POLYMERIC MATERIALS

A polymer is a macromolecule having high molecular mass more than 10,000.

Formation of such molecule requires combination of large number of small molecules. Such
small molecules are called monomers and they should possess at least two functional groups
or unsaturated bonds that can combine with similar or different type of simple molecules. The
process involved in combining of monomers to get a polymer is called polymerisation. The
number of times the monomer units repeat in a polymer is called degree of polymerisation.

Eg:
Polymerisation
H2C CH2 H2C CH2
n
Ethylene Polythene

HC CH2 HC CH2
n
Polymerisation

Styrene Polystyrene

Where n is called degree of polymerisation.

Classification of polymers:
Polymers are classified in following ways.

1. Based on method of polymerisation: Addition polymers and Condensation polymers.

2. Based on effect of heat: Thermoplastic and thermosetting polymers

3. Based on the way of repeating units linked: Linear, branched and cross linked polymers.

4. Based on origin: Natural and Synthetic polymers.

5. Based on arrangement of molecules: Crystalline and amorphous polymers.

Methods of Polymerization
To carryout polymerization in a test tube or small flask may be difficult. However, problems
are encountered when the process is scaled up to industrial level (large scale production). The
problems like increase in temperature due to exothermicity of the reaction and very high
increase in viscosity are most common. It is also expected that the products obtained must be
able to serve the purpose (as fibre, adhesive, plastic, foam, and rubber.etc.) without much
purification Manufacturing techniques can be classified into following types based on the
conditions maintained.
1. Bulk Polymerisation

It is the simplest technique. The monomer in liquid form and an initiator soluble in
liquid monomer are taken in a reactor. Which forms a homogeneous system. The reaction is
initiated by heat or photo chemically. As free radical polymerizations are exothermic heating
need not be continued. Instead excess heat liberated has to be taken out. Almost the whole of
the monomer (bulk) gets converted into polymer.

The advantages of this technique are:

(i) Product obtained will be pure as no other substance other than initiator is added.
(ii) Product will have good optical clarity as no impurities exist.
(iii) Percentage conversion is almost hundred
(iv) The method is simple and needs simple equipments.
(v) Polymer recovery is easy

Disadvantages of the process are:

(i) As the polymerization progresses, viscosity of the material increases. This makes it
difficult to stir the product.

(ii) The reactions are exothermic. So lot of heat is generated. Unless heat is removed, there is
a chance of explosion and degradation of polymer.

(iii) Temperature control is difficult due to viscosity increase. Heat cannot be extracted out
easily as stirring becomes difficult. Low thermal conductivity and specific heat of the
polymer add to the problem.

(iv) As the movement of the molecules gets restricted due to viscosity increase, rate of
termination decreases. Growth propagation of large number of chains to the site of monomers
leads to hot spot formation again leading to decomposition of the polymer.

(v) The polymer obtained will not have good molecular weight distribution as chain growth
will not occur uniformly, throughout the bulk.

Polymers like polystyrene, poly (methyl methacrylate), low density polyethylene and many
condensation polymers are prepared by this method.

1. Solution Polymerisation

In this method monomer and initiator are dissolved in a suitable solvent to form a
solution. So it is polymerization in homogeneous condition. The solution is heate to start
polymerization. The solvent selected should have suitable boiling point and chain transfer
characteristics After the reaction is over solvent is removed to get the polymer. Important
organic solvents used are aliphatic and aromatic hydrocarbons, esters, ethers and alcohols.

The advantages of the process are:

(i) Because of the presence of solvent, the viscosity build up is low. This makes
stirring easy and reduces the chances of hot spot formation and explosion.
 (ii) As stirring is easy, heat transfer is effective.
(iii) The paste (of polymer in the solvent) can be directly used as an adhesive and in
paints.

