Module 2: The Chemistry of Engineering Materials

CHAPTER 6 - POLYMERS

Contents Hours
1. Introduction to Polymers
2. Classification
3. Types of Polymerization (Chain & Step growth);
4. Plastics: Thermoplastic & Thermo setting resins
5. Properties and engineering applications of ABS, PVC,
Teflon and Bakelite
6. Compression, injection, extrusion, Transfer moulding
methods of plastics

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1. Introduction to Polymers

Introduction
Polymers : Poly + mers
Poly means many; mers means units or parts
Polymers - Many parts or many units

Definition of Polymer
Polymers are macromolecules (giant molecules of higher molecular
weight) formed by the repeated linking of large number of small
molecules called monomers.
Example:
n CH2 = CH2 (CH2-CH2-CH2-CH2-)n

ethylene (monomer) polyethylene (polymer)

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1. Introduction to Polymers

Terminology: mer: a unit

Monomer : one unit (A)

Dimer : two units (A-A)
Trimer : three units (A-A-A)
Tetramer : four units (A-A-A-A)
Polymer : many units (-A-A-A-A-A-A-A-A-A-A-A-)n

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 Why would a polymer form?

Synthetic polymers:

energy-rich monomers: exothermic reaction

polycondensation: release of small molecule: entropy gain

ring-opening polymerization: release of ring strain

addition polymerization: convert Pi to sigma bond

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1. Introduction to Polymers

Degree of Polymerisation
The number of repeating units(n) in a polymer chain

5 CH2 = CH2 -CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-

Degree of polymerisation is 5

Oligo Polymers:
low degree of polymerisation, Mwt ranges from 500-5000
High Polymers:
High degree of polymerisation; Mwt ranges from 10,000-2,00,000

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1. Introduction to Polymers

Homopolymer
A polymer containing same type of monomers is known as Homopolymer
Example: Polyethylene, Polypropylene
---- M – M – M – M – M – M ----

Copolymerisation
It is the polymerisation in which two (or) more different monomers combine to give
a polymer. High molecular weight polymers, obtained by copolymerisation, are
called copolymers.
C6H5 C6H5
Copolymerisation
n CH2 = CH - CH = CH2 + n CH2 = CH -(-CH2 - CH = CH - CH2 - CH 2 - CH -)n

Butadiene Styrene Polybutadiene-co-styrene

(Styrene butadine rubber, SBR)

Cl OCOCH3
Cl OCOCH3
Copolymerisation
n CH2 = CH + n CH2 = CH -(-CH2 - CH - CH2 - CH -)n
vinylchloride vinylacetate
Polyvinyl chloride-co-vinylacetate
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Polymers are a high molecular weight compounds with repeating units.
(monomer)
Eg: Products made using plastics and rubber materials are based on
polymers.
Polymers are operating in a variety of environment. They have useful
range of deformability and durability.

Degree of polymerization
Functionality
Mechanism: Addition, Condensation
Cationic, anionic, Zeigler Natta
 Classification of polymers
thermoplastics, thermosets and elastomers.
Thermoplastics
amorphous, crystalline polymers.
*which exhibit elastomeric properties. They can be
stretched easily to high extensions and will spring
back rapidly when the stress is released.
Crystalline polymers are thermoplastic materials having regularly
arranged molecular structures. The amorphous polymers are
irregularly arranged molecules. Liquid crystalline polymers are stiff,
rod like structures which are organized in large parallel arrays or
domains in both the melt and solid state.
 Further classifications…………….

based on the reacting monomer.

They classified,
inorganic (Si and Ge) or organic.
commodity polymers, engineering polymers and
high performance polymers
• Commodity polymers have relatively low physical
properties. They are used for making consumer
products of low cost, materials of low stresses, low
temperature resistance, limited product life and high
volume production.
• Eg. Low Density Polyethylene (LDPE), Polyvinyl
chloride (PVC).
 Engineering polymers

• Engineering polymers have good strength and

thermal resistance. They are costlier when
compared with commodity polymers. They are
used in housing load bearing members,
machine enclosures and for applications
requiring wear resistance, long life expectancy,
flame resistance and ability to endure cyclic
stress loading. Eg. Polyethyleneterephthalate
(PET), Polycarbonate (PC).
 High performance polymers

• High performance polymers are very high in

strength and thermal resistance. They are very
expensive and priced above most engineering
polymers. They are used for high temperature
and high stress applications in harsh
environments. Eg. Polyetheretherketone
(PEEK) Polyethersulphone (PES).
1. Introduction to Polymers

Tacticity
• Orientation of functional groups in a polymer chain which can takes order or
disorder manner with respect to carbon main chain.
• They are Isotatic, Syndiotatic and Atactic

• Isotactic Polymer: Functional groups are

arranged on the same side of the main chain.

