forces present in them because
the mechanical properties of polymers are governed by
intermolecular forces, e.g., van der Waals forces and hydrogen bonds
present in the polymer
c) Elastomer or Rubber
An elastomer is a polymer with viscoelasticity ( both viscosity and
elasticity) and very weak inter-molecular forces, generally having
low Young’s modulus and high failure strain compared with other
materials
Elastic polymer, is often used interchangeably with the term rubber
Natural rubber – Isoprene

It has a coil like structure

Which is responsible for increase in chain length when it is stretched

Isoprene exists in cis and trans form
Cis form has more elastic behaviour because of free rotation where as
trans isomer is rigid due to restriction in free rotation

Synthetic rubber: Neoprene

Invented in 1930 by DuPont company

Neoprene is actually more resistant than natural rubber to water, oils,
solvents and heat
Vulcanization of rubber
Drawbacks of raw rubber
• becomes soft at high T and too brittle at low T
• attacked by oxidizing agent and undergoes oxidation in air due to
presence of c=c double bond
• high water absorption
• when stretched too long, it suffers deformation
In order to improve the properties of rubber, chemicals like S, H2S,
PhCOCl, etc., are added
S is added to rubber and heated at 100-140oC
S combines with C=C double bonds and prevent the intermolecular
movement of rubber springs
The hardness of rubber depends on % of S rubber
Tyre rubber – 3-5% Battery case rubber – 30%
Vulcanization of rubber
d) Fibers
Fibres are the polymer which have strong intermolecular forces
between the chain. These forces are either hydrogen bonds or
dipole dipole interaction
Because of strong forces, the chains are closely packed giving
them high tensile strength and less elasticity
These Polymers are long, thin and thread like and can be woven in
fabric which can be used for making fibres
Natural Fibers – cotton and Linen from polysaccharides and wool
and silk from protein
Synthetic Fibers
polyamide (Nylon)
polyester (PET in bottles)
polyacrylonitrile
polypropylene (in diapers or filters)

Semi-synthetic (Rayon, Modal, Tencel etc.)

Nylon 66
Fibers are formed when polymer chains are all lined up in the same
direction
Mechanism of addition polymerization
A single monomer undergoes polymerization in the presence of heat or
light

Addition Polymerization

Ionic Free radical

Cationic Anionic
These polymerization processes involve three major steps

i) Initiation step :
Formation of free radical/cation/anion

Attack of respective species on monomer

ii) Propagation step
Addition of more number of monomers and growth of the polymeric
chain
iii) Termination step
Completion of the reaction and formation of end polymer
Mechanism of Free radical polymerization
Formation of free radical
Initiation

Propagation

Termination

30
 Properties of polymers
Molecular weight
n CH2=CH2 ➝ [-CH2-CH2-]100 + [-CH2-CH2-]200 + [-CH2-CH2-]400
• When ethylene molecules (monomer) undergoes polymerization,
polymer polyethylene is obtained with different chain lengths
• Because the termination step is a random process ie. The chain
growth depends on chain transfer reaction (addition) and availability
of functional groups (condensation)
• A polymeric material, therefore, cannot be characterized by a single
molecular weight like an ordinary substance
• Instead, a statistical average calculated from the molecular weight
distribution has to be used
• One way is average of molecular weight contributed by the individual
molecules, ie. Number average molecular weight, Mn
• Another way is contribution of individual weight to the total weight ie
Weight average molecular weight, Mw
Number average molecular weight, Mn (measured from
colligative properties)
𝑛1𝑀1+𝑛2𝑀2 +𝑛3𝑀3 +⋯ 𝑁𝑖𝑀 𝑖
Mn = 𝑛1+𝑛2+𝑛3+⋯
Mn = 𝜮 𝑁𝑖

Weight average molecular weight (measured from light scattering and

Ultra centrifugation techniques)
𝑛1𝑀12+𝑛2𝑀22 +𝑛3𝑀32 + …. 𝑁𝑖𝑀 𝑖2
Mw = 𝑛1𝑀1 +𝑛2𝑀2 +𝑛3𝑀3+ ….
Mw = 𝜮 𝑁𝑖𝑀 𝑖

