POLYMER

Lecture By:
Dr. Harminder
Kaur
 Introduction to Polymers
• Polymers are a large class of materials consisting of many small molecules
(called monomers) that can be linked together to form long chains, thus they
are known as macromolecules.
• A typical polymer may include tens of thousands of monomers. Because of
their large size, polymers are classified as macromolecules.
• Humans have taken advantage of the versitility of polymers for centuries in
the form of oils, tars, resins, and gums.
• However, it was not until the industrial revolution that the modern
polymer industry began to develop.
• In the late 1830s, Charles Goodyear succeeded in producing a useful form of
natural rubber through a process known as "vulcanization." Some 40 years
later, Celluloid (a hard plastic formed from nitrocellulose) was successfully
commercialized.
• Despite these advances, progress in polymer science was slow until the 1930s,
when materials such as vinyl, neoprene, polystyrene, and nylon were
developed. The introduction of these revolutionary materials began an
explosion in polymer research that is still going on today.
 The Polymers are made from petroleum or natural gas
raw materials.
Primary Resources Basic Petrochemicals Polymer Materials End Products

Crude Oil Plastics

Ethylene PE
Propylene PP
Styrene PS Elastomers
Vinyl Chloride PVC
Natural Gas
Butadiene ABS Fibres
Cyclohexane PA
SBR
Acetylene Adhesives +Coatings
Etc.
Chlorine Nitrogen Acrylonitrile

Other non-
petrochemical raw
materials

Production of Polymer based products from raw materials

A Polymer is a long chain molecule formed by the joining together of thousands of
small Molecular units by chemical bonds. Due to their large size, sometimes they are
called MACROMOLECULES.
The Chemical process leading to the formation of Polymer is known as POLYMERIZATION.

The number of monomeric units contained in the polymer is known as

DEGREE OF POLYMERIZATION.

Small molecules which combine with each other to form polymer molecules are known as
MONOMERS.

For Example,

Where n is the degree of Polymerization, it can be 10⁴ or

more.
 Functionality
• Functionality means the number of Bonding sites in a monomer. The double
Bond in vinyl monomers can be considered as a site for two free vacancies.
When the double bond is broken, two single bonds become available for
combination.

• For Example,

When Functionality=2, linear or straight chain polymer molecule is

formed. Ex: All Vinyl monomers, Hexamethylene, Adipic Acid.

When Functionality=3, three dimension network polymer molecule is formed.

Ex: Phenol, Melamine.
Formation of linear and
branched and branched
chains on the basis of
Functionality.
 Polymer Classification
1. Based on Structure/Shape: A polymer molecule may be linear, Branched
or cross-linked.

Polymer Structure Examples

Linear HDPE (High density

polythene)

Branched LDPE( Low density

polythene)

Cross-linked XLPE( Cross-linked

Polythene), Rubbers,
Themosets
2.Based on physical state: A polymeric material can be Amorphous (e.g. LDPE, Rubbers)
or Semi-Crystalline( e.g. HDPE , Nylon).

3.Based on its behaviour when heated to Processing temperatures.

Polymeric materials are broadly divided into two categories on this
basis. Thermoplastics and Thermosetts.

4.Based on end use: These include Fibres, Plastics, Elastomers, Films, Adhesives,
Paints, Membranes etc.

5. Based on Origin: natural or Synthetic

6. Based on Conductance: Insulator or Conducting

7. Based on environment friendly nature

8. Based on type of monomers: Polar or Non polar

9. Based on number of monomers: Homopolymer or copolymer

 10. Based on Tacticity ( or configuration)

Polymer Structure Model Description

Isotactic Side Groups are all

on the same side

Syndiotactic Arrangement of side

groups in alternating
sidess

Atactic Arrangement of side

groups is at random
around the main
chain.
Summary of Classification Based on
Origin
of Polymers •Natural
•Synthetic

Based on Structure/Shape Based on Conductance

• Linear •Insulators
• Branched •Conducting
• Cross-Linked
Based on Environment friendly
Based on Physical State nature
• Amorphous
•Biodegradable
• Semi-Crystalline
•Durable
Based on Response to Heat
Based on type of Monomers
• ThermoPlastics
• Thermosets •Polar
•Non-Polar
Based on End-Use
• Fibres Based on Number of Monomers
• Plastics
•Homopolymer
• Elastomers
•Copolymer
• Films
• Adhesives Based on type of Atoms present in
• Paints the Polymer
• Membranes
•Organic Polymers
•Inorganic Polymers
Based on Tacticity
• Isotactic Based on Growth Mechanism
• Atactic of Polymerization
• Syndiotactic
 Advantages offered by
Advantages offered by Polymers in Comparison with metals, wood,
Polymers
ceramics and other conventional materials:

❑Polymers have low densities, this leads to production of light weight products,
hence costs of transportation and general handling are low.

❑ Polymers have excellent resistant to Corrosion.

❑ Polymers are usually thermal and electrical Insulators.

❑ Some polymers, especially rubbers, are inherently flexible.

❑ Polymeric materials are easily mouldable even into complex shapes.

❑Polymeric materials have the ability to take variety of colours, shades etc.
which do not fade easily since colouring is not usually restricted to the
surface but is throughout the mass.
❑ Polymeric materials are tailor made.
 Drawbacks in Polymers compared
with Traditional materials
Disadvantages of by Polymers in Comparison with metals, wood,
ceramics and other conventional materials:

❑ Lower Strength and stiffness, they get easily deformed under Load.

❑Temperature Limitations ( hot or cold) in service, they have low heat resistance
and low temperatures, embrittlement occurs.

❑ Time dependent properties. They show “creep”.

❑ They are combustible, but metals and ceramics are not.

 Industry wise, typical Applications of
End –Use Characteristics Required Typical Examples Polymers
Polymers
Industry
Electrical Excellent insulation properties, Wire and Cable Insulation, PE, PVC
Industry flame retardant characteristics,
toughness, durability Plugs, Sockets
PF
Building Economical, Durable, Piping,, flooring, window PVC
Industry Aesthetics frames
Packaging Light Weight, Aes-thetics, Films- For food HDPE, PP,
Industry Protection For Textile PET,PVC

Bottles
Auto-motive Light Weight(Fuel Economy), Electrical Equipments, Speciality
Industry Safety, economy in manu- batteries, flux, plug, switches Plastics
facture, ease of maintenance,
Aesthetics
Leisure Performance, Aesthetics, Photographic Films. PET, PS,,Glass
Industry Durability Audiotapes, CD’s, Rackets or carbon
fibre
reinforced
materials
 Polymerization
It is the process by which simple(monomer) molecules join together to form
Very large ( polymer) molecules. Hence, the synthesis of large molecular
weight polymers is called Polymerization.
There are three different ways for doing Polymerization:

By opening a double
Bond

By opening a
ring

By using molecules
having two functional
groups
 Thermodynamics of Polymerization
reactions
The spontaneity of a polymerization reaction is indicated by negative values of free
energy change (∆G)
We know that ∆ G = ∆H - T ∆S
where ∆H is the enthalpy of polymerization, ∆ S is the entropy of
polymerization (= Entropy of a polymer - Entropy of a
monomer), and T is the polymerization temperature.

Generally, ∆ H values are negative since polymerisation reactions are exothermic.

The ∆ S values are also negative as there is a change from disorder to order
polymerization [(i.e., the entropy of a polymer (Sp) is less than the entropy of
monomers (Sm) and ∆ S = Sp - Sm= Negative)].

An increase in polymerisation temperature increases T ∆ S term whereas it does not

change significantly.
This decreases the magnitude of ∆ G and at a certain temperature a condition is
achieved when ∆H = T ∆ S, i.e., ∆ G=0. The polymerization reaction is now said to be in a
state of dynamic equilibrium.
 The rates of polymerization and de polymerization are the same. The temperature
at which the equilibrium is attained is known as the ceiling temperature (Tc) of
the polymer under study. The Tc imposes the upper limit of polymerisation.

Above Tc, no polymerization can occur. The ceiling temperatures for

some commonly used monomers are :

Similarly there is a lower temperature limit referred to as the floor

temperature (Tf) below which no appreciable reaction occurs.
Monomer Styrene Α-methyl Methyl Ethylene
styrene Methaacrylate
Tc( degree 310 61 220 677
celsius)

The optimum temperature for polymerisation reactions fall between the Tc and
Tf
 Addition Polymerization
Polymer synthesized by addition polymerization has the same empirical formula
as that of monomer. No molecule is evolved during polymerization and the
polymer is an exact multiple of the original monomeric molecule.

For Example,

Where,

-SG (Substituent -H -CH3 -Cl -C6H5

Group)
Polymer Polythene Polypropylene Poly Vinyl PolyStyrene
Chloride
 Condensation Polymerization

It takes place by the condensation of two different bi- or poly functional

monomers having functional groups which have affinity for each other.