• Syndiotactic Polymer: Functional groups are

arranged in an alternating fashion.

• Random or Atactic Polymer:

Functional groups are arranged randomly

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• .
2. Classification of polymers

2. Classification of polymers
• Natural polymers : Polymers isolated from natural materials
e.g. Silk, cotton wool and rubber

• Synthetic polymers : Polymers synthesized from low molecular

weight compounds
e.g. Polyethylene, PVC, nylon

• Organic polymers : Polymers whose backbone is made of carbon

atom
e.g. Bakelite

• Thermoplastic polymers : Polymers which soften on heating and stiffen

on cooling
e.g. nylon, PVC

• Thermosetting polymers: Polymers which becomes infusible and

insoluble mass on heating
e.g. Phenol formaldehyde plastic or bakelite 19
3. Types of Polymerization (Chain & Step growth)

Definition of Polymer:
Polymers are macromolecules (giant molecules of higher molecular weight)
formed by the repeated linking of large number of small molecules called
monomers.
Types of Polymerization:

i). addition or chain polymerisation

ii). condensation or step-wise polymerisation

Addition and Condensation polymerization [classification is based

on the composition or structure of polymers]
or
Chain and Step growth polymerization [classification is based on the
mechanisms of the polymerization]

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3. Types of Polymerization (Chain & Step growth)
Condensation (Step-Growth) Polymerization:

Some of the earliest useful polymeric materials, the Bakelite resins formed from the condensation
of phenol and formaldehyde, are examples of step-growth processes.

In general, step-growth polymers such as polyesters and polyamides possess more

robust mechanical properties, including toughness, stiffness, and higher temperature
resistance, than polymers from addition polymerization processes such as polyolefins
and other vinyl-derived polymers.

Some naturally occurring polymers such as cellulose, starch, wool, and silk are classified as
condensation polymers
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3. Types of Polymerization (Chain & Step growth)
Condensation (Step-Growth) Polymerization:

Typical Condensation Polymerization

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3. Types of Polymerization (Chain & Step growth)
Condensation (Step-Growth) Polymerization:

In Step-growth polymerization only

after 100 % conversion or at the end of
the reaction we get maximum
molecular weight as shown in bellow
figure
Polymer

Molecular weight vs % conversion in step-growth polymerization

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3. Types of Polymerization (Chain & Step growth)

i). Addition or Chain polymerisation

• 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 this addition polymerisation there is no elimination of any molecule.
Heat / pressure
- CH2 - CH2)-
)
n CH2 = CH 2 n - CH 2 - CH2 -
Catalyst n
Ethylene Bif unctional monomer Polyethylene (PE)

Cl Cl
Cl
Heat / pressure
- CH2 - CH -)
)
n CH 2 = CH n - CH2 - CH
Catalyst n
Vinyl Chloride Bifunctional monomer Polyvinylchloride (PVC)

CN CN
CN
Heat / pressure
- CH2 - CH -)
n - CH2 - CH )
n CH 2 = CH n
Catalyst
Acrylonitrile Bifunctional monomer Polyacrylonitrile (PAN)
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3. Types of Polymerization (Chain & Step growth)
Addition (Chain-Growth) Polymerization:

Typical Addition Polymerization

In Chain-growth polymerization maximum

molecular weight will be obtained at the
beginning of the reaction irrespective of the
monomer conversion as shown in bellow
figure

Molecular weight vs % conversion in

chain-growth polymerization
25 25
4. Plastics: Thermoplastic & Thermo setting resins

Plastics

• Plastics are high molecular weight organic materials,

that can be moulded into any desired shape by the
application of heat and pressure in the presence of a
catalyst
• Plastics or resins are classified into two types
A). Thermoplastic resins
B). Thermosetting resins

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4. Plastics: Thermoplastic & Thermo setting resins

A). Thermoplastic resins

• They are prepared by addition polymerisation.

• They are straight chain (or) slightly branched polymers and
various chains are held together by weak vanderwaal’s forces
of attraction.
• Thermoplastics can be softened on heating and hardened on
cooling.
• They are generally soluble in organic solvents
• Examples: Polyethyene, Polyvinylchloride

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4. Plastics: Thermoplastic & Thermo setting resins

B). Thermosetting resins

• Thermosetting resins (or) Thermosets

• They are prepared by condensation polymerisation
• Various polymer chains are held together by strong covalent
bonds (cross links)
• Thermosetting plastics get harden on heating and once
harden, they cannot be softened again
• They are almost insoluble in organic solvents.
• Examples: Bakelite, Polyester

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4. Plastics: Thermoplastic & Thermo setting resins