Mw is a good measure for the expected statistical size of the polymer,

whereas Mn is a measure for the chain length

The weight average is particularly sensitive to the presence of higher

molecular weight molecules
whereas the number average is very sensitive to the presence of lower
molecular weight molecules
Viscosity average molecular weight
- measured by using viscometer and the molecular weight
obtained by this technique is called viscosity average
molecular weight
The molecular weight of the polymer solution is very high so
the viscosity of polymer solution is very high compared to
that of pure solvent.
From the Mark-Houwink equation the relationship among the
molecular weight and viscosity,
[𝛈] - intrinsic viscosity
M – molecular weight
K & 𝛼 – constants for a particular
polymer solvent system
a – a constant
Molecular weight distribution
For all synthetic polymers, Mw > Mn
In order to be equal, the polymer should be homogeneous
Problems
1. Calculate the Mn and Mw of PE with the following composition
[-CH2-CH2-]400 is 25%, [-CH2-CH2-]800 is 35% and [-CH2-CH2-]600
is 40%
Solution
Molecular mass of Monomer is 28
n M N
I 400 11200 25
II 800 22400 35
II 600 16800 40

𝑁𝑖𝑀 𝑖 𝑁𝑖𝑀 𝑖2
Mn = 𝜮 𝑁𝑖
Mw = 𝜮 𝑁𝑖𝑀 𝑖
Problem 2
Calculate the number average, molecular weight and polydispersity
index of –
i) A polypropylene sample with a degree of polymerization of 15000
and Mw of 6.3x105 g/mol
ii) A polystyrene sample with a Dp of 2600 and a Mw of 3.4x105 g/mol
Comment on the PDI values of both

i) Dp = Mn/42 15000 = Mn/42 Mn = 6.3 x 105 g/mol

PDI = Mw/Mn = 6.3 x 105 / 6.3 x 105 g/mol = 1
The polymer polypropylene is monodisperse

ii) 2600 = Mn/104 Mn = 2600 x 104 = 270400 g/mol

PDI = Mw/Mn = 3.4 x 105/270400 = 1.26
The polymer Polystyrene is polydisperse
Problem 3
In a polymer sample, 40% molecules have a molecular mass of 25000.
35% have a molecular mass of 40000 and the rest have 50000.
Calculate Mn and Mw

Mn = 36500 g/mol Mw = 39,315 g/mol

Glass Transition Temperature, Tg
Tg is one of the most important thermophysical properties of
amorphous polymers
When a rubber ball is cooled below -70oC, it becomes hard and brittle
and when it is heated it becomes soft and flexible

There exists a boundary for each polymer where the physical state
changes

This change of state is different for amorphous and crystalline polymer

For amorphous polymer, Tg is change of state from hard and brittle to
soft and flexible or rubbery state

For crystalline polymer this change of state is known as melting point,

Tm
Tg
Tg

In actual practice, it is difficult to get 100% crystalline polymer

Most of the synthetic polymers consist of crystallites (hardness)
embedded in an amorphous matrix (flexibility)
Factors affecting Tg
1. Crystallinity – the molecular chains are orderly arranged and free
rotation is restricted which leads to less flexibility of polymer molecule
If the polymer is less flexible, Tg value increases
2. Molecular weight - a polymer with long chains has less free volume
than one with short chains. Thus, low molecular mass gives lower values
of Tg
3. Cross linking and branching - the presence of cross-links between
chains restricts rotational motion and raises Tg
4. Intermolecular Forces- stronger intermolecular forces lead to a higher
Tg. PVC has stronger intermolecular forces than polypropylene because
of the dipole-dipole forces from the C-Cl bond
5. Plasticizer - plasticizers are low molecular weight compounds added
to plastics to increase their flexibility and workability. They weaken the
intermolecular forces between the polymer chains and decrease Tg
Ex: dibutylphthalate, tricresylphosphate
Tg values