For example, - COOH and - OH or - COOH and - NH2 carrying monomers

undergo condensation polymerization.
It always accompanies with the elimination of small molecules like H20, HCl etc.

For example :
 Difference b/w Addition and
Condensation Polymerization
S.No Addition Polymerisation
1 It requires the presence of double
bonds in the monomer.
2 No by product is formed.
3 Homo-chain Polymer, generally a
Thermoplastic is Obtained.
4 The growth of chain is at one active
centre.
5 Example: Polymerization of ethylene
to form Polyethylene(PE)
Condensation Polymerization
It requires two reactive functional groups
to be present at both ends of the
monomer.
Generally, a by-product is formed.
Hetero-chain Polymer either Thermo-
plastic or Thermoset can be obtained.
The growth of chain occurs at minimum
of two active centres.
Example: Condensation Polymerization of
Hexamethylene diamine and Adipic Acid
to form Nylon 66 (polyamide)
 Step Growth
It proceeds by step-wise fashion:
Polymerization
Monomer Dimer
Monomer n step-growth Trimer
olymerization s Oligomer
capable of mbining with self Polymer
or with ot
ispecies present
p with equal ireactivity, hence
coit disappearsitearly in the reaction.
any

The degree of polymerisation and hence the molecular weight of the polymer rises
steadil throughout the reaction. The reactivity is governed by the functional groups.

Longer reaction time is essential for getting higher molecular weight polymer. It can be
eit addition or condensation polymerisation.

For example : (i) Addition (step-growth) polymerisation (ii) Condensation (step-growth)

 Chain Growth Polymerization
It proceeds by chain mechanism and high molecular weight polymers formed almost
immediately after the start of the reaction.
Longer reaction time have a little effect on molecular weight, but gives higher yield. (Thus,
number of polymer molecules continuously increase with reaction time).

At any stage, either unreacted monomer or high molecular weight polymer is

there. No oligomers, molecules with intermediate range of molecular weights, are
there.
Free radical
For chain growth polymerization, initiators e.g., Cationic
Benzoyl initiators e.g.,
Initiators are used and they can be : peroxide H+

Anionic Hetrogeneous
initiators e.g., (Zeigler Natta)
R- Na+ initiators
Types of Chain Growth Polymerization

Addition (chain-growth) Polymerization

Condensation( step-growth)
Polymerization
(i) Addition ( chain-growth) Polymerization.

High molecular weight polymers can be synthesized from vinyl monomers

by Carefully conducted radical or ionic polymerization.

Examples of Vinyl monomers which can be polymerized by this method are:

(ii) Condensation ( step-growth) Polymerization

 Condensation( step-growth)
Polymerization
It proceeds by stepwise intermolecular condensation. The product formed at each step, when
bifunctional reactant molecules react together, still has the functional group for further
reaction and thus the reaction will continue until one of the monomer is completely
consumed. When this happens, we generally get a big, polymer, molecule.

For example; let us consider the synthesis of Nylon 66 starting from its monomers Adipic acid
HOOC — (CH2)4 — COOH and hexamethylene diamine H2 N (CH2)6 NH2.

It can be seen from the above mechanism that carboxylic acid and amino functional groups are
at the ends of Dimer (I) and Tetramer (II). Hence, tetramer will behave like a dimer and thus
the chain will grow in the same fashion, till we get a polymer molecule.

Hence, if we condense n molecules of adipic acid with n molecules of hexarnethylene diamine

a Polymer (Nylon 6,6) of the following structure will be obtained.
Reaction:
Mechanism:
 Addition( chain-growth)
Polymerization
It takes place with compounds having the multiple bonds such as vinyl
monomers

CH2= CH

SG

Where SG is the Substituent Group, it can be

-H, -CH3, -Cl, -CN, -C6H5 etc.

 Mechanism:
(i) Chain Initiaton Step(s) : Interaction of Monomer(M) with Initiator(In)
for
its activation and generation of reactive particle (M *) occurs in this step.

M M*
(ii) Chain Propogation Steps: It consists of a series of consective reactions
to carry the chain growth process by the interaction of M * with other
monomer molecules.
For Instance: M1*
M* + M
M1* +M M2*
M2* +M M3*
(n-1) number of similar steps, to generate M*n-1.

(iii) Chain Termination Steps: The chain growth is finally terminated by

this step. M*n Mn

Where Mn* is activated growing polymer chain and Mn is inactive polymer

molecule.
Types of Addition(chain-growth)
Polymerization

Free Radical
Polymerization

Ionic Polymerization
(a) Cationic and
(b) Anionic

Coordination
Polymerization
 Free radical Polymerization
In free-radical polymerization, monomer is activated by its transforrmation into radical by the
action of light (as in photochemically initiated), heat (as thermally initiated), ionizing radiation
such as alpha, beta or Gamma radiations (as in raditiation initiated) or by adding chemicals,
known as initiators, (as in chemically initiated) free radical polymerization.

Initiators are the compounds which readily decompose into free radicals. that monomer
molecules can interact with these free-radicals for their activation.

Examples of well known initiators are benzoyl peroxide and azobis butyronitrile (AIBN). They
generate free radicals according to the following reactions :
 Mechanism of Free radical
Polymerization
Chain Initiation

It involves two steps viz, decomposition of the initiator

In 2R
And the addition of the first vinyl monomer CH2=CH molecule to the
free
SG
Radical(R) and the formation of (I) as Intermediate.

Where SG is the Substituent Group.

Chain propagation
It is accomplished by the addition of monomer molecules to (I) leading to the
formation of macro-radicals. In general

The chain propagation steps determine

(i) The rate of Polymerization,
(ii) The molecular weight of the Polymer,
(iii) The structure of the Polymer chain (the degree of branching due to chain
transfer reactions) and
(iv) The mode of monomer addition, as the reactive particle can attack an asymmetric
vinyl monomer at ether carbon atom of the double bond.

Generally, in a final polymer, monomer units are linked together in such a manner
that they have substituents on alternate carbon atoms.
This is known as head-to-tail or H - T or 1, 3-placement of monomer units. This H
- placement is favored on both steric and resonance grounds.
Chain Termination

The growing polymer chain can be terminated by

(i) Recombination :which consists of combination of two radicals
either

Or
At T=60 C, “ Polystyrene and acrylonitrile chains terminate mainly
by recombination”

(ii) Disproportionation : It involves the transfer of a hydrogen atom of macro-radical

to another to form two macromolecules, one of them with a double bond at its
end

“At T>= 60 C, PMMA and vinyl acetate chains terminate mainly

disproportionation”
(iii)Reaction with Polymerization inhibitors: Growing polymer chain can also
be terminated.
By its reaction with Polymerization inhibitors like hydroquinone and trinitrobenzene.

Oxygen is also a powerful inhibitor as it reacts with radicals to form the

unreactive peroxy radical that reacts with itself or another propogating radical
by coupling and disproprotionation reactions to form inactive products.

(iv) Reaction with the Solvent molecules ( like Carbon Tetra Chloride)
 Kinetics of Free radical Addition
Polymerization
The mechanism of a simple free radical initiated addition
polymerization is rewritten below:
For simplicity, assuming termination by combination.

In the above mechanism, M, In, M* and I* indicate monomers, initiators their radicals
respectively, each initiator yielding two radicals.

Let f is the fraction of radicals which initiate chains, i.e., the initiator efficient and [In] is the
concentration of initiator.
As kd « ka -So, decomposition of In is rate determining step for initiation.
Thus, the rate of initiation, R, is given by
Ri = 2f kd [In]
The rate of propagation Rp is governed by the concentration of growing chain [M'] and of
monomers [M]. This is also , in effect, the rate of monomer consumption so Rp also becomes
the overall rate of polymerization
Rp = kp [M] [ M*]

The termination rate in mutual termination is determined by the concentration of growing

radicals. This reaction is of second order as two radicals are involved in each termination :

Rt= Kt[--M*]
Thus, the rate of radical formation ( Ri) becomes equal to the rate of radical disappearance,
(Rt). i.e., [Ri] =[Rt]

This value of M* is then substitued, we get,

Above equation Indicates that Rp α [In], this is also found to be experimentally true.

The equation also indicates that Rp α [M]. But experimentally , some deviation w.r.t [M]
are found. These deviations may in some cases be attributed to the dependency of f on
[M] particularly. At low efficiencies and in solution polymerizations, certain solvents may
also affect the rate Rp α [M].

The Average Kinetic Chain Length (r) : It is defined as the number of monomeric
units consumed per active centre formed.
 Ionic Polymerization ( Cationic)
These are dependent on formation and propagation of ionic species. Relatively low or
moderate temperatures are also needed to suppress termination, transfer, and other chain
-breaking reactions which destroy propagating centers.

