Polymer an Insight in to the learning topics

Introduction :
Thermoplastics- PVC, PTFE
Thermosetting plastics - properties and industrial applications
of Bakelite, ABS

Moulding of plastics into articles:

Compression,
injection,
transfer and extrusion methods.
Conducting polymers: Properties and applications

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 WHAT IS A POLYMER
 A word polymer is a combination of two Greek words,
“Poly” means “many” and “Meros” meaning “parts or
units”.
 A polymer is a large molecule of which is formed by
repeated linking of the small molecules called
“monomers”.

n(CH2-CH2) (-CH2-CH2-)n
ethylene polyethylene
 DEGREE OF POLYMERIZATION
 The number of repeating units in the chains of which
a polymer is made up is called degree of a
polymerization (n).

 Polymers with high degree of polymerization are

called the “High Polymer”, and those with low degree
of polymerization are called “Oligopolymers”.

 High polymers have very high molecular mass (10000

to 1000000 u) and are called macromolecules.
Degree of Polymerization (P) = M/m;
Where, M= Mass of Polymer; m = mass of monomeric unit

Polymerisation
3 CH2 CH2 CH2 CH2
3

Ethylene
polyethylene

Degree of polymerisation (P) = 3

Mass of this polymer M = (28 x 3) = 84Da

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LINKING OF POLYMERS
 Polymers can be linear, branched or cross-linked. The
monomer may be arranged in the chain at random or
regularly.

(LINEAR POLYMER)
A A A A … … B B B

A A A A A A

A A A A A

A A A

(BRANCHED POLYMER)
 A A

A A A

A A A A A A

A A A

A A A A A A

(CROSS-LINKED POLYMER)
 Functionality
The number of reactive sites present in a monomer is called functionality

1.

O
Linear chain polymer is formed if the functionality of the
HO C CH2 NH2
monomer is only two (Bifunctional)

2. Ex. Glycine

O
O
HO C CH2 NH2
OH CH2 CH C OH
NH2

Ex. Serine
O
OH CH2 CH C OH Cross linked chain polymer is
formed if the functionality of the
NH2 monomer is more than two
(multifunctional)
11/26/2018 Glycine 7
Definition
 These are linear or slightly branched long chain
polymers, which can be softened on heating &
reversibly hardened on cooling repeatedly.
 Their hardness is a temporary property & varies with
temperature.
It can be reprocessed, so sometimes also referred as
green plastics.
Structure
 Thermoplastics possess weak intermolecular
forces(e.g. Van der Waal) & don’t have crosslinks.
Examples
 Cellulose derivatives
- 1) Cellulose acetate
- Cellulose nitrate
 Polyethenic/vinyl resins
- 2) Polyethylene
- 3) Polypropylene
- 4) Polyvinyl acetate
- 5) Polyvinyl chloride
- 6) Polystyrene
- 7) Teflon
- 8) Acrylic
- 9) Polysulfone
- 10) Polyester
Polyvinyl chloride
 It is a vinyl polymer constructed of repeating vinyl
groups (ethenyls) having one of their hydrogens
replaced with a chloride group.

 Obtained by heating a water emulsion of vinyl

chloride in presence of benzyl peroxide/ hydrogen
peroxide in an autoclave under high pressure.
  Properties:
1. Colurless & odourless
2. Non-inflammable & chemically inert
3. Resistant to light,O2, inorganic acid & alkalis.
4. High softening points 148
5. Greater stiffness & rigidity than polyethylene but
brittle.
Uses: Third most widely produced plastic
 Unplasticized PVC: Highly rigid but brittle, for
making sheets, tank lining, helmets ,mudguards etc.
 Plasticized PVC(by adding plasticizers e.g.
phthalates): Making continuous sheets of varying
thickness, hoses, pipes, construction, table covers,
conveyor belts etc.
Polytetrafluoroethylene (TEFLON)
• It is obtained by polymerization of water-
emulsion of tetrafluoro ethylene, under pressure
and in the presence of benzoyl peroxide as a
catalyst.
Properties
 Due to presence of high electronegative fluorine in
structure of TEFLON, strong interchain forces are
present which make it extremely tough.
 High softening point (350°c).
 It has high chemical resistance.
 It has good mechanical and electrical properties(high-
performance substitute for polyethylene)
Uses
 It is used in insulating motor, transformers.
 It is used in making wires.
 Non-stick cookware coatings are made
from TEFLON for eg. In frying pan.
 Also used for making gaskets, tank linings, pipes and
tubes for chemical industries.
 Used for making non lubricating bearings.
 one of the lowest coefficients of friction against any solid.
 AcrylonitrileButadieeneStyrene