Tg = -70oC

Tg = 69oC

Tg = -20oC Tg = 100oC

-a benzene ring, can catch on neighbouring chains like a "fish hook" and
restrict rotational freedom, increases Tg

Tg = 105oC Tg = 20oC

- flexible pendant groups, such as aliphatic chains, tend to limit how

close chains can pack. This increases rotational motion and lowers Tg
Tacticity
It is the relative stereochemistry of adjacent chiral centers within a
macromolecule
or) orientation of groups in a molecule, applied to addition polymers
where one substituent is non H
Tacticity : polystyrene
Isotactic Syndiotactic Atactic
The substituent Substituents have Substituents are
phenyl groups are alternate positions placed randomly along
present on the same along the chain the chain
side
Formed by Ziegler Formed by Formed by free radical
Natta catalyst Metallocene catalyst polymerization
Pure crystalline and Crystalline and A hard plastic and
used for making fibers doesn’t melt below completely
270oC amorphous

The physical properties such as melting range, Tg, solubility, etc. will
depend on the stereospecific arrangement
The variation is more pounced when the substituent groups are bulky
Polydispersity
When a chemical compound contains number of molecules, each
molecule has same molecular weight (monodisperse)
Where as a polymer contains molecules, each molecule has different
molecular weight (polydisperse)
Because of this polydispersity concept, molecular weight of a polymer is
taken as average molecular weight
- a measure of heterogeneity
Defined as characteristic of a polymer
which has an inconsistent size, shape
and mass distribution
It is expressed as Polydispersity index (PDI)
𝑀𝑤
PDI = 𝑀𝑛 > 1 for synthetic polymers

In natural polymers, molecules are arranged in a systematic manner and

PDI is 1
Techniques of polymerization (Free radical)
In the free radical polymerization, the initiator (free radical is added
with monomer) and a polymer is formed
Two important factors should be taken care during polymerization
i) The reaction is exothermic – the heat liberated during the reaction
process should be dissipated/removed
ii) Viscosity control – the reaction mixture becomes highly viscous
Polymerization process is classified into –
i) Homogeneous Polymerization – Polymerization occurs in a single
phase. ie. Monomer is dissolved in a suitable solvent to form a
homogeneous solution or monomer taken in molten state
Ex: Solution and Bulk Polymerization
ii) Heterogeneous Polymerization – monomer and solvent form two
different phases (heteorogeneous)
Ex: Emulsion and Suspension Polymerization
Solution Polymerization
• Monomer is dissolved in a suitable solvent and then the initiator is
added to start polymerization
• When the reaction is over, polymer is precipitated
• It is filtered, washed and dried

Ex: polymerization of acrylonitrile and acrylic acid

Advantages
• Solvent has low viscosity, reaction mixture can be stirred
• Solvent reduces viscosity, making processing easier
• Solvent acts as a diluent and aids in removal of heat of
polymerization
• Thermal control is easy
• Cheap materials for the reactors (stainless steel or glass lined)
Disadvantages
• Solvent may terminate the growing polymer chain(by chain
transfer), leading to low molecular weight polymers
• Reduce monomer concentration which results in decreasing the
rate of the reaction and the degree of polymerization
• Difficult to remove solvent from final form, causing degradation of
bulk properties
• Fire and toxicity may be increased by the addition of solvent
Bulk polymerization
• It is the simplest method and used for addition and condensation
polymerization
• Monomer is taken in liquid state and the initiator is dissolved in the
monomer itself
It involves two stages-
Pre polymerization stage
• Initially (about 10%) polymerization
is slow and then becomes fast
• After 25-30%, the reaction mixture
becomes viscous
Post polymerization stage
• Viscous mixture is transferred to a reactor and maintained at constant
T
• After some time, the content is poured into methanol where in
polymer is precipitated out
Ex: Styrene, vinyl chloride, methyl methacrylate
Advantages
• The system is simple and requires thermal insulation
• The polymer obtained is pure
• Large castings may be prepared directly
• Molecular weight distribution can be easily changed with the use of a
chain transfer agent
• The product obtained has high optical clarity