(A) Cationic Polymerisation. Monomers with electron releasing substituents (such as —

OCH3, — 0C2H5 and — C6 H5, etc.) undergo cationic polymerization in the presence of
Lewis acids and Friedel Craft catalysts (like Al C13, BF3, Sn C14 etc.) . They add on to the
monomer forming a carbornium ion. An essential feature of cationic addition
polymerisation is that it takes place at very high rates, even at very low temperatures.
Monomers like a — methylstyrene, and isobutylene are preferably polymerized by this
method as they do not polymerise well by other methods. Electron releasing
substituents such as alkyl, alkoxy, and phenyl increase the e- density at the carbon-
carbon double bond and facilitate its bonding to cationic species. Moreover, these
substituents stabilize the carbocation intermediates in propagation steps by resonance
like
Ist Step IInd Step
Polymerization Mechanism of Styrene

Initiation

Propogation

Termination
Polymerization Mechanism of IsoButylene
Initiation

Propogation

Termination

+
 Ionic Polymerization ( Anionic)
(B) Anionic Polymerisation. Monomers with electron attracting substituents , (such as –
CN, – COO CH3 and – C6 H5 etc.) undergo anionic polymerization; presence of sodium
or potassium amide, alkali metals (such as Na, K) and Grignard reagent as catalysts.
Thus, strong bases are typical catalysts.

Mechanism. In anionic Polymerisation, the catalyst interacts with the monomer to

generate a carbanion as the active centre for chain growth. As the intermediate
carbanion is stabilized by electron-withdrawing substituents hence an polymerization is
favourable with the monomers having such substituents.
For, example,
 Mechanism(Anionic)
Initiation

Propogation

Termination
Coordination Addition
Polymerization
These polymerisation reactions are catalysed by Zeigler Natta catalysts
formed between triethyl aluminium Al (C2 H5)3 and titanium halide Ti Cl3.

A coordination complex is formed between these two, in which the ethyl

group is coordinated to titanium, this is an active catalyst and its structure is
shown below :
 Mechanism:
Initiation In the initiation step, π – cloud of alkene overlaps with an empty orbital
of titanium , then there is insertion of alkene molecule between the Ti-C
bond.

Propogation As intramolecular rearrangement again generates a vacant site of

Titanium, each time one monomer molecule can be added in the same
fashion.

Termination It can be done by the addition of molecules containing active Hydrogen like
HX.
 Copolymerization
Copolymerisation has been used by nature in polypeptides which may contain as
many as 20 different amino acids. Chemists are still far behind, but copolymers of
two monomers, or terpolymers of three monomers, are now being widely
produced. Copolymerisation is a polymerisation of two or more monomeric species
together.
For examples,
 Properties of Copolymers
The properties of Copolymers depend on the type of monomers and how they link together
in copolymers. Let us start with two monomers M1 and M2. The dependence on their
linking, the following four types of monomers are possible:
Copolymers Structure Description

Alternate Monomers are arranged in

regular alternate fashion.

Block A block of repeating unit of

one kind of monomer is
followed by a block of
repeating unit of other kind.

Random Monomers are randomly

distributed along the polymer
chain.
Graft Have branched structures in
which the monomer
segments on the backbone
and branches differ.
 Polymerization Techniques
Polymerization reactions are exothermic. The main concern during polymerization is to
effectively dissipate this heat from the reaction mixture to avoid explosion and/or
running the heat-sensitive polymer product. The math polymerisation processes are
given below :

Solution
Homogeneous
Bulk
Polymerisation
processes
Emulsion
Hetrogeneous
Suspension
 Homogeneous Polymerization
In this method the polymerization reaction takes place in one homogeneous phase. This may
occur in solvent or in a reactor vessel containing only monomer. So there are basically two
methods viz. Solutior polymerization and bulk Polymerization respectively :

These methods are briefly discussed below :

(a)Solution polymerization : In solution polymerization, the monomer is initially dissolved in a

suitable solvent and then the initiator is added to start the polymerization. When the
reaction is over the polymer is obtained by precipitation. The polymer is filtered off, washed
and dried before use. An ,Acrylic acid

b)Bulk Polymerization : Bulk polymerization is the simplest method of polymerisation. Both

addition and condensation polymerisations can be carried out in a bulk polymerization
reactor. The monomer is taken in the liquid state and the initiator is dissolved in the
monomer itself. Polymerisation is then carried out in pre-and post polymerisation stages for
controlling the heat of polymerisation. Till about 10% conversion, reaction is quite slow
subsequently it becomes fast When it gets polymerised to 25-30%, the reaction mixture
becomes viscous. In the second stage (post-polymerisation stage), the viscous mixture is
transferred to the main reactor maintained at constant temperature. After a known period of
time, the contents are poured into methanol when the polymer gets precipitated out.
 Heterogeneous Polymerization
(a) Emulsion polymerisation : In this method the monomer is dispersed in an aqueous
phase as fine droplets (10^-5 to 10^-6 mm in size), which are then stabilised
(emulsified) by adding surfactants (detergents) or protective colloids. The surfactants
will form micelles when their conc. exceeds critical micelle conc. (CMC) that are
dispersed throughout the solution. The addition of initiator leads to initiation of
reaction in the micelles. Eg persulphates
PVC,PVA

(b) Suspension polymerisation : In this method, the monomer is dispersed, large droplets
(0.1 — 1 mm in size) in water and kept in suspension by mechanic agitation. Stabilizers like
gelatin and water soluble cellulose derivatives are used. The initiators are soluble in
monomer and polymerization continues in each droplet till 100% conversion and the
polymer is obtained as pearls or spherical bead. Add stabilizer(Mg silicates,aluminium
hydroxide
Monomers which can be polymerised by this method are : styrene, vinyl chloride, methyl
methacrylate etc.
Pros : The purity of polymer is high compared to that synthesized by
emulsion polymerisation. Viscosity is low throughout and temperature can be easily
CRYSTALLINITY
IN .

POLYMERS
 • Even a polymer with regularity of molecular structure does not
exist entirely in cyrstalline form . This is because of their large size.
As solidification begins , the viscosity of the polymer rises.

Crystallinty is influenced by:

❖ Molecular weight
❖ symmetry of repeat unit
❖ Chain branching
❖ Cross linking
 Factors affecting the glass transition
temperature Tg
❖ Chain flexibility- Greater the intrinsic chain flexibility smaller will
be Tg.

❖ Configuration- Tg (PE)> Tg (cis-1,4- polybutadiene) because

inclusion of double bonds stiffen the chains at the point of
inclusion.
❖ Intermolecular forces Tg (PE)>Tg(PVC)
❖ Molecular weight- Tg is directly proportional to molecular weight
❖ Cross links- Greater cross linking has higher Tg
❖ Plasticizer- Plasticization decreases the Tg.
❖ Copolymerization - Random copolymers have lesser Tg.
Crystallinty affects the following properties of the polymer:-

❖ With increase of crystallinty

❖ strength and stiffness of polymer increases.

❖ solubility and permeability of polymer decreases

❖ density and melting point of polymer increase

❖ Opacity of polymer increases

 PLASTICS
Broadly speaking , the plastic can generally be of two types:-
❖ Thermoplastic
❖ Thermosetting

❖ Thermoplastic polymers:
Thermoplastics have either linear or branched structure. They can be amorphous
or semi crystalline materials . Neighbouring polymers are held together by weak
vander wall forces or hydrogen bonding. Examples-PVC,PE,PP,PMMA.

❖Thermosetting polymers:
They have 3-d,cross linked networked structure. Neighbouring polymeric chains
in thermosets are held together by strong intermolecular forces . Heating does
not soften them as softening requires breaking of covalent bonds. Examples:
PF, UF, MF, vulcanized rubber.
STRUCTURE PROPERTY
RELATIONSHIP
IN POLYMERS
 Structure Property Relationships
Between The Polymers
Polymer properties are influenced by the structure of
the polymer. Structutal details which affect the
properties of polymers include:

▪ chemical composition
▪ sequence of monomer units
▪ types of bonds present
▪ nature of packing
▪ molecular weight
1. Mechanical Properties

Structure of a polymer significantly influences the

mechanical properties of a polymer.
Mechanical properties such as strength, elasticity,
hardness etc are largely affected by the crystallinity of
the polymer.
Other mechanical properties such as tensile strength
and impact resistance are related to the molecular
weight of the polymer.
 A.) Strength
The strength of the polymer depends upon – intermolecular
forces of attraction between the molecules and molecular weight
of the polymer.

In straight chain and branched chain polymers, individual chains

are held together by weak intermolecular forces of attraction and
strength of these forces increases with the chain length and
molecular weight.
Polymer shows appreciable mechanical strength if it contains
chain length of upto 150- 200 units which corresponds to
molecular weight of roughly 20,000.
High molecular weight polymers are tougher and more heat
resistant whereas low molecular weight polymers are soft, gummy
and brittle.
Hence strength of the polymer can be varied with molecular
weight and chain length.
 Fig : Shows relation between molecular weight and mechanical
properties such as tensile and impact strength.