The disadvantages of the process are:

(i) Yields will be less due to the presence of large of the solvent.
(ii) Product will be impure as removal of last traces of solvent is difficult.
(iii) There is a need to recover the solvent. Therefore the technique requires a separate
solvent recovery unit.
(iv) Costly solvent increases the cost of the process.
(v) High molecular weight products cannot be obtained as solvent acts as a chain
transfer agent this increases the possibility of termination.

Polystyrene, polyvinyl chloride (PVC) poly butadiene polyacrylamide etc. are prepared
by this technique.

3. Suspension polymerization (Bead or pearl polymerization)

In this process monomer is suspended in water as droplets (50-200μm or micrometer in
diameter). An initiator soluble in monomer is added. So each of the droplets contains
monomer and the initiator (similar to bulk polymerization). A chain- transfer agent is added
to control the molecular weight of the polymer. The droplets show a tendency to coalesce
(like oil in water). This is prevented by:

(a) Addition of a protective colloid like poly vinyl alcohol And

(b) Constant agitation (stirring) of the mixture.

The mixture is heated to about 600C. The droplets harden as polymerization progresses to
give beads. Each droplet acts as a miniature reactor and polymerises as in bulk
polymerization.

The advantages of the processes are :

(i) Heat transfer is efficient as water having high specific heat forms the continuous
phase.
(ii) Agitation or stirring is easy due to negligible viscosity build up.
(iii) It is economical as solvent (water) cost is low.
(iv) Polymer (which is in the form of beads) can be easily recovered by a simple
filtration and then washing.

The disadvantages of the process are:

(i) Polymer obtained is not pure. It is contaminated by additives like protective

colloids.
(ii) Reactor cost is relatively high.

Polystyrene, polymethyl methacrylate, poly vinyl chloride ,polyacrylonitrile etc. are prepared
by this technique.
3. Emulsion Polymerisation
Dispersion of a liquid in another liquid that are immiscible is called emulsion. In this
process a liquid monomer is emulsified in water and the emulsion is stabilized by adding
soap or detergent (emulsifying agent). A water soluble initiator (in suspension polymerization
initiator is monomer soluble) and a chin transfer agent are added. The monomer droplets are
very much smaller (typically 0.5-10μm in diameter) when compared to suspension
polymerization.

Fig .7.1:

The emulsifying agent also called a surfactant is usually sodium or potassium salt of a
fatty acid. It will have hydrophilic (water liking) and hydrophobic (water heating) ends. The
surfactant molecules arrange around monomer droplets with their hydrophobic end pointing
towards monomer and hydrophilic end towards water as shown in above figure. The left out
surfactant forms micelle.

Micelle provides hydrocarbon environment at the interior. Monomer gets solubilised

in this giving a monomer containing micelle. Generally water soluble initiator like
persulphate, hydrogen peroxide or red-ox initiator is added.

H-O-O-H→ OH (Radical)

S2O8-2+Fe+2→Fe+3+SO42-+SO4

(persulphate) Radical

Appreciable amount of initiator is present at the surface of the micelle. Polymerisation

therefore starts at the surface of the micelle and proceeds inwards. As the monomers inside
the micelle are consumed, more monomer from outside diffuse into it. The micelle swells due
to polymerization and bursts. At the end of polymerization the system contains fine particles
of polymer stabilized by emulsifying agent and dispersed uniformly in aqueous.

GLASS TRANSITION TEMPERATURE (Tg)

In crystalline solids (Eg:KCl) there will be orderly arrangement of particles, where as
amorphous solids particles are arranged randomly. Incase of crystalline solids a definite
quantity of energy is required to separate the particles. Hemce crystalline solids show sharp
melting points. But in case of amorphous solids melting points are not sharp.

Polymers are generally amorphous in nature as the polymer chains are coiled,
interwined and entangled giving a random arrangement. Therefore behaviour of polymers on
heating is different from that of crystalline solids.