Disadvantages
• Heat transfer and mixing become difficult as the viscosity of reaction
mass increases
• The problem of heat transfer is compounded by the highly
exothermic nature of free radical addition polymerization.
• The polymerization is obtained with a broad molecular weight
distribution due to the high viscosity and lack of good heat transfer
• Very low molecular weights are obtained
• Gel effect should be there
Emulsion polymerization
• Monomer is dispersed in an aqueous phase as fine droplets (10-5 to
10-6 mm in size)
• Stabilized by adding surfactants (soaps, detergents)
• Surfactants form micelles (when their concentration exceeds CMC
that are dispersed throughout the solution)
• Addition of initiator (water soluble) leads to initiation of reaction in
the micelle
• Because of polymerization, the micelle size increases and the
monomer diffuses form its droplets
• Termination is less likely to occur because polymerization sites are
isolated from each other
• High molecular weight polymer are formed in the form of latex
Polymers find application in adhesive, surface coating
Ex: Styrene, vinyl chloride, vinyl acetate
Advantages
• The continuous water phase is an excellent conductor of heat that
allows the heat to be polymer molecules are contained within the
particles, so it is method to increase the rate of many reactions
• Since polymer molecules contained within water viscosity remains
close to that of water and is not dependent on molecular weight
• The final product can be used as it is and does not generally need to
be altered or processed

Disadvantages
• The polymerization process is costly
• The end polymer has high residual impurity because of surfactant
• It is difficult to remove emulsifying agent
• Polymer is translucent, inferior electrical insulation characteristics
Suspension polymerization
• Monomer (water insoluble) is dispersed as large droplets (0.1 – 1
mm) in water and kept in suspension by mechanical agitation
• Stabilizer like Gelatin and water soluble cellulose derivative are used
to keep the monomer droplets to be isolated
• Initiator (oil soluble peroxide) soluble in monomer is added
• Polymerization starts at each droplets and continues till completion
• Polymer in the shape of pearl
or spherical is formed
• The water phase becomes the
heat transfer medium. Since
water is a continuous phase,
• viscosity changes very little
as the monomer converts
to polymer, so the heat
transfer is very good
Ex: Styrene, vinyl chloride, methylmethacrylate
Advantages
• Purity is high
• Viscosity is low and temperature is controlled due to high heat
capacity of water

Disadvantages
• Polymerization is sensitive to agitation therefore difficult to control
the size of the particles and surface characteristics
• Size of the particle depends on monomer-water ratio, concentration
of stabilizing agent and speed of agitation

Application
• The polymers find application in ion exchange resins, polystyrene
foam
 INDIVIDUAL POLYMERS

Polycarbonate (PC)

Properties
• a high-performance tough, amorphous and transparent thermoplastic
polymer
• High impact strength
• High dimensional stability
• Good electrical properties amongst others
• Protection from UV Radiations
• Heat Resistance - thermally stable up to 135°C
• Transmittance – PC is an extremely clear plastic that can transmit over 90%
of light as good as glass
Applications
• Appliances - refrigerators, air conditioners, coffee machines, food
mixers, washing machines, hair dryers steam iron water tanks etc.
• Automobile - its high heat resistance allows its use in light housing,
headlamp bezel and lenses
• Construction - a suitable alternative to
glass invarious glazing applications
• Consumer products - suitable for the manufacturing CDs/DVDs, ideal
for objects, including shatterproof sunglasses, face shields, protective
glasses or even as a component in bullet-proof windows
• Telecom - Mobile phone housings, pager parts
• Urban equipment - Street lamp covers, anti- vandal glazing, food
processors
• Sports - Ski clamp parts, helmets, protective eye visors to protect
children and athletes from injuries
Nylon 6