The nature of the curve is valid for all polymers.

Every polymer has a threshold value for its degree of
polymerisation belw which polymer exists as liquid resin and
doesnot possess any strength.
Intermolecular forces of attraction
Polymer strength can be increased by increasing the molecular
weight.
Other way to increase the polymer strength is through the
introduction of polar groups such as –COOH, -OH , -Cl , -F etc
which increases the intermolecular forces of attraction.
The strength of the polymer is also affected by the Crystallinity
of polymer.
For a partially crystalline polymer, its crystalline and amorphous
region exhibits different properties even though both the
regions are chemically similar.
Density of Crystalline regions will be higher than the amorphous
regions.
Hardness and tensile strength of crystalline polymer is higher as
compared to amorphous polymer.
 Fig : Showing dependence of Physical properties of polymers on their
molecualr weight and crystallinity
Strength of the polymer is greatly influenced by the
configuration of the polymer units.
Polyethylene (PE) has simple and uniform shape as a result of
which the molecules can slip past each other.
In Polyvinyl chloride (PVC) , the molecules are restricted due to
the presence of larger chloride atoms. Hence, PVC is stronger
and tougher than PE.
B.) Elastic Deformation
The term ‘ elasticity’ refers to the recoverance of original shape after a
derformation stress is released
Whether the polymer will behave as elastomer or not depends upon its
geometrical structure as well as type of interchain arrangement within the
chain aggregates.
For example- rubber band is an elastomer as it exhibits elasticity and can be
elongated to many times its length.
A substance behaves as elastomer if it consists of long chain of molecules
having free rotating groups.
In unstretched conditions, these chains are irregularly coiled and as the
polymer is stretched, the chains begin to straighten out as shown in figure
below.
 C.) Plastic Deformation
If a substance at any stage of its formation is capable of
flowing (plastic stage) is called plastic.

Plastics can be moulded into different shapes under flow

condition and they retain their shape on cooling.

The materials which can undergo plastic deformation by

application of heat or pressure are called thermoplastics.

The plasticity of a polymer is related to the secondary bonds

present in the polymer molecules.
The linear long chain polymers show the greatest degree of
plastic deformation due to the presence of weak van der waals
forces between different molecules. Under high temperature
conditions, van der waals forces become more weak and
polymer starts to flow.

The cross linked polymers donot undergo plastic deformation

due to the presence of strong covalent bonds . The molecules
cannot slip past each other due to strong directional covalent
bonds.

These crosslinked polymers are referred to as thermosets.

 2. Solubility
Dissolution of polymer into solvent is divided into 2 steps- In
first step, solvent slowly diffuses into the polymer to produce
swollen gel. In second step, solvent disintegrates the polymer
and solution of the polymer in solvent is obtained.
The process of dissolution of a polymer is slow as compared to
simple molecules . It sometimes takes weeks for a high polymer
to dissolve.
Diffusion of solvent into polymer depends upon
polymer-solvent interaction which leads to expanding of polymer
and allows penetration of solvent molecules.
The dissolution of the polymer is affected by-
a.) Chemical nature of polymer and solvent
b.) Molecular weight of polymer
c.) Chain flexibility of polymer
d.) Packing density in solid polymer
 The general principle that like dissolves like also prevails for polymeric
solutions.
Non polar polymers form solutions in non-polar solvents.
Cross linked polymers donot dissolve but swell only if they interact at all
with the solvent.
Linear polymers are soluble in some solvent. The solvent molecules can
get inbetween the chains and chains begin to move freely. Hence the
substance swells and as more solvent gets into the mass, a viscous solution
results.
Amorphous polymers with bulky polar substituents readily swells in polar
solvents but donot form solutions at room temperature.
Crystalline polymers donot easily dissolve due to close packing between
the chain segments and require high temperature to break the crystalline
order to facilitate contacts between individual segment and solvent
 3. Chemical Reactivity
Polymers containing only C-C and C-H bonds such as polyethylene etc. are
inert and undergo only substitution reactions.
In case of branched polymers, oxidation may takes place at tertiary carbon
atom.
Polymers containing double bonds are vulnerable to oxidation and undergo
scission of the chain.
Esters, amides and carbonate groups are susceptible to hydrolysis. However,
in case benzene ring is present adjacent to such groups it protects them from
hydrolyzing.
Polymers containing C-F bonds (PTFE) are very stable and inert.
Cellulosic polymers having free hydroxyl (-OH) group can be attacked by no.
of reagents leading to useful modification of properties. For example-
reaction with nitric acid produces nitro-cellulose from which gun cotton and
celluloid are formed.
4. Electrical properties
In general, polymers are insulators, that is, they are bad conductors of
heat and electricity.
Polymeric materials especially plastics have been used in many
electrical applications which are related to their insulating capacity.
Important electrical properties include dielectric strength, dielectric
constant and dissipation factor.

Dielectric strength
The insulating property of a material is determined by its dielectric
strength.
Higher the resistance of the material for electrical flow, larger is the
insulating capacity or dielectric strength.
The dielectric strength of the material is defined in terms of maximum
voltage the material withstands and beyond which the dielectric nature of
the material is lost
Dielectric strength can be expressed as voltage per unit thickness.
Dielectric strength = V/mm
 Dielectric Constant
❖ Dielectric constant is the ratio of the capacitance formed by two plates
with an insulator sandwiched between them to the capacitance of the
same plates without the material i.e. with vacuum as a medium
between them.
❖ Also referred as relative permittivity.
❖ It is a dimensionless parameter.
❖ It describes the ability of a dielectric to store electrically separated
charges (electro-static charges).
Structure of the polymer and electrical
properties
❖ In non polar dielectrics such as benzene, polyethylene,
polytetrafluoroethylene etc only electronic polarisation is
responsible for the dielectric constant. It is independent of
temperature and frequency. These materials have low
dielectric constant (usually less than 3)
❖ In polar dielectrics, both electronic as well as dipole
polarisation contributes towards overall dielectric constant .
The extent of dipole polarisation decreases with increase in
frequency. Electronic polarisation involves movement of the
electrons whereas dipole polarisation involves movement of a
part or whole of a molecule . Hence the dielectric constant is
high and lies between 3 and 7.
Dielectric Strength of some of the polymers are given in table below

Material Dielectric Constant

(ε)
❑ Dielectric properties in a polar material would depend
upon the location of dipole in the structure. For example-
if dipole is located in main chain then the polarization
would depend upon the segmental movement of the
chain.
❑ The polarization would be low below Tg and material will
act as insulator only at temperature below Tg.
❑ Electrical properties of a polymer are also affected by
humidity. It lowers the resistivity of a material. Moreover
it may also cause plasticising effect and thereby raises the
value of the dielectric constant.
 5.Light Transmission
Polymers differ in their ability to transmit light.
Some plastics are transparent, exhibiting properties similar to
glass. Other plastics are opaque, and donot allow any light to
pass through .
Similarly, Translucent plastics allow some light to pass through
them, but images are cloudy and unfocused. Lastly , some
plastics are semi-opaque, allowing enough light to pass through
them to make out shadows and vague outlines.
The polymer crystallinity plays a major role in determining the
optical properties of plastics.
Amorphous polymers such as the acrylic, polycarbonate and
polystyrene donnot form crystals and have constant value of
refractive index throughout the material. Thus no scattering of
light takes place and material appears transparent.
.
 In Crystalline polymers, the refractive index arises due to
difference in densities of the crystalline regions. This causes
scattering of light and polymer appears translucent.
.
In general, amorphous polymers are transparent and crystalline
polymers are translucent

Sometimes, even crystalline polymers appear transparent. If the

crystalline structures are smaller than the wavelength of light ,
they donot interfere with passage of light. As a result polymer
appears transparent

Amorphous polymer has uniform refractive index but if any

additive or impurity is present in amorphous polymer , then also
amorphous polymer will become translucent.
6. Permeability
In packaging industry one of the most important property to be
considered is permeability.
Permeability is defined as the rate of penetration of liquid or
gas through the polymer matrix.
In crystalline polymers because of close packing, the
permeability is quite low. As crystallinity increases permeability
decreses.
In amprphous polymers, above glass transition temperature,
there is enough free volume for the passage of liquid or gases .
Hence, they are permeable.
 ADDITIVES FOR POLYMERS
❖ The words polymers and plastics are not synonymous . The pure material
which results from the process of polymerisation , which have long chain
molecules is known as polymer. In general , the usefulness of pure polymers
is extremely limited.