•Monomers:-Acrylonitrile , Butadieene, Styrene

•Formula :-(C8H8·C4H6·C3H3N)n

•Production :-Copolymer 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.

•Properties :-The styrene gives the plastic a shiny, impervious surface. The
butadiene, a rubbery substance, provides resilience even at low
temperatures.Mechanical properties vary with temperature.

•Application :-
1. Used to make light, rigid, molded products such as piping .
2. Musical Instruments such as plastic clarinet.
3. Golf club heads :- Used due to its good shock absorbance
4. Used as a colorant in tattoo inks.
Bakelite, a phenol-formaldehyde polymer, was the first
completely synthetic plastic, first made by Leo Baekeland
in 1907. Baekeland and an assistant started their research in
1904 looking for a synthetic substitute for shellac.
Bakelite was commercially introduced in 1909. Bakelite was
first used to make billiard balls, but, later, was used to
make molded insulation, valve parts, knobs, buttons, knife
handles, many types of molded plastic containers for radios
and electronic instruments, and more.
Phenolic reins set to rigid, hard, scratch resistant, infusible, water resistant, insoluble
solids, which are resistant to non-oxidizing acids, salts and many organic solvents,
but are attacked by alkalis, because of the presence of free hydroxyl group in their
structures, They posses excellent electrical insulating character.

Phenol - formaldehyde polymers are the oldest synthetic polymers. These are
obtained by the condensation reaction of phenol with formaldehyde in the
presence of either an acid or a base catalyst. The reaction starts with the initial
formation of o-and/or
p-hydroxymethylphenol derivatives, which further react with phenol to form
compounds having rings joined to each other through –CH2 groups. The initial
product could be a linear product – Novolac used in paints.
Novolac on heating with formaldehyde undergoes cross linking to form an infusible
solid mass called bakelite.
1.Plastic items like telephone parts,cabinets,heater handles.
2.Phonograph records
3.Electrical switches and berings used in propeller shafts in paper industry.
4.Soft bakelite used as binding glue for
laminated,wooden plants and in varnishes
5.Sulphonated bakelite are used as ion exchange resins.
6.For impregating fabrics,wood and paper.

valve parts, knobs, buttons, Phonograph records

 Processing (or) moulding (or) compounding of plastics

Compounding or moulding is a process by which the polymer resins are

mixed with some additives like fillers, plasticizers, stabilizers etc to impart
some special properties to the moulded final product.

Ingredients of a plastic

Additives Examples Function/Importance

1. Resins Thermoplastic and Basic binding materials and holds
thermosetting resins the constituents together. Major part
of the plastics. Thermosetting resins
transferred in to crosslinked plastics
during moulding in presence of a
catalyst
2. Plasticizers Dioctylphthalate (DOP) To improve the elasticity and to
Adipate, Oleate, reduce the brittleness of the plastics.
Organic Phosphate Also improves the flow of polymer
during the process

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 Additives Examples Function/Importance

3. Fillers (or) Mica, quartz, Limestone, Increases the tensile and compressive
Extenders Nylon strength of plastics. They reduce the
shrinkage during the process of setting

4. Lubricants Waxes, Oils, soaps To make the moulding process smooth and
give the glossy finish to the final product

5. Stabilizers Stearates of Pb, Ba and Cd To increase the thermal stability of a

polymer

6. Pigments TiO2, ZnO (white), chromium

oxide (green), carbon black, To provide colours to the moilded articles
Read Lead

Phenyl, n-napthyal amine, Protection against oxidation

7. Anti-Oxidants
Diphenyl-p-
phenylenedimaine

8. Catalyst H2O2 and Benzoyl peroxide Added only in the case of thermosetting
resins to increase the rate of polymerisation

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 Different types of Moulding technique

The moulding is different for various polymer depends on their thermal

behaviour and nature of the resins.