Properties
• Tough, possessing high tensile strength, as well as elasticity and
lustre
• They are wrinkle proof and highly resistant to abrasion and
chemicals such as acids and alkalis
• The fibres can absorb up to 2.4% of water, although this
lowers tensile strength
• Better weathering properties; better sunlight resistance.
• High melting point (256 °C, 492.8 °F)
• Superior colorfastness
• Excellent abrasion resistance
Applications
Nylon 66

Properties
• High mechanical strength.
• High toughness, stiffness and hardness.
• Good fatigue resistance.
• Good impact resistance.
• Excellent wear resistance.
• Good electrical insulating properties.
• No resistance to UV rays.
• Lightweight; sometimes used in applications in place of metals
Applications
 NYLON 6 NYLON 66
Less crystalline More crystalline
Lower mold shrinkage Exhibits greater mold shrinkage
Lower melting point Higher melting point
Lower heat deflection
Higher heat deflection temperature
temperature
Higher water absorption rate Lower water absorption rate
Poor chemical resistance to acids Better chemical resistance to acids
Withstands high impact and
Better stiffness, tensile modulus
stress and better stands up to
and flexural modulus
hydrocarbons
Lustrous surface finish, easy to More difficult to colour
colour
KEVLAR
Properties of Kevlar
• It's strong but relatively light. The specific tensile strength (stretching or
pulling strength) is over eight times greater than that of steel wire
• Unlike most plastics it does not melt: it's reasonably good at withstanding
temperatures and decomposes only at about 450°C (850°F)
• Unlike its sister material, Nomex, Kevlar can be ignited but burning usually
stops when the heat source is removed
• Very low temperatures have no effect on Kevlar
• Like other plastics, long exposure to ultraviolet light (in sunlight, for
example) causes discoloration and some degradation of the fibers in Kevlar
• Kevlar can resist attacks from many different chemicals, though long
exposure to strong acids or bases will degrade it over time
• Kevlar remain "virtually unchanged" after exposure to hot water for more
than 200 days and its super-strong properties are "virtually unaffected" by
moisture
Applications of Kevlar
• Body armour: bullet-proof vests and helmets
• Ropes and cables
• Belts and hoses for industrial applications
• Composites for aircraft body parts, boats, and sporting
goods
• Fibre-optic cables for communication,
data transmission and ignition
• Friction products such as brake pads, clutch linings, gaskets.
It is often employed as a replacement for the carcinogenic
asbestos
• Sailing/motorcycle outerwear
• Adhesives and sealants
Polyurethane
Methylene diphenyl
isocyanate +
Ethylene glycol

Properties
• Good Abrasion Resistance
• Good Impact Resistance
• Good Toughness
• Low Viscosity
• High Elongation
• Good Flexibility
• Good tear Strength
• Low Shrinkage
• Hydrolytically Stable
• Resillent
Applications of polyurethane
• The manufacture of flexible, high-resilience foam seating
• Rigid foam insulation panels
• Microcellular foam seals and gaskets
• Durable elastomeric wheels and tires(such as roller coaster
wheels)
• Automative suspension bushings
• Electrical potting compounds
• High performance adhesives
• Surface coating and surface sealants
• Synthetic fibres
• Carpet underlay
• Hard plastic parts(e.g, for electronic
instrument)
• Hoses and skateboard wheels
Compounding and Fabrication Techniques
Plastic is compounded with other ingredients in order to impart
certain definite properties to the finished product
-customizes with various additives to achieve colour, property, and
performance requirements
Ingredients
Resins - forms the major portion of the body of plastics
It is the binder, which holds the different constituents together