❖ Compounding of plastics is a process by which polymer resins are mixed with

some additives to impart some special properties in the end use product.
 FILLERS
Blowing plasticisers
agents

ADDITIVE TYPES lubricants

Cross linking
Agents
flame retarder
colourants STABILISERS
 FILLERS
❖ These additives either act as extenders or they improve the mechanical
properties of a plastic
❖ Different grades of fillers differ from each other in particle shape and
porosity , average particle size and size distribution , chemical nature of the
surface and presence of metal ions as impurity.

❖ They can be classified as:-

❖ GASES
❖ PARTICULAR FILLERS
a) inert
b) reinforcing
❖ FIBROUS
❖ RUBBERS
 PLASTICIZERS
❖ They are high boiling pt liquids which act as spacer between the polymer
molecules hence they improve softness and flexibility and decrease the melt
viscosity and temperature of plastic.

❖ Examples:-

a) Nylon is plasticized by water

b)doctyl phthalate is used in pvc.

 LUBRICANTS
❖ They have low compatibility with polymer and great affinity with metals
because of presence of polar groups . They form an interface between molten
layer and metal surface during processing and facilitate processing. They also
impart a flawless and glossy finish to the product.

❖ Example;
1% stearic acid is used as lubricant in PVC.
 FLAME RETARDERS
❖ They function as chemically interfering with flame propagation mechanism or
they produce large volumes of incombustible gases which dilute the air supply
or they react , decompose endothermally , thus absorbing heat.

❖ Example:-use of tri bromo toluene and antimony oxide in PVC.

 COLOURANTS
❖ They are generally used for mass coloration of plastics.
❖ It is desired that they should have strong covering power and stability to
processing . Generally , Dyes are used in transparent polymers and pigments
are used in all polymers.
 STABILISERS
❖ They prevent deterioration the polymer either during processing or
during end use. Following types are generally used;-
❖ a) heat stabilisers - they prevent degradation at high temperatures during
processing.
❖ b) anti oxidants- they prevent either slow oxidative degradation or rapid
oxidative degradation at high temperature.
❖ c) anti ozonants-protect unsaturated polymers against degradation
❖ d) UV absorbers- most polymers degrade quickly in sunlight unless
protected by UV absorbers. Most efficient UV absorbers are carbon black
and titanium dioxide
 ACTIVATOR AND CROSS LINKING
AGENTS
❖ An activator is added to start the cross linking process and once it has started ,
accelerator is added to speed up the reaction. The processor seeks a ‘safe
time’ during which he can till the mould and shape the polymer before it
begins to cross link , hence the use of a delayed action accelerator. They are
also added for accelerating polymerization of fusible thermosetting resins
during moulding operation , into cross linked infusible form.
 NUCLEATING AGENTS
❖ In partially crystallizable thermoplastics , these agents prevent supercooling
and thus help in attaining uniform microstructure with small spherulites. The
resultant polymer is less brittle and more transparent.
 BLOWING AGENTS
❖ They help in making a cellular structure. Foamed products have
higher bending stiffness per unit weight but they can burn readily.

❖ Example;-

Azodicarbonamide is incorporated in PE and during extrusion

the blowing agent decomposes with the evolution of gas.
CONDUCTING
POLYMERS
 HOW CAN A POLYMER BECOME
CONDUCTIVE?
❖For a polymer to become 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. It is obtained
by polymerisation of acetylene, shown in the figure.
 CONDUCTING POLYMERS
❖ Polymers are good electrical insulators
❖ Polyethylene and polypropylene have sigma bonds and electrons are not
mobile
❖ However for more than a decade from now researchers have shown that
certain classes of polymers which are conjugated (those have possess an
extended pi-conjugation along the polymer backbone), exhibit
semiconducting behavior
❖ The discovery of doping led to a further dramatic increase in the conductivity
of such conjugated polymers to values as high as 105 S/cm (conductivity of
copper is 106 S/cm).
❖ Doping is a process in which a polymer is oxidized or reduced so as to create
charge carriers
❖ Conjugation is alternate double and single bonds
❖ S/cm = Siemens per centimeter which is a unit of connectivity
 BAND THEORY AND PROPERTIES OF
MATERIALS
❖ The poor conductivity of polymers is explained by the band theory;

❖ Band theory explains the existence of valence and conduction band..

❖ While valence band are continuous energy levels placing the valence
electrons;
❖ Conduction band are continuous higher energy levels that are empty.
❖ The band gap determines he conducting nature of materials
❖ The fig. shows the band structure of
❖ monovalent metallic conductors
❖ divalent metallic conductors,
❖ insulators
❖ semiconductors
❖ Polymers belong to semiconductors
 CONDUCTING NATURE OF POLYMER
❖ Polyacetylene, polypyrrole, polyaniline have extended conjugation causing
mobility or delocalization of pi electrons across the polymer carbon chain.

❖ Extensive delocalization of pi electrons over the entire polymeric backbone

results in the formation of valence and conduction bands.
❖ Significant band gap exists in such polymers. Such
polymers exhibit semiconducting properties

❖ Electrical conductivity in such polymers results only after appropriate thermal

or photolytic activation

❖ The electrons in valence band get sufficient energy to jump the gap and reach
the lower energy level of the conduction band; resulting in electrical
conductivity;
 TWO CONDITIONS TO BECOME
CONDUCTIVE:
1) 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.
2) The second 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).

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

 DOPED CONDUCTING POLYMERS
❖ Doping i.e addition of external agent into the conjugated polymer can lead to
a dramatic increase in electrical conductivity to values as high as 105 S/cm.

❖ In the presence of a dopant, positive or negative charges are created on the

polymer backbone as a result of oxidation or reduction.

❖ When conducting polymer is exposed to Lewis acid, oxidation occurs and

positive charges are developed on polymer backbone (p type doping),
example of such dopants are I2, Br2, ,PF6.

❖ When conducting polymer is exposed to Lewis base, reduction occurs and

negative charges are developed on polymer backbone (n type doping).
Examples of n dopants are FeCl3.
 CLASSIFICATION OF CONDUCTING POLYMER

Conducting Polymers

Intrinsically Extrinsically Co-ordination

conducting conducting or Inorganic
Polymers Polymers conducting
Polymers

Conducting Doped
Polymers having conducting
conjugated π polymers
–electrons in
backbone
P-Dopi N-
ng Doping
Conductive Blended
element filled conducting
polymers polymers
 1.Intrinsically conducting polymers
These types of polymers have a solid backbone made up of extensive
conjugated system, which is responsible for conductance. They may be of
two types:

( i ) Conducting polymers having conjugated π-electrons in the backbone : These

polymers essentially contain a conjugated π-electron backbone responsible for
electrical charge. Under the influence of electrical field conjugated π -electrons
of the polymer get excited, which can then be transported through the solid
polymer. Further, overlapping of orbitals of conjugated π -electrons over the
entire backbone results in the formation of valence bands as well as conduction
bands, which extend over the complete polymer molecule. The presence of
conjugated π -electrons in polymers increases its conductivity, e.g.,
EXAMPLE OF CONDUCTING POLYMERS

Polyacetylene Polyaniline Polythiophene Polypyrrole

(PA) (PANI) (PT) (PPy)

Polyfluorenes
Poly(p-phenylene vinylene)
(PF) Poly(3,4-ethylenedioxythiophene)
(PPV) (PEDOT)

Poly(p-phenylene) Poly(p-phenylene ethynylene)

12
(PPP) (PPE)
(ii)Doped conducting polymers: The conducting polymers obtained by exposing
the polymer to a charged transfer agent in either gas phase or in solution are
called doped conducting polymers.

Doping is the process by which conductivity of the polymers may be increased by

creating negative or positive charge on the polymer backbone by oxidation or
reduction.

Doping may be of two types:

(A) p-Doping : It is done by oxidation process. In this process, the
conducting polymer is treated with a Lewis acid (A)
❖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.
 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.
 (B) n-Doping : It is done by reduction process. In this process, the conducting
polymer is treated with a Lewis base(B)

Advantages of intrinsically conducting polymers :

(i) Their conductivity

(ii) Their ability to store a charge.

(iii) Their ability to undergo ion exchange.

(iv) They can absorb visible light to give coloured products.

(v) They are transparent to X-rays.

 Limitations of intrinsically conducting
polymers:
❖ Their conductivities are inferior to metals.

❖ improcessability

❖ poor mechanical strength

❖ They are less stable at high temperatures.

❖ Poor storage stability leading to loss in conductivity.

 2. Extrinsically conducting polymers
Those conducting polymers which owe their conductivity due to the presence
of externally added ingredients in them are called extrinsically conducting
polymers. They are of two types :

(i) Conductive element filled polymers : In this type, polymer acts as a binder to
hold the conducting elements together in solid entity.

The minimum concentration of the conductive filler, which is added to let

the polymer start conducting is called the percolation threshold.
 Important characteirstics of these polymers are :

(a)They possess good bulk conductivity.