A solid polymer will be hard, stiff and glossy as the chains occupy definite positions
in the solid and virtually all the chain movements are frozen. When temperature increases the
localised units (chain segments) within a long chain molecule starts moving. This movement
is called segmental motion. If the temperature increases further the whole chain starts
moving. This type of movement is called molecular motion.

Eg: The entangled noodles whose ends can be moved but not the whole strand, is segmental
motion. Earth worm in a bowl that keeps wagging its head and tail without actually moving,
is segmental motion.

The parts of polymer where the local segments have started moving is like liquid
phase where as the molecule as a whole whose mobility is forbidden is like solid phase. This
state is a combination of solid and liquid state and it is called rubbery state.

The temperature at which a polymer transforms from stiff, hard, glossy state to
rubbery state is called glass transition temperature (Tg). The temperature at which the
polymer melts and starts flowing is called flow temperature. (Tf or Tm).

SIGNIFICANCE OF Tg
i) It is used as a measure for evaluating the flexibility of a polymer and the type of response
the polymeric material would exhibit to mechanical stress.
ii) Tg is very useful in choosing the right processing temperature for fabrication (molding,
calendering and extrusion)
iii) Tg is very useful in determining the coefficient of thermal expansion, heat resistant
refractive index, electrical property etc.

FACTORS AFFECTING GLASS TRANSITION TEMPERATURE:

Any structural features or externally imposed conditions that influence chain mobility
will also affect the value of Tg. Some of these structural factors include chain flexibility;
stiffness, including steric hindrance, polarity, or interchain attractive forces; geometric
factors; copolymerization; molecular weight, branching; cross-linking; and crystallinity.
External variables are plasticization, pressure, and rate of testing.

1. Chain Flexibility: Chain flexibility is determined by the ease with which rotation occurs
about primary valence bonds. If there exists a free rotation along carbon chain of the polymer
the polymer is flexible. Linear polymer chains containing only single bonds have high degree
of freedom for rotation and are more flexible. More the flexibility more will be the segmental
mobility and hence lower will be the Tg.
Eg:

Polymer Tg Remarks

H2C CH2
n -110̊ C Free rotation is possible
Polythene

CH2 CH CH CH2 Contains double bond so

n -85̊ C there will be restricted
Polybutadiene rotation

O Free rotation restricted, not

n
+83̊ C
flexible (Rigid)
Polypheneleneoxide

2. Presence of side groups: (Bulky groups)

Presence of side groups restricts the free rotation or movement of polymer chain the polymer
becomes more rigid and the Tg increases.

Eg:

Polymer Tg Remarks

H2C CH2 No side groups, free rotation is

n -110̊ C
Polythene
possible

HC CH2
n Presence of phenyl groups on the
100̊ C polymer backbone, becomes rigid,
so higher Tg
Polystyrene

HC CH2
n Presence of methyl substituted
phenyl groups on the polymer
170̊ C
backbone, becomes still rigid, so still
CH3
higher Tg
Methyl substituted Polystyrene
3. Inter molecular forces:

Presence of intermolecular forces in the polymer chain due to polar groups, dipoles
etc exerts strong force of attraction like hydrogen bonding with neighbouring chains. This
restricts the segmental mobility and hence increases the Tg.

Eg: Tg of polypropylene is -18̊ C where as taht of nylon-6,6 is 57̊ C. This is because nylon-
6,6 contains polar amide bonds, there will be hydrogen bonding as shown below.
N C (CH2)4 C N (CH2)6 N
H O O H H

O H H O O
C N (CH2)6 N C (CH2)4 C

4. Molecular mass:

Tg increases with increase in the molecular mass up to 20,000. Molecular mass

beyond 20,000 will have negligible effect on Tg. Under high molecular mass, long polymeric
chains coil and entangle with one another. This restricts free mobility of the chains and thus
increases Tg. Under low molecular mass, more number of small chains will have number of
loose ends. This leads to segmental motion at the loose end resulting in lower Tg.

5. Crystallinity