Plasticizers - added to enhance the plasticity of the material and to

reduce the cracking on the surface and to increase the flexibility &
toughness
Plasticizers also increase the flow property of the plastics
Ex : Tricresyl phosphate, Dibutyle oxalate , Castor oil
Fillers - generally added to thermosetting plastics to increase
elasticity and crack resistance.
Fillers improve thermal stability, strength, non combustibility,
water resistance, electrical insulation properties & external
appearance
Ex : Carbon black, Calcium carbonate, Calcium sulphate
Pigments - These are added to impart the desired colour to the
plastics and give decorative effect. e.g.:- Lead chromate (yellow),
ferro cyanide (blue)
Stabilizers - to improve the thermal stability of plastics
At moulding temperature, PVC undergoes decomposition &
decolourisation
During their moulding, stabilizers are used
Ex: White Lead, Lead Chromate
Lubricants - added to the plastics, allow it easily extract from the
Equipment
It prevents sticking of the plastics to the equipment.
Ex: Oils, Waxes, Soaps
Catalysts - added to the thermosetting resins increases the
rate of polymerisation reaction
To produce a highly Cross-linked finished Product
Ex: ZnO, Ag,Cu
Reinforcements - added mainly to improve the tensile and
flexural strength properties of the plastic material. Most of
them are in the fibrous form
Ex: glass, asbestos, boron, carbon, ceramic
Recently, synthetic fibres of nylon, polyehtylene and
acrylonitrile have also been used
Fire Retardants
Plastic compounds may also contain components that
improve the fie resistance of the end product
The most commonly used are compounds containing
halogen, derivatives of antimony, boron, nitrogen and
phosphorous
Fabrication
Fabrication of plastic is the technique of giving any desired
shape to the plastics by the use of mould
Because of the properties of polymers it is possible to mould
them and change their shape using a number of different
repetitions manufacturing processes
A proper method is to be selected depending upon the shape
and type of resin being used
• Extrusion moulding
• Injection moulding
• Blow moulding
➢ Extrusion blow moulding
➢ Injection blow moulding
➢ Stretch blow moulding
• Calandering
Injection moulding
Applicable mainly to thermoplastic resins
A polymer analogue for die casting for metals
A process in which molten polymer is forced under
high pressure into a mold cavity through an opening (sprue)
Polymer material in form of pellets is fed into an Injection Molding machine
through a hopper. The material is then conveyed forward by a feeding screw
and forced into a split mold, filling its cavity through a feeding system with
sprue gate and runners
Screw of injection molding machine is called reciprocating screw since it not
only rotates but also moves forward and backward according to the steps of
the molding cycle
It acts as a ram in the filling step when the molten polymer is injected into the
mold and then it retracts backward in the molding step
Heating elements, placed over the barrel, soften and melt the polymer.
The mold is equipped with a cooling system providing controlled cooling and
solidification of the material
The polymer is held in the mold until solidification and then the mold opens
and the part is removed from the mold by ejector pins
Injection moulding is used for manufacturing DVDs, pipe fittings, battery
casings, toothbrush bases, bottle lids, disposable razors, automobile
bumpers and dash boards, power-tool housing, television cabinets,
electrical switches, telephone handsets, etc.,
Advantages
Fast production Low labour costs Design flexibility
Good product consistency Produce very small parts
Disadvantages
High capital cost of the machine Moulds are also costly
Extrusion moulding
Extrusion is a process of manufacturing long products of constant cross-section (rods,
sheets, pipes, films, wire insulation coating) forcing soften polymer through a die* with an
opening

Polymer material in form of pellets is fed into an extruder through a hopper. The material is
then conveyed forward by a feeding screw and forced through a die, converting to
continuous polymer product

Heating elements, placed over the barrel, soften and melt the polymer. The temperature of
the material is controlled by thermocouples

The product going out of the die is cooled by blown air or in water bath

Extrusion of polymers (in contrast to extrusion of metals) is continuous process lasting as

long as raw pellets are supplied
Extrusion is used mainly for Thermoplastics but Elastomer and Thermosets also may also be
extruded
In this case cross linking forms during heating and melting of the material in the extruder