(b) They are cheaper.

(c) They are light in weight.

They are mechanically durable and strong.

They are easily processable in different forms, shapes and sizes

(ii) Blended conducting polymers: These types of polymers are obtained

by blending a conventional polymer with a conducting polymer either
physically or chemically. Such polymers can be easily processed and
possess better physical, chemical and mechanical properties.

❖ For example,upto 40% of polypyrrole will have little effect on tensile strength
and also give a much higher impact strength than obtainedwith carbon black
filled compound with only 10% loading
Coordination Conducting Polymers
Coordination conducting Polymers or inorganic polymers is defined as the
polymers formed from the reaction of a metal atom with a polydentate ligand.
The degree of polymerization of such polymers is very low (≤20).

Type I polymers have the metal group

tethered to the conjugated backbone by
a linker moiety such as an alkyl group. In
these
cases the polymer acts as a conductive
electrolyte and the metal ions act in
similar way to an untethered group
present in the polymer matrix.
Type II polymers have the metal directly
coupled to the polymer backbone or
coupled to the backbone by a conjugated
linker group, which makes it easier for
Type III of polymer has the metal group directly
the polymer and the metal group to incorporated into the conjugated backbone. In this
affect each other's properties directly. type the metal group has the greatest influence on
the properties of the conducting polymer.

20
 FACTORS THAT AFFECT THE
CONDUCTIVITY
1 Denesity of charge carriers.
2 Thier mobility.

3 The direction.

4 presence of doping materials (additives that facilitate the polymer

conductivity)

5 Temperature.
The conductivity of conductive polymers decreases with falling temperature in
contrast to the conductivities of typical metals, e.g. silver, which increase with
falling temperature.
 APPLICATIONS
❖ Anti-static substances for photographic film

❖ Corrosion Inhibitors

❖ Compact Capacitors

❖ Anti Static Coating

❖ Electromagnetic shielding for computers

❖ "Smart Windows“
❖ Transistors

❖ Light Emitting Diodes (LEDs)

❖ Lasers used in flat televisions

❖ Solar cells
Shield for computer screen
against electromagnetic smart" windows
"smart" windows
radiation

Solar cell
Photographic Film Light-emitting diodes
 CONCLUSION
❖ For conductance free electrons are needed.

❖ Conjugated polymers are semiconductor materials while doped polymers are

conductors.

❖ The conductivity of conductive polymers decreases with falling temperature in

contrast to the conductivities of typical metals, e.g. silver, which increase with
falling temperature.

❖ Today conductive plastics are being developed for many uses.

Degradation of Polymers
Any change in polymer during its service, whether good or
bad, can be technically termed as degradation. For example, if
a plastic bucket is left for long in the sun and rain, it loses its
lustre and strength. In other words it has undergone
degradation.

A polymer can suffer degradation at 2 stages-

1. During the fabrication process which involves
heating, in which a polymer may not withstand and
degardes.
2. During the usage of polymer when it is subjected to
mechanical stresses, radiation, atmospheric oxygen,
moisture etc.
Types of polymer degradation
Polymer degradation can be of 2 types:
1. Chain end degradation: In chain end degradation, the
degradation starts from the chain end resulting in the release of
monomer units.

2. Random degradation: It takes place at any random point along

the polymer chain. In this type of degradation, the polymer
undergoes degradation into low molecular weight fragments but
unlike first case, no monomer units are released.
Factors responsible for degradation:
Degradation of polymers can be brought by:

▪ physical factors such as heat, light etc.

▪ chemical agents such as oxygen, ozone, acids or alkalies.

Thermal Degradation:
Degradation under the influence of heat is known as thermal degradation.
The thermal stability of polymer is dependent upon stability of C-C bond.
In general, bulkier substituents decrease the stability of C-C bond.
For example- polybutylene is less stable than polyethene.
 Presence of aromatic groups in polymer backbone increase the thermal
stability whereas presence of oxygen atom in the polymer chain decreases
the thermal stability.

Polymer degradation is also possible because of the breaking of

substituent groups but not the main chain. Example poly(vinyl chloride)
PVC degrades at about 200 ОC releasing HCl.

As a result of degradation PVC changes colour from white to black ( white

→ pale yellow → orange → brown → black) depending upon the
concentration of conjugated double bonds
Photo Degradation
It is brought about by ultra-violet (UV) light having wavelength below 400
nm and energy corresponding to about 390 KJ/ mole.
Some transparent plastics become yellowish and brittle on storage due to
photodegradation.
The energy required to break C-H, C-C and C=C bonds is 99, 83 and 145
KJ/mole respectively. Hence, these bonds undergo homolytic bond fission
in UV light to give free-radicals which can react with oxygen present
leading to the oxidation of polymer chain
This is the phenomenon of “ ageing or weathering”.
Oxidative Degradation:
It results in hardening, discolouration and surface changes of the polymer.
It depends upon the structure of the polymer. The double bonds in
polymers such as polyisoprene or polybutadiene are easily attacked by
oxygen
In first step of polymer degradation, free radicals are formed by attack of
molecular oxygen or ozone on polymer chain.
Sometimes free radicals are also formed by thermal decomposition of
initiator molecule which may be present as impurity.
Mechanism of Oxidative Degradation
The polymers are protected against oxidative degradation by incorporating
chemical compound called antioxidants.
Steps involved in Oxidative degradation
In the first step, free radicals are formed by thermal decomposition of
initiator molecule.
Then oxygen adds on the radical site forming peroxide radical.
Peroxide radical then attacks the polymer chain and generates a new radical
site.
The hydroperoxide can form several free radical sites.
Recombination reactions of free radicals results in the termination of the
chain reactions.
 Mechanical Degradation
When a polymer material is subjected to a mechanical stress, most
vulnerable part of the structure gets ruptured, thus bringing about
degradation in the polymer called as mechanical degradation.
For example- when polystyrene dissolved in a suitable solvent is
subjected to vigorous stirring, it undergoes considerable molecular
degradation.
In rubber industry, rubber is converted into soft mass from hard and
tough material through mechanical degradation.
The process is called as mastication in which rubber is passed through
rotating rollers to decrease its molecular weight.

The CH2-CH2 links undergo fission during mastication because they are
the weakest links.
POLYMERIC FIBERS
MATERIALS
 FIBERS
❖ They are thin , long thread like materials which have great tensile
strength in the direction of fibers. The strength of fiber depends on the
strength of the chemical bonds of the polymer chains.

❖ The molecular shape of the fiber forming material is linear . This linear shape

permits side by side alignment .

❖ The long thin and thread like polymer molecules lie stretched along
side each other, lined up in fiber direction.

❖ They have strong intermolecular forces which maintain the alignment and
prevent the “slipping” of one molecule past each other.

❖ These intermolecular forces can be vander walls forces , dipole dipole

interactions and H- bonding.
NATURAL FIBERS REGENERATED SYNTHETIC FIBERS

ANIMAL Cellulose ORGANIC

Wool Nylon 6
Silk(proteins) Cellulose acetate
VEGETABLE Cellulose Nylon 66
Cotton Jute triacetate Natural INORGANIC
MINERAL rubber Carbon
asbestos Graphite
Glass
 Natural Fibres
❖ A fibre is a thin thread of a natural
❖ or artificial substance, especially one that is used to make cloth
or rope.

❖ Fibres can be classified into 2 main categories:

❖ Natural and synthetic.

❖ Natural fibres are obtained from natural sources such as

animals and plants
 Plant Fibres
❖ Cotton: Cotton fibre is obtained from the cotton plant. It is the
traditional fibres used in the textile industry.

❖ Linen: Linen fabric is obtained from the flax plant. The

properties of linen fabric are very much similar to cotton fabric.

❖ Jute: It is obtained from the jute plant. On account of its high

strength, it is perfect for use in packaging material.
 Animal Fibres
❖ Silk: Silk is obtained from silk worms. The most popular kind of silk is obtained
from the mulberry silk worm.

❖ Wool: Wool is commonly obtained from sheep. Wool fabric is soft to the
touch and provides warmth to the weather, due to which it is the preferred
choice for winter apparel.
 SYNTHETIC FIBRES
❖ The first synthetic fibre named nylon was made by Carothers in 1938

❖ So far only a few polymer fibres have been produced

❖ The fibre must have sufficiently high melting point to withstand laundering and
ironing

❖ The melting point depends upon shape of the molecules

❖ The closer the packing of the chain, higher is the melting

point Hence fibre molecule should be capable of close

packing

❖ Thus polymers with bulky side chains are not very suitable for making fibres
They belong to the following classes:

❖ Polyester Fibres

❖ Polyamide Fibres

❖ Polyalkene Fibres

❖ Polyacrylic Fibres

❖ Polyvinyl Fibres

❖ Polyurethane Fibres
 Polyester
❖ Alcohol and organic acid react together to make compounds called
esters which are polymers

❖ Polyesters come under the brand names of ‘Terylene’,‘Dacron’, ‘Terene’

and ‘Polyester’.