1. Compression moulding Used for moulding the

2. Transfer moulding thermosetting polymers

3. Injection moulding Used for moulding the

thermo polymers
4. Extension moulding and

5. Blow moulding Used for moulding the

bottle type articles which
has narrow neck

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 1. Compression Moulding of plastics
Pressure • The process of molding a material in a confined
Pressure = 70 kg/cm2 shape by applying pressure and usually heat.
• Almost exclusively for thermoset materials
• Used to produce mainly electrical products

Top moulding part of the die

(plunger)
•A force of 2900psi is usually
required for moldings up to 1inch
(25 mm) thick.
Guide pins •An added 725psi should be
provided for each 1inch (25 mm)
increase.

Molten polymer with ingredients

in the cavity at 200oC

Bottom moulding part of the die with cavity

(the shape of the cavity decides the shape of
the final product)

Extraction pin
Pressed plastic
material
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 2. Transfer Moulding of plastics
This is exclusively used for thermosetting plastics. The resin ingredients mixture is preheated in a
preheating chamber. When the moulding mixture becomes plastic then it is forced through a orifice into
the hot mould by using the plunger. After setting time it is taken out. Complicated shapes can be made.

Heaters
Plunger (top molding
part)

Charger (plastic ingredients)

Sprue

Molding Cavity

Bottom molding part

Ejector pin

A process of forming articles by fusing a plastic material in a

chamber then forcing the whole mass into a hot mold to
solidify.
Used to make products such as electrical wall receptacles and
circuit breakers Molded
plastic

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 3. Injection Moulding of plastics
Clamping Molding part Injection part

*
Cavity
Hopper Hydraulic
screw
Barrel drive

Heater bands

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 Pressing of molten polymer using die and plunger in Injection Molding

The feeding or injection of

hot plastic

This method is generally used for

thermoplastics.

Die The moulding composition is heated in

The cavity in which the molten
plastic will be fed and pressed
Plunger
a suitable chamber connected by a
duct leading to the mould.
The hot softened plastic is then forced
under high pressure into the relatively
cool mould cavity where it is set by
cooling and the moulded object is then
ejected.
The temperature range used is 90 to
260oC.

*11/26/2018
Source: http://www.idsa-mp.org/proc/plastic/injection/injection_process.htm 30
 4. Extrusion Moulding of plastics
It is a process in which the molten plastic material is forced through a die
which produces a continuous extrudate (product) in the form of final product.
This process is used mainly for the production of films tubes, rods, hoses.
It also used for the coating cables with PVC and other plastics.

Raw materials
Molten
polymer Die

Extruded pipe

Screw Heater
conveyer Cooling of
final product

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Conducting Polymers
 Introduction
 Polymers (or plastics as they are also called) are
known to have good insulating properties.

 Polymers are one of the most used materials in

the modern world, with their application
ranging from containers to clothings.

 They are used to coat metal wires to prevent

electric shocks.
 Noble Prize Winners

Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa changed the view of
polymers with their discovery that a polymers like polyacetylene, can be made
conductive almost like a metal.
 What is conductivity?
 Conductivity can be defined simply by Ohm’s law, V= IR

 Where R is the resistance, I the current and V the voltage present in

the material.

 The conductivity depends on the number of charge carriers

(number of electrons) in the material and their mobility.

 In a metal it is assumed that all the outer electrons are free to carry
charge and the impedance to flow of charge is mainly due to the
electrons "bumping" in to each other.

 Insulators however have tightly bound electrons so that nearly no

electron flow occurs so they offer high resistance to charge flow. So
for conductance free electrons are needed.
 What makes the material conductive?
Three simple carbon compounds are diamond, graphite and
polyacetylene. They may be regarded as 3D-, 2D- and 1D-forms
of carbon materials .

Diamond, which contains only σ bonds, is an insulator and its

high symmetry gives it isotropic properties.
Graphite and acetylene both have mobile π electrons and are,
when doped, highly anisotropic metallic conductors.
 How can plastic become conductive?
 Plastics are polymers, molecules that form long
chains, repeating themselves.
 In becoming electrically conductive, a polymer
has to imitate a metal, that is, its electrons need
to be free to move and not bound to the atoms.
 Polyacetylene is the simplest possible
conjugated polymer.
 Different types of conducting polymers
 Intrinsically conducting polymer (ICP) or
conjugated π – electrons conducting polymer
 Doped conducting polymer:
a) P-Doped and b) N-Doped
 Extrinsically conducting polymer:
a) Conductive element filled polymer
b) Blended conductive polymer
 Coordination conducting polymer
 ICP – Polymeric backbone comprising of
delocalized electron-pair or residual charge
 The first condition for this is that the polymer consists of
alternating single and double bonds, called conjugated double
bonds.

 In conjugation, the bonds between the carbon atoms are

alternately single and double.

 Every bond contains a localised “sigma” (σ) bond which forms a

strong chemical bond.

 In addition, every double bond also contains a less strongly

localised “pi” (π) bond which is weaker.
 In an electric field, the conjugated π-electrons of the
polymers get excited, thereby can be transported along
the solid polymer backbone through orbital overlapping.

 This results in the formation of valence bands and

conduction bands over the entire polymer molecule.

 Polyacetylene polymers – poly-p-phenylene,

polyquinoline
 Condensed aromatic rings – polyaniline,
polyanthrylene
 Heteroaromatic and conjugated aliphatic units –
polypyrrole, polythiophene, polybutadienylene
Doped conducting polymer
 It is obtained by exposing a polymer to a charge transfer agent in
either gas phase or in solution.
 ICP possess low conductivity (10-10 Ω-1 cm-1) but due to their low
ionisation potential and high electron affinities they can be
easily oxidized or reduced.
 Conductivity of ICP can be increased by creating either positive
or negative charges on the polymer backbone by oxidation or
reduction
 The condition is that the plastic has to be disturbed either
by removing electrons from (oxidation), or inserting them
into (reduction), the material. The process is known as
Doping.
 There are two types of doping:
1) Oxidation with halogen (or p-doping) or with lewis acid
– positive charges are created on polymeric backbone

2C2 H 2 n  3I 2  2C2 H 2 n I 3


2) Reduction with alkali metal (called n-doping) or with

lewis base – negative charges are created

CHn   xNa  CHn  x

 xNa 
 The above game offers a simple model of a doped polymer.
 The pieces cannot move unless there is at least one empty
"hole".
 In the polymer each piece is an electron that jumps to a
hole vacated by another one. This creates a movement
along the molecule - an electric current.
 Doping process
 The halogen doping transforms polyacetylene to a good
conductor.

Oxidation with iodine causes the electrons to be jerked

out of the polymer, leaving "holes" in the form of
positive charges that can move along the chain.
 The iodine molecule attracts an electron from the polyacetylene
chain and becomes I3ֿ.
 The polyacetylene molecule, now positively charged, is termed a
radical cation, or polaron.

• The lonely electron of the double bond, from which an

electron was removed, can move easily.
• As a consequence, the double bond successively moves
along the molecule.
• The positive charge, on the other hand, is fixed by
electrostatic attraction to the iodide ion, which does not
move so readily.
Factors that affect the conductivity
 Density of charge carriers.
 Mobility
 Charge flow direction.
 Presence of doping materials (additives that
facilitate the polymer conductivity)
 Temperature.
 Applications
Conducting polymers have many uses.
The most documented are as follows:
 anti-static substances for photographic film
 Corrosion Inhibitors
 Compact Capacitors
 Anti Static Coating
 Electromagnetic shielding for computers "Smart
Windows"

A second generation of conducting polymers have been

developed these have industrial uses like:
 Transistors
 Light Emitting Diodes (LEDs)
 Lasers used in flat televisions
 Solar cells
 Displays in mobile telephones and mini-format
television screens
Shield for computer screen
against electromagnetic smart" windows
"smart" windows
radiation

Solar cell
Photographic Film Light-emitting diodes