*A die is a manufacturing tool used to shape or cut material via a press, or machine that
uses pressure to compact or otherwise reshape an object
Advantages
To make long shape of object Low machine cost
Mass production volume Good mixing of metal
Disadvantages
Uniform cross sectional shape
only manufactured
Simple complexity of parts
Blow moulding
a process in which a heated
hollow thermoplastic tube
(parison) is inflated into a
closed mould conforming the
shape of the mould cavity

• The process is similar to injection moulding and extrusion

• The plastic is fed in granular form into a 'hopper' that stores it
• A large thread is turned by a motor which feeds the granules through
a heated section
• In this heated section the granules melt and become a liquid and the
liquid is fed into a mould
• Air is forced into the mould which forces the plastic to the sides,
giving the shape of the bottle
• The mould is then cooled and is removed
Disposable containers of various sizes and shapes, drums, recyclable
bottles, automotive fuel tanks, storage tanks, globe light fixtures, toys,
tubs, small boats are produced by Blow moulding method
Three major techniques
1. Extrusion Blow moulding involves manufacture of parison by
conventional extrusion method using a die similar to that used for
extrusion pipes
Extrusion Blow moulding is commonly used for mass production of
plastic bottles
The parison is extruded vertically in downward direction between two
mould halves
When the parison reaches the required length the two mould halves
close resulting in pinching the top of parison end and sealing the blow
pin in the bottom of the parison end
Parison is inflated by air blown through the blow pin, taking a shape
conforming that of the mould cavity. The parison is then cut on the top
The mould cools down, its halves open, and the final part is removed
Extrusion Blow moulding
2D product is obtained
Die is used to get final
product
2. Injection blow moulding
• In Injection Blow moulding method a parison is
produced by injecting a polymer into a hot injection
mould around a blow tube or core rod.
• Then the blow tube together with the parison is
removed from the injection mould and transferred to a
blow mould
• Injection Blow moulding is more accurate and
controllable process as compared to the Extrusion Blow
moulding.
• It allows producing more complicated products from a
wider range of polymer materials.
• However production rate of Injection Blow moulding
method is lower than that of Extrusion Blow moulding.
3D product is obtained
Mould is used to get final
product
3. Stretch Blow moulding
• Stretch Blow moulding is similar to Injection blow Molding
• Stretch Blow moulding involves injection moulding of a
parison, which is then stretched in the downward direction
by means of the blow tube
• The extended parison is then inflated in a blow mold
• In this method biaxial molecular orientation is produced
The specific molecular orientation provides higher
mechanical strength, rigidity and transparency of the
material
• Material, commonly used in this method is Polyethylene
terephthalate (PET)
• Stretch Blow moulding is used for manufacturing containers
for carbonated beverages
Calendaring moulding

Calendering is a continuous process where melted plastic,

paper, rubber or fabrics are squeezed between pairs of rollers,
making plastic sheets and plastic film
• In the calendering process, molten plastic is extruded and
then passed between pairs of heated rollers that squeeze
the molten plastic into a sheet The thickness of the plastic
sheet depends upon the gap between the pairs of rollers.
Very thin plastic sheet is called plastic film
• The calendering process usually involves using four or more
pairs of rollers that gradually reduce the plastic thickness,
polish the surface, add a texture or emboss a pattern into
the plastic sheet. After the sheet passes between the final
pair of rollers, it is cooled and fed to a winding station
where it is coiled and edge trimmed
• Plastic laminates and plastic/fabric laminates are also
produced by calendering
• Plastic films may be laminated, i.e. bonded, by squeezing the plastic
films between pairs of heated rollers under great pressure
• Fabrics may be bonded to plastic film by squeezing the two materials
together between pairs of heated rollers under great pressure
• Two fabrics may be bonded by passing one of the fabrics through a
tank of adhesive and then passing the two fabrics between pairs of
rollers that squeeze the fabrics together under great pressure

The plastics used to create film and sheets by calendering are:

• polyvinyl chloride (PVC) - modified polyethylene (PE)
• polypropylene (PP) - acrylonitrile-butadiene-styrene (ABS)
• thermosetting compounds