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Radical Polymerization
The molecular weight of the polymer can be controlled by
a process known as chain transfer
Chain-growth polymerization of monosubstituted
ethylenes exhibits a marked preference for head-to-tail
addition
Head-to-tail addition of a substituted ethylene results in a
polymer in which every other carbon bears a substituent
Head-to-tail addition is favored for steric reasons

Groups that stabilize radicals also favor head-to-tail

addition
Branching of the Polymer Chain
Branched polymers are more flexible
Cationic Polymerization

the alkene monomer

reacts with an electrophile
The carbocation intermediates formed during
polymerization can undergo rearrangement
Monomers that are best able to undergo cationic
polymerization are those with electron-donating
substituents
 Anionic Polymerization

Nonterminated chains are called living polymers

The chains remain active until they are killed

Ring-Opening Polymerization
Stereochemistry of Polymerization

substituents on the same side

substituents regularly alternate on both sides

Long, unbranched polymers can be prepared using an
aluminum–titanium initiator (Ziegler–Natta catalyst)
Polymerization of Dienes
Synthesis of Synthetic Rubber
The product resulting from polymerization of different
monomers is called a copolymer
Four Types of Copolymers
Progress of a Step-Growth Polymerization
Nylon 6 is an example of a step-growth polymer formed
by a monomer with two different functional groups
The incorporation of aromatic rings into polymers
improves the physical strength of the polymers
Polyesters are step-growth polymers in which the
monomer units are joined together by ester groups
Polyesters with two ester groups bonded to the same
carbon are known as polycarbonates
Epoxy resins are the strongest adhesive known
A urethane (carbamate) is a compound that has an
OR group and an NHR group bonded to the same
carbonyl compound
 Thermosetting Polymers
Very strong and rigid materials can be obtained by
cross-linking
 Oriented Polymers
These polymers are stronger than steel

They can conduct electricity

 Biodegradable Polymers
These polymers can be broken into small segments by
enzyme-catalyzed reactions
 Other Polymers

Thermoplastic polymers have both ordered crystalline

regions and amorphous, noncrystalline regions

Elastomers are polymers that stretch and then revert to

the original shape

Plasticizer is an organic compound that is added to a

polymer to make it more flexible
5. Properties and engineering applications of ABS, PVC, Teflon and Bakelite

Acrylonitrile butadiene styrene(ABS)

ABS is a ter-polymer

It is polymerized by the polymerization of acrylonnitrile, butadiene

and styrene

It is an amorphous and thermoplastic polymer

Mainly ABS can be prepared in two different grades: 1. for extrusion

and 2. for injection moulding.

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5. Properties and engineering applications of ABS, PVC, Teflon and Bakelite
Acrylonitrile butadiene styrene(ABS)
Properties of ABS:
• Cost effective
• Good Impact Strength
ABS can be recycled
• Good Chemical Resistance
• High Gloss Surface Finish
• Good Flexural Properties
• Can prepare in different grades as per the requirement
Applications of ABS:
• musical instruments (recorders, plastic clarinets, and piano movements)
• automotive trim components, automotive bumper bars
• medical devices for blood access
• White-water canoes
• buffer edging for furniture and joinery panels
• luggage and protective carrying cases
• small kitchen appliances
• Keyboard keycaps
• toys, including Lego and Kre-O bricks
• golf club heads (because of its good shock absorbance)
• Household and consumer goods 71
5. Properties and engineering applications of ABS, PVC, Teflon and Bakelite.

Polyvinyl Chloride (PVC)

Polyvinyl Chloride (PVC)

Preparation: Preparation of PVC involves the following two steps

I step: Vinyl chloride is prepared by treating acetylene with hydrogen

chloride at 60-80oC in the presence of metal chloride at catalyst

II step: Polyvinylchloride is obtained by heating water emulsion of vinyl

chloride in presence of benzoyl peroxide (or) hydrogen peroxide under
pressure

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5. Properties and engineering applications of ABS, PVC, Teflon and Bakelite.

Properties of PVC:
1. PVC is colourless, odourless and chemically inert powder
2. It is insoluble in inorganic acids and alkalis, but soluble in hot chlorinated
hydrocarbons such as ethylchloride
3. It undergoes degradation in presence of heat (or) light

Uses of PVC
1. It is used in the production of pipes, cable insulations, table covers and rain-
coats etc.,
2. It is also used for making sheets, which are employed for tank-linings, light
fittings, refrigerator components, etc.,
Polyvinylchloride (PVC)

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 TEFLON OR FLUON(PTFE)
Obtained by polymersation of water-emulsion of tetrafluoloro etylene under p, in
presence of small amount of benzoyl peroxide.

F
F F
F Polymerisation
n C=C
C=C
F F n
F F
Polytetrafluoloro etylene
tetrafluoloro etylene
Properties; Due to the presence of strong electro negativity of fluorine atoms
in polytetrafluoloro etylene, there exists a very strong attractive forces
between the Different chains , which results in
extreme toughness, high density 2.1-2.3gcm-3
high softening point 350C.
High chemical resistance ( alkali metal, hot fluorine)
This polymer is a hard, strong,
high melting point and very low surface friction.
Hydrophobic polymer
Very tough,
very low co-efficient of friction
Extremely good electrical mechanical properties
It can be mechined, punched and drilled
Disadvantages;
It can not be dissolved it wont exist in molten state
Around 350C it can be sinters to form very viscous, opaque mass
which can be moulded to certain shapes under ‘P’.
Uses
Insulating material. Packings, pump parts, tank links, chemical
carrying pipes, tubings tanks
For coating and impregnating glass fibers,
Asbestos fibers, non lubricating bearings,
non sticking stop-cocks
5. Properties and engineering applications of ABS, PVC, Teflon and Bakelite.

TEFLON

Uses of TEFLON
• In motors, transformers coils, capacitors, pipes, tanks and storage of
chemicals
• Non-stick appliances
• Where TEFLON is used as a lubricant, it reduces friction, wear and energy
consumption of machinery.

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5. Properties and engineering applications of ABS, PVC, Teflon and Bakelite.

Bakelite
Bekalite is obtained by the condensation polymerisation of phenol and
formaldehyde in the presence of acid or alkali catalyst
Preparation
The reaction involves the following 3 steps

Stage:1
The first step is the reaction between phenol and formaldehyde to produce
methylol phenols (mono, di and tri-methylol phenols)

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5. Properties and engineering applications of ABS, PVC, Teflon and Bakelite.

Bakelite
Stage 2: Synthesis of linear polymer Novolac
• When methylol phenols are heated with excess of formaldehyde in presence
of alkaline catalyst. The methylol phenols condense either through
methylene linkages or through ether linkages to form resoles.
• Resole is a low molecular weight linear polymer. It is completely soluble in
alkaline solution

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5. Properties and engineering applications of ABS, PVC, Teflon and Bakelite.

Bakelite
Stage 3: Synthesis of cross linked polymer Bakelite
or phenol formaldehyde resin
By reacting the methylol pheonls in the presence of a curing
agent (hexamethylene tetramine) produces hard, rigid, infusible,
cross-linked polymer called bakelite

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5. Properties and engineering applications of ABS, PVC, Teflon and Bakelite.

Bakelite
• Properties of Bakelite
• Bakelite is resistant to acids, salts and most organic solvents,
but it is attacked by alkalis because of the presence of –OH
groups
• It possesses excellent electrical insulating property

• Uses of Bakelite
• Bakelite is used as an adhesive in plywood laminations &
grinding wheels, etc
• It is also widely used in paints, varnishes
• Cooker with Bakelite Handles
• It is used for making electrical insulator parts like plugs,
switches, heater handles, etc.,

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6. Moulding methods of plastic

Moulding Process
• This process involves fabrication of plastic material into
desired shape under the influence of heat and pressure in a
closed chamber. Some moulding process is given below
a). Compression Moulding
b). Injection Moulding
c). Transfer Moulding
d). Extrusion Moulding

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Additives Example Functions
Resins Thermoplastic resins, Binding material to hold the constituents, they are major
Thermosetting resins part of plastics.
Thermosetting resins are supplied as linear polymers have
low molecular weights, conversion to cross linked form
takes place during moulding using catalysts.

Plasticisers DOP-dioctyl phthalate, Improve flow for processing by reducing the intermolecular
oleate, adipate, organic forces, reduce brittleness.
phosphates

Fillers or Particulate Fillers include, Increase tensile, compressive strength. Reduce shrinkage
Extenders mica, quartz, limestone,
Fibrous fillers include
Nylon, acrylics,

Lubricants Waxes, oils, soaps Make moulding process easier, proper finish
Stabilizers Stearates of lead, Ba, Cd Increase thermal stability during processing

Pigments TiO2, ZnO-white chromium Provide colours

oxide-green
Carbon black,
Red laed-red
Antioxidants Pheny-p-napthyl amine, Protect against oxidative degradation.
dipheny-p-phenylene-
diamine
Catalysts or Hydrogen or benzoyl Added only to Thermosetting resins inorder increase the
Accelerators peroxide polymerization of fusible resin into infusible cross-linked
form durind moulding.
6. Moulding methods of plastic

a). Compression Moulding

• This method is applied to both thermoplastics and thermosetting

plastics
• Figure shows a typical method used for compression moulding
• The mould is made up of two halves, the upper and the lower
halves.
• The lower half usually contains a cavity in the shape of the article to
be moulded.
• The upper half has a projection, which fits into the cavity when the
mould is closed.
• The material to be moulded is placed in the cavity of the mould.
Then the mould is closed carefully under low pressure
• Finally the mould is heated to 100-200o C and simultaneously high
pressure (100-500 kg/cm2) is applied on the top of the mould.
Curing is done either by heating or cooling. After curing the
moulded article is taken out by opening the mould parts.

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6. Moulding methods of plastic

a). Compression Moulding

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Compression Moulding Compression moulding & Transfer
moulding are the fabrication
methods used for moulding of
thermosetting plastics.
Compression moulding involves
application of heat (upto 200 C)
& pressure (70 Kg/cm2) to the
mould having the compounded
resin.
Applicable for both thermosetting &
thermoplastics.
Two halves: upper half & lower half
Excess material pass via
extrusion pin hole.
Manual or Mechanical process.
6. Moulding methods of plastic

b). Injection Moulding

• This method is mainly applicable to thermoplastics.
• The powdered plastics material is fed into a heated cylinder through the
hopper (Fig).
• The plastic material melts under the influence of heat and becomes fluid.
• The hot fluid is injected at a controlled rate into a tightly locked mould by
means of a screw arrangement or by a piston
• The mould is kept cold to allow the hot plastic to cure and becomes rigid.
After curing the mould is opened and the object is ejected.
• Telephones, buckets etc., are made by this method.
Advantages
1. Low mould cost
2. Low finishing cost
3. Low loss of materials
4. High speed production

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6. Moulding methods of plastic

b). Injection Moulding

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6. Moulding methods of plastic

c). Extrusion Moulding

• This method is mainly used for continuous moulding of
thermoplastic materials into articles of uniform cross section
like rods, tubes etc.
• In this method, the powdered plastic material is fed into the
heated cylinder through the hopper
• The molten plastic material is then pushed by means of a
revolving screw conveyor into a die having the required shape
of the object to be manufactured. The finished product that
extrudes out is cooled by atmospheric air. A long conveyor
carries away the cooled product.

88
6. Moulding methods of plastic

c). Extrusion Moulding

89
Extrusion Moulding
Used mainly for continuous moulding of thermoplastic materials
into articles of uniform cross-section like tubes, hoses, rods,
strips, insulated electric cables.
 Ingredients are heated to
plastic condition and then
pushed by means of
screw conveyor into a
die, having the required
outer shape of the article
to the manufactured.
 Plastic mass gets cooled
by atmospheric exposure.
 This process is used to
coat the wires and cables
with PVC or other plastics
6. Moulding methods of plastic

d). Transfer Moulding

• This method is used for thermosetting plastics
• The principle is same as that of the injection moulding
• The powdered moulding materials is taken in a heated
chamber, maintained at low temperature, at which the
material just begins to become plastic. This plastic is then
injected through an orifice into the mould by a plunger
working at high pressure
• Due to the great friction developed at the orifice during
ejection, the temperature of the material rises to such an
extent that the moulding powder becomes almost liquid. So
that it flows quickly and easily into the mould.
• Then the mould is heated upto the curing temperature
required for setting. Finally the moulded article is ejected
from the mould

91
6. Moulding methods of plastic

d). Transfer Moulding

92
 Transfer moulding
Principle: principle of injection moulding for thermo setting plastics;

*The moulding powder is placed in a heated chamber- temperature

maintained minimum temp at which moulding powder just become plastic

The plastic material -injected through an orifice into the mould by the plunger,
working at pressure. Due to the great friction developed at the orifice, the temp
of the material at the time of ejection from orifice, rises to such an extent that
moulding powder almost liquid consequently it flows quickly into the mould,
which is being heated up to the curing temp required for setting. The moulded
article then ejected mechanically.
 Advantages
1.Since the mix flows into the mould cavity in a highly plasticized condition
very delicate articles can be handled without distortion or displacement.
Fine wires and glass fibers may be inserted into the mould.
2. Intricate shapes not attainable by compression moulding can be produced
3. Article produced free from flow marks.
4. Thick pieces cure almost completely and uniformly
5. Owing to uniform through cure, distortion and shrinkage are minimum-
mechanical strength and density is higher.
6.Finishing cost is entirely eliminated. Gases are expelled in the plasticizing chamber
itself
7. Mould cost is less, since it involves very low abrasive action
 Degradable Polymers
• Conventional non-degradable polymer systems are used
for applications like packaging, medical, automobile and
agricultural areas.
• These polymers cannot be degraded easily and hence it
litters the environment.
• Recycling is obviously a better choice at a higher cost
but most countries cannot afford to recycle all its polymer
wastes. Moreover, many polymers lose their quality
• on recycling. This leads to the quest for new modified
degradable polymers to replace the existing synthetic
polymers.
• The degradable polymers have properties that are sufficiently
comparable to those of the conventional polymers. The term
degradable polymer relates to the polymeric materials that
disintegrate under environmental conditions in a reasonable
and demonstrable period of time. Degradation of polymers
may occur by any of the following.
1. Bio degradation:
It is promoted by enzyme and may be either aerobic or
anaerobic and provides for complete removal of the polymer
from the environment.
2. Photo degradation:
It is promoted by irradiation Eg. sun light. It rarely leads to
complete removal, though small fragment may be produced
for subsequent bio degradation.
3. Environmental erosion:
This is promoted by weather elements such as wind, rain,
temperature and larger animals. This also cannot remove the
polymer completely.
4. Chemical degradation:
This is promoted by chemical reactions through additives. Eg.
metals and poly functional groups, which produce smaller
fragments of the polymers.

• However, by using the above methods we should be able to

remove the polymers almost completely from the
environment and biodegradation is found to be a best
method.
Biodegradable Polymers
The biodegradation of polymer proceeds by hydrolysis and
oxidation. The presence of hydrolysable and oxidizable
linkages in the polymer main-chain, the presence of suitable
substituents, correct stereo-configuration, balance of
hydrophobicity and hydrophilicity and conformational flexibility
contribute to the biodegradability of the polymer.

Biodegradable polymers may be divided into three classes.

i) Natural polymers (eg.Protein).
ii) Biosynthetic polymers (eg. Poly-hydroxy alkanoates).
iii) Synthetic polymers (polycaprolacyone and polylactic acid).
• Natural polymers like cellulose and starch cannot be
thermally processed as such. Cellulose has a degradation
temperature below its melting point. Moreover, due to its
complex morphology of crystalline regions and hydrogen
bonding, cellulose is difficult to dissolve in common
solvents.
• However, processing with the help of suitable solvents like
N-methylmorpholine-N-oxide(N-MMNO) and water or
dimethylacetamide. Hence spinning of cellulose into
lyotropic liquid crystalline fibers is possible even though
which is complicated and dangerous. However, cellulose
ester can be melt processed as a thermoplastic polymer,
since its melting temperature can be significantly reduced
below degradation point. Similarly, modified starch has
been incorporated into polymer blend systems to provide
bio degradability.
• Polyhydroxy alkonates are high molecular weight bio
degradable polymers. These can be melted and moulded.
These polymers find use in both medical and industrial
applications due to their bio-compatibility and bio
degradability.
• Cellulose is a high molecular weight, stereo-regular and linear
polymer of repeating β-D-glucopyranose units. Cellulose is the
chief structural element and major constituents of cell wall of
trees and plants.
• Degree of polymerization is the average number of glucose
unit in each cellulose molecule of a pulp sample. It is a high
molecular weight, stereo-regular and linear polymer of
repeating β-D-glucopyranose units. It is the chief structural
elements and major constituents of the cell wall of trees and
plants.
Substance Degree of Mol. Wt
polymerization
Native cellulose >3500 >5,70,000
Purified carbon 1000 – 3000 1,50,000–5,00,000
Wood pulp 600 – 1000 90,000 – 1,50,000
Commercial 200 – 600 30,000 – 1,50,000
Regenerated
Cellulose (eg. Rayon)
β – Cellulose 15 - 90 3,000 – 15,000
γ – Cellulose < 15 <3000
Dynamite
Nitrocellulose 3000 – 5000 7,50,000–8,75,000
Plastic Nitrocellulose 500 – 600 1,25,000-1,50,000
Commercial
Cellulose Acetate 175-300 45,000- 1,00,000
• Hemicellulose (constituent of wood) is a polysaccharide but
less complex and easily hydrolysable.
• Lignin (complex constituent of wood) connecting cellulose
fibers together. Brown in colour and responsible for the
strength and rigidity of plants. Amorphous, aromatic
biopolymer - Obtained from almost all types of natural wood
based resources. It is byproduct of pulp and paper mills and
is conveniently treated as waste material having low
economical usage. It is separated from the cellulose either
by strong alkaline or acidic solutions or by high pressure
steam treatment followed by solvent extraction. Unmodified
lignin has poor solubility and a thermoplastic melt having
flow characteristic like cellulose. But esterification of lignin
improving the properties and used as a thermoplastic
polymer. Lignin was found to be useful as a mould lubricant.
Moreover, lignin and its derivatives are bio degradable.
 Conducting Polymers
Introduction
Polymers are typically insulators due to their very high resistivity. Insulators
have tightly bound electrons so that nearly no electron flow occurs, and
they offer high resistance to charge flow.
For conductance free electrons are needed. Conductivity in polymers can
be induced by delocalizing their orbitals with conjugated p-electron
backbones.

Alan J. Heeger, Alan

G. MacDiarmid and
Hideki Shirakawa
discovered that
Polyacetylene can be
made conductive
almost like a metal
(Nobel Prize for
Chemistry in 2000).
 Conducting Polymers
• Polymeric materials –poor conductor of electricity(non
availability of free electrons)
• Now a days synthesized polymeric material possess
electrical conductivity. Such polymers are called as
conducting polymer
• Ex. Polyaniline, polypyrrole, polyacetylene
• Types
• 1. Intrinsically conducting polymer (ICP) or
• conjugated p-electrons conducting polymer
• 2. Doped conducting polymer- The polymer has to be
disturbed - either by removing electrons from (oxidation), or
inserting them into (reduction) the material. The process is
known as Doping.
• 3. Extrinsically conducting polymer
 1. Intrinsically conducting polymer(ICP) or
conjugated -electrons conducting polymer
• Polymer whose backbones or associated groups consist
of delocalized electron-pair or residual charge
• Such polymers essentially conjugated pi-electrons
backbone, which is reponsible for electrical charge
• In an electric field, conjugated pi electrons of the polymer
get excited and transported through the solid polymeric
materials
• Overlapping of orbitals (conjugated pi-electrons)over the
entire backbone results in the formation of valence
bands as well as conductions bands, which extends over
the entire polymer molecule
• Presence of conjugated pi-electron in a polymer
increases its conductivity to a larger extent.
• Ex: Polyacetylene, polyphenylene, polyphenylene-co-
vinylene
What are the two conditions for a insulating polymer to become a conducting polymer?:
1st Condition: The polymer should consist 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 localized “sigma” (σ) bond which forms a strong chemical bond.
In addition, every double bond also contains a less strongly localized “pi” (π) bond which
is weaker.

Polyacetylene

2nd Condition: The polymer structure has to be disturbed - either by removing

electrons from (oxidation), or inserting them into (reduction), the material. The
process is known as Doping.

Doping process:
Polyacetylene upon doping with halogens exhibit conductivity upto 10 5 S/cm.
When doped with Iodine, polyacetylene undergoes oxidation causing electrons to
be removed from the polymer, leaving "holes" in the form of positive charges that
can move along the polymer chain.
 2. Doped conducting polymer
• The polymer 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).

3x
CH n   I  CH n   I 3
2
2- Reduction with alkali metal (called n-doping).

x
CH n   xNa  CH n   xNa 
• The 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.
 Conductivity Mechanism in
Polyacetylene
• p-type doping process
• The halogen doping transforms polyacetylene to be 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.
 Conductivity Mechanism in Polyacetylene
n-type doping process
The mechanism followed by polyacetylene for the transfer of charge from one chain
to another is called intersoliton hopping.

What is a soliton? The soliton is a charged or a neutral defect in the polyacetylene

chain that propagates down the chain, thereby reducing the barrier for
interconversion.
In n-type doping (This can be done by dipping the film in
THF solution of an alkali metal) soliton is a resonance-
stabilized polyenyl anion of approximately 29-31 CH units in
length, with highest amplitude at the centre of the defect.
The solitons (anions) transfer electrons to a neutral soliton
(radical) in a neighboring chain through an isoenergetic
process.
The charged solitons are responsible for making
polyacetylene a conductor.
 DOPING - FOR BETTER
MOLECULE PERFORMANCE
• Doped polyacetylene is, e.g., comparable to good conductors
such as copper and silver, whereas in its original form it is a
semiconductor.

Conductivity of conductive polymers compared to those of other

materials, from quartz (insulator) to copper (conductor). Polymers
may also have conductivities corresponding to those of
semiconductors.
3.Extrinsically conducting polymer
• Polymers whose conductivity is due to the
presence of externally added ingredient in
them.
• Two types
• Conductive element-filled polymer
• Blended conducting polymer
 Conductive element-filled polymer

• Resin or polymer filled with conductive elements such as

carbon black, metallic fibres, metal oxides etc
• Polymer acts as binder to hold the conducting elements
together in the solid entity.
• These polymers possess resonably good bulk
conductivity
• Advantages: 1. Low cost
2. Light in weight, mechanically durable and
strong
3. Easily processable in different forms,
shapes and sizes
Conducting Polymers
polymers especially with a conjugated pi-bond system often
yield higher conductivity after the doping process. But,
the conducting polymers are having poor mechanical
properties.
Thus the combination of electronic and mechanical
properties with conventional polymers seems to have
great promise for many applications. Since the
conducting polymers are stable and retain the
mechanical properties of the host polymers, film fibers
and coatings can be fabricated by solvent evaporation or
by melt processing for use in anti-static applications, for
electromagnetic shielding and absorption for transparent
conducting films etc.
 A bifunctional linkage is used to increase the force of
attraction between two polymeric components. Eg. the
effect of p-hydroxybenzenesulphonic acid which serves
as a bifunctional linkage between polyaniline and
polycaprolactum.

Polyaniline/Polycaprolactum interpolymeric complex with PHBSA as the bi functional linkage.

The purpose of adding bifunctional linkage is to increase
the system’s conductivity and to promote stronger
interaction between poly aniline and poly caprolactum.

Polyaniline is a conducting polymer because of conjugated p-bond

system and in aniline the pz orbitals and ring pelectrons are part of the
conjugated system. The conjugated double bonds permit easy electron
mobility throughout the molecule because the electrons are delocalized.
This condition allows electrons to move more easily thereby making the
polymer electrically conductive. Polyaniline was chosen for this
experiment because of easy method of obtaining and presence of
conjugated double bond structure, the benzenoid ring change during the
conversion of quinonoid imine to benzenoid amine structures, which
renders the polymer as an electrically conductive.
Polyaniline exists in three forms namely
leucoemeraldine (fully reduced or only benzenoid amine structures),
emeraldine (neutral or partially reduced and partially oxidized) and
pernigraniline (fully oxidized or only quinonoid imine structure).

The emeraldine based form of polyaniline is the most stable of the three
states because leucoemeraldine is easily oxidized when exposed to air
and pernigraniline is easily degraded. It is also having good conduction.
Doping is a process by which insulating and semiconducting polymers
are synthesized and exposed to charge transfer agents in the gas or
solution phase or through appropriate electrochemical oxidation or
reduction. This process will increase the polymer’s ability to conduct
electricity because of the increased concentration of charge carrier.

Polyaniline was doped with p-hydroxy benzenesulphonic acid in a 1:2

ratio or for every repeating unit of poly aniline, two molecules of p-
hydroxy benzenesulphonic acid was used. Conductivity of electrically
conducting polymers can be increased several fold by doping them with
oxidative and reductive substituent.
Pure polyaniline, in the undoped state, is a poor semiconductor with
conductivity of about 10-8 S/cm. However, once it is doped, its
conductivity could increase by a factor of 10 or more depending on the
dopant. Doping with acid such as p-hydroxybenzenesulphonic acid can
increase conductivity because doping forms a polaron/bipolaron
structure that will increase polyaniline’s charge due to increased
relocalization.
The bipolaron structure is the initial result of
protonating emeraldine based polyaniline with p-
hydroxybenzenesulphonic acid. The hydrogen ions
from p-hydroxybenzenesulphonic acid will attach
themselves to the quinonoid nitrogen atoms. This
is highly unstable because of the high energy this
structure possesses. Thus the C=N bond of the
quinonoid imine structure will break, transforming
the quinonoid ring into a more stable benzenoid
ring, with lower energy, by aromatization creating
the bipolaron structure of doped polyaniline.
Structure of doped polyaniline and polycaprolactum blend
system
Bipolaron structure of polyaniline emeraldine based
The new benzenoid ring, although more stable than it was previously
still has high energy because of the repulsive force from the
adjacent positive charges. To stabilize the structure,
the positive charge of one of the hydrogen ions will attract electrons
from the neighboring benzene ring, neutralizing the charge.
This will create new positively charged nitrogen with a neutral nitrogen
atom in between the positive ones.
The increased distance between two positive charge results in the
polaron structure, which has a lower energy level than the bipolaron
structure (Fig.26). Since the ionic interactions between polyaniine
and p-hydroxy benzenesulphonic acid anions are weak, the p-
hydroxy bezene sulphonic acid anions are able to migrate to the
newly formed positively charged nitrogen atom as the doped
polyaniline complex stabilizes itself by transforming into the polaron
structure. The migration of p-hydroxy benzenesulphonic acid is
easier in the solution form.
APPLICATIONS OF CONDUCTING POLYMERS

S= siemen = mho
Shield for computer screen
against electromagnetic smart" windows
"smart" windows
radiation

Solar cell
Photographic Film Light-emitting diodes
 APPLICATIONS OF CONDUCTING POLYMERS
Group 1 Group 2
Electrostatic materials Molecular electronics
Conducting adhesives Electrical displays
Electromagnetic shielding Chemical, biochemical and thermal sensors
Printed circuit boards Rechargeable batteries and solid electrolytes
Artificial nerves Drug release systems
Antistatic clothing Optical computers
Piezoceramics Ion exchange membranes
Active electronics(diodes, transistors) Electromechanical actuators
Aircraft structures 'Smart' structures and Switches

The first group utilizes their conductivity as its main property.

The second group utilizes their electroactivity