❖ polyesters formed by condensation of ethylene glycol (a diol) and terepthalic

acid
Synthesis of polyesters from anhydrides and diols
Synthesis of polyesters from di-acid/ its derivatives and
diols
 Properties
❖ The polyester is a good fibre-forming material and is converted into
commercial fibres because of its relatively symmetrical structure and presence
of numerous polar groups

❖ Such fibres have high stretch-resistance (due to high stiffness of polymer

chains), high-crease and wrinkle-resistance

❖ resistant towards atmospheric corrosion and acids.

Uses:
❖It is mostly used for making synthetic fibres like terylene, dacron,

❖For blending with wool to provide better crease and wrinkle resistance.
 Uses:

❖It is mostly used for making synthetic fibres like terylene, dacron,

❖For blending with wool to provide better crease and wrinkle resistance.

❖As glass reinforcing material in safety helmets, aircrafts battery boxes.

 Advantages of terylene over cotton:
Terylene clothes
are:
i)Strong
ii) do not stretch,

iii) are highly resistant to acids and chemicals,

iv) dry rapidly due to their low moisture absorbing capacity

v) high creases and wrinkle resistant

vi)blend able with cotton, wool, etc., and the blends possess better finish,

crease and wrinkle resistance and enhances the life of cotton or woolens.

vii) Terylene is used for making good insulators, aircraft and automobile

parts, sheets, rods, tubes, switches, gears, etc.

 POLYAMIDES
❖ Polyamides are synthetic polymers, which have recurring amide groups

❖ Nylons, used in mostly making fibres, belong to this class

❖ Nylon-6:6 is obtained by the polymerization of adipic acid with hexamethylene

diamine.
NYLON 66
 Properties of nylons:
❖ Have high impact strength, greater toughness, flexibility and abrasion resistance.

❖ The mechanical properties are considerably affected by the amount of

crystallinity

❖ The principle structure difference between different fibres is the length of the
aliphatic chain separating the amide groups in the polyamide.

❖ Crystallinity readily occurs and gives materials of high melting point and
tensile strength
 Applications
❖ Textile fibres are usually prepared from nylon 66 or nylon 6 because these
polymers have the highest tensile strengths.

❖ Brushes, sports equipment and surgical instruments are normally made of

nylon 6, nylon or nylon 11, which have greater flexibility and water
resistance.

❖ Nylon fibres have satisfactory electrical insulating ability under low

frequencies and dry conditions.

❖ Nylon fibres are soluble in acetic acid, formic acid, and phenols.

❖ The oxidation of nylons occurs in air exposure to UV light and or temperature

above 70ₒC.
 Polyurethanes
❖ Obtained from organic isocyanates (RNCO). When an isocyanate reacts with an
alcohol a urethane is obtained.

❖ Dihydroxy alcohols copolymerize with di-isocyanates, polyurethanes are

produced

❖ Polyurethanes are thermoplastics and used for heat and sound insulation
 Applications of Polyurethane

❖The primary application of polyurethane is in the production of foams.

❖These foams are used in a variety of materials such as upholstery fabrics,

domestic furniture, and refrigerator sheets.

❖Polyurethane is also used in some garments.

❖Polyurethane mouldings are also used in columns and door frames

❖The low-density foams are widely used in mattresses and other forms of
bedding.

❖They are also used in automobile seats and upholstery.

❖Used in the manufacture of partially elastic straps and band

❖Used to make bathroom and kitchen sponges.

❖ Used in seat cushions and couches.
 Rayon
❖ Rayon is prepared from cellulose.
❖ Though cellulose is a natural polymer it needs extensive chemical treatment to

form rayon.

❖ It is also called artificial silk.

❖ It absorbs moisture and is comfortable to wear.
❖ It can be easily dyed in various colors.
Properties of Rayon:

❖Rayon is a versatile fiber and is widely claimed to have the same comfort
properties as natural fibers,

❖It can imitate the feel and texture of silk,

wool, cotton and linen.

❖Rayon fabrics are soft, smooth, cool, comfortable, and highly absorbent
 Blending Fibres
❖ Terylene and cotton blend, known as terrycot is used for making dress materials.

❖ Terylene and wool blend is known as terrywool is used as a substitute for costly
woollen clothes.

❖ Polyester and cotton blend is more crease-resistant.

❖ Acrylic and wool blend trousers are less

 Advantages of Synthetic fibres
❖ Strong
Synthetic fibres are strong so they can take up heavy things easily.

❖ Retain their original shape

Synthetic fibres retain their original shape so it's easy to wash and wear.

❖ Elastic
Can easily be stretched out.

❖ Soft
Synthetic fibres are generally soft so they are used in clothing materials.

❖ Colour
Varieties of colours are available as they are manufactured.
 Disadvantages of Synthetic Fibres
❖ Does not absorb moistures

❖Synthetic fibres do not absorb sweat, trapping heat in ourbody.

❖ Rough feel

❖Synthetic fibres may give rough feel, making it unsuitable for lower and

undergarments etc.

❖ It is dangerous to wear near fire, as they catch fire easily.

❖ They cannot be easily ironed as they melt very easily.
 High performance polymer fibers

Applications:

❖ High performance fibers

❖ Excellent mechanical properties like stiffness, strength and toughness

❖ Light weight

❖ Ultrafine electro spun fibers

❖ Excellent electrical and mechanical properties

❖ Smaller diameters and high surface area

Examples of High performance polymer
fibers
 Kevlar : Example for liquid crystal
polymers
❖ Monomer: 1.4 Dianmino benzenea and Terphthaic acid dichlor

❖ The formation of intermolecular hydrogen bonds and stacking of rings

results in fiber with tensile stiffness (E) of 130-185 GPa and tensile
strength (σ) of 3.4-4.1 Gpa
❖ Mechanism: Condensation polymerisation

1.4 Dianmino benzene Terphthaic acid dichloride kevlar

 Applications of Kevlar
❖Kevlar® and Twaron® are the two leading commercial fibers based on
Poly(p-phenylene terephthamide)PPTA

❖ Kevlar is used in both defense and commercial applications that take advantage
of its excellent mechanical properties and thermal resistance.

❖ Most famous for its high impact resistance,

❖ Kevlar is the fabric of choice for bullet-proof soft body armour.

❖Modern racing cars contain Kevlar-reinforced fuel tanks. The high tensile strength
of Kevlar makes the fuel tanks inherently difficult to puncture in this case of an
accident.

❖Kevlar is used to bring rigidity to parts of the tire. Adding Kevlar to the tire also
makes it more resistant to puncture. This is important for off-road vehicles
travelling over sharp rocks and rough terrain.

However, PPTA fibers are susceptible to humidity and ultraviolet radiation.

 Poly methyl methacrylate (PMMA)
• It is a kind of thermoplastic polymer.
• PMMA is also known as orlon, lucite or plexiglass.
• It is a colourless, transparent in nature.
• It is strong and light weight.
• It has outstanding optical properties.
• Soluble in organic solvents.
• It has high softening point of about 130-140oC but it starts behaving as
rubber-like above 65oC.
 Poly methyl methacrylate (PMMA)
Applications
• It is used as an alternative to glass under the name of plexiglass or lucite.
• Used for making aquarium glasses.
• Used for making hard contact lenses due to its high transparency.
• Used for making emulsions, adhesives, paints etc.
• Used in making acrylic paints
Bakelite (Phenol-formaldehyde Resins)
• It is thermosetting type of plastics (on heating these resins become highly
crosslinked, forming insoluble and infusible solids).
• It is classified under phenolic resins (formed by the condensation of
polymerization of phenol derivatives such as phenol, resorcinol etc. with
aldehydes such as formaldehyde etc.)
• Bakelite is obtained from condensation of phenol and formaldehyde in the
presence of basic catalyst.
 Bakelite (Phenol-formaldehyde Resins)

Properties:
• Phenolic resins are hard, scratch resistant, infusible, water resistant and insoluble
solids.
• Resistant to non-oxidizing acids, many organic solvents but are attacked by alkalis
because of the presence of free hydroxyl group.
• The exhibits electrical insulating character.
Bakelite (Phenol-formaldehyde Resins)
Uses:
• Making electrical insulator devices such as switches, plugs, heater handles
etc.
• For impregnation of wood and fabrics.
• Soft bakelite with low degree of polymerization are used as glue for
binding laminated wooden plates.
 Epoxy Resins
• It is also a thermosetting type of plastics.
• It is prepared from condensation reaction between epichlorohydrin (a
colorless toxic liquid) and bisphenol at 60oC in presence of a basic catalyst.

• The linear epoxy resins are converted into thermosets by reacting many types
of materials such as polyamines, polyamides etc.
• The reaction results into a formation of 3-D cross-linked structure.
Properties:
• The epoxy resin could be in the form of easy flowing liquid (M.Wt. 350) or a
solid (M.wt. 8000)
• Due to very stable ether linkages it is much resistant to chemicals.
• They are tough and heat resistant.
• Polar nature results gives it adhesion quality.

Uses:
• Low M.Wt epoxy resins are used in casting and adhesives and high molecular
wt. epoxy resins are used in surface coatings.
• Used for making moulds to produce electrical equipment.
• Epoxy resins are used applied over cotton, rayon and bleached fabrics to impart
crease resistant.

Epoxy adhesives Floor coatings

 Nano fabrics
Nano fabrics are textiles engineered with small particles that
give ordinary materials advantageous properties such
as superhydrophobicity (extreme water resistance, also see
"Lotus effect"), odor and moisture elimination, increased
elasticity and strength and bacterial resistance.

Depending on the desired property, a nanofabric is either

constructed from nanoscopic fibers called nanofibers, or is
formed by applying a solution containing nanoparticles to a
regular fabric.

Applications of nanofabrics have the potential to revolutionize

textile manufacturing and areas of medicine such as drug
delivery and tissue engineering.
Manufacture
(i) Sol-gel

1.) The sol-gel process is used to create gel-like solutions which can be applied to
textiles as a liquid finish to create nanofabrics with novel properties. The process
begins with dissolving nanoparticles in a liquid solvent (often an alcohol).

2.) Once dissolved, several chemical reactions take place that cause the
nanoparticles to grow and establish a network throughout the liquid. The network
transforms the solution into a colloid (a suspension of solid particles in a liquid) with
a gelatinous texture.

3.) Finally, the colloid must go through a drying process to remove

excess solvent from the mixture before it can be used to treat fabrics.
The sol-gel process is used in a similar fashion to make polymer nanofibers, which
are long, ultra-thin chains of proteins bonded together.
(ii)Electrospinning
1.Electrospinning extracts nanofibers from polymer solutions (synthes
ized by the sol-gel process) and collects them to form nonwoven
nanofabrics. A strong electric field is applied to the solution to charge
the polymer strands.

2.The solution is put into a syringe and aimed at an oppositely

charged collector plate. When the force of attraction between the
polymer nanofibers and the collector plate exceed the surface
tension of the solution, the nanofibers are released from the
solution and deposit onto the collector plate.

3.The deposited fibers form a porous nanofabric that can aid in drug
delivery and tissue engineering depending on the type
of polymer used.
 Ultrafine fibers: nanofibers
Electrospinning: Versatile and efficient method to fabricate 1D nanofibers (ultra
fine fibers having diameter less than 1 μm) derived from metals, metal oxides
and hydrocarbons One has control over the diameter of fibers produced using
the electrospinning method.

❖Nanofibers made from electrospinning method possess unique properties such

as a high surface-area-to-volume and aspect ratio, low density, and high pore
volume.

❖These nanofibers have application in solar cells, fuel cells and

❖hydrogen energy harvesting devices
 Electrospinning: Methodology

•Application of high voltage on

solution

•Formation of pendant drop

and its deformation into
conical droplet

•Ejection of jet of polymer from

the tip of the needle
Set up for producing ultrafine fibers

❑ The interaction between the electric field and the surface tension of
the fluid stretches the jet stream and makes it undergo a whipping
motion leading to the evaporation of the solvent
❑ The jet stream gets elongated as a thin fibers and gets deposited on the
collector
 Advantages of electrospining

❖ Proton exchange mebranes

❖ Nafion: commercially used polymer electrolyte membraneused in

proton exchange membrane(PEM) fuel cells

❖ Nafion nanofiber fabricated using electrospin technology exhibits

superior proton conductivity compared to bulk nafion film
 Applications of Nano fabrics
Swimming Suit:
▪ The most widely recognized application is in the shark-skin suit worn during
world-record breaking Olympic swimming championship.
▪ The suit includes a plasma layer enhanced by nanotechnology to repel water
molecules designed to help the swimmer glide through the water.

Sporting Goods:
▪ Running shoes, tennis racquets, golf balls, skin creams, and a range other
sporting goods have also been enhanced by nanotechnology.
▪ A garment that senses their surroundings and interacts with the wearer is an area
of considerable interest.
▪Such textile-based nano sensors could provide a personalized healthcare system,
monitoring vital signs while running or responding to changes in the weather.
Application in properties of textile
material:
The properties imparted to textiles using nanotechnology
include
1. Water repellence
2. Soil resistance
3. Wrinkle resistance
4. Anti-bacteria
5. Anti-static
6.UV-protection
7.Flame retardation
8.Improvement of dye ability
9. Self-cleaning fabrics

Among them important applications are described shortly.

Water Repellence:
1. ) Nano-Tex improves the water-repellent property of fabric by
creating nano-whiskers, which are hydrocarbons and 1/1000 of the
size of a typical cotton fiber, that are added to the fabric to create a
peach fuzz effect without lowering the strength of cotton.

2.) The spaces between the whiskers on the fabric are smaller than
the typical drop of water, but still larger than water molecules;
water thus remains on the top of the whiskers and above the
surface of the fabric.

3.) However, liquid can still pass through the fabric, if pressure is
applied. The performance is permanent while maintaining breath
ability.
UV Protective Finish:
1.) The most important functions performed by the garment are to
protect the wearer from the weather. However it is also to protect
the wearer from harmful rays of the sun.
2.) The rays in the wavelength region of 150 to 400 nm are known as
ultraviolet radiations.
3.) The UV-blocking property of a fabric is enhanced when a dye,
pigment, or ultraviolet absorber finish is present that absorbs
ultraviolet radiation and blocks its transmission through a fabric to
the skin.
Self-cleaning Fabrics:
1.) A self-cleaning cotton fabric known as nano-care was developed
and is marketed by an American Company, Nanotex and stain-resistant
jeans and khakis are available since 1990.

2.) Nanocare fabrics are created by modifying the cylindrical structure

of the cotton fibres making up the fabric.

3.) At the nano scale, cotton fibres look like tree trunks. Using nano
techniques, these tree trunks are covered in a fuzz of minute whiskers
which creates a cushion of air around the fiber. When water hits the
fabric, it beads on the points of the whiskers, the beads compress the
air in the cavities between the whiskers creating extra buoyancy. In
technical terms, the fabric has been rendered super-non wet able or
super-hydrophobic.
Anti-static Finishes:
1.) Static charge usually builds up in synthetic fibers such as nylon and polyester
because they absorb little water.
2.) Cellulosic fibers have higher moisture content to carry away static charges, so
that no static charge will accumulate.
3.) As synthetic fibers provide poor anti-static properties, research work concerning
the improvement of the anti-static properties of textiles by using nanotechnology
were conducted.
4.) It was determined that nano-sized titanium dioxide, zinc oxide whiskers, nano
antimony-doped tin oxide (ATO) and silane nano sol could impart anti-static
properties to synthetic fibers.
5.) TiO2, ZnO and ATO provide anti-static effects because they are electrically
conductive materials. Such material helps to effectively dissipate the static charge
which is accumulated on the fabric.
6.)On the other hand, silane nano sol improves anti-static properties, as the silane
gel particles on fiber absorb water and moisture in the air by amino and hydroxyl
groups and bound water.
Nano Technology for Wrinkle Free
Treatment:

1.) Nano-Tex has launched a new nanotechnology-based wrinkle-free treatment

that is said to offer an improved performance while preserving fabric strength and
integrity providing an alternative to harsh traditional processes.
2.) Chemicals and processing methods reduce a fabrics tear and tensile strength.
3.) This means there are certain fabrics and garments that are Wrinkle-free textiles
are popular and convenient for time-pressed consumers, but traditional not
candidates for wrinkle-free technology, such as lightweight fabrics or slim fitting
garments.
4.) Sometimes fabrics also need to be over-engineered or beefed up in order to
withstand the fiber degradation caused by traditional wrinkle-free solutions.
5.) Either way, current technologies either do not work on all fabrics or the
brand/retailer has to incur additional expense just to accommodate the destructive
properties of wrinkle-free chemistry.
Anti-bacterial Finishes:
1.) For imparting anti-bacterial properties, nano-sized silver, titanium dioxide and
zinc oxide are used.
2.) Metallic ions and metallic compounds display a certain degree of sterilizing
effect.
3.)It is considered that part of the oxygen in the air or water is turned into active
oxygen by means of catalysis with the metallic ion, thereby dissolving the organic
substance to create a sterilizing effect.
4.) With the use of nano-sized particles, the number of particles per unit area is
increased, and thus anti-bacterial effects can be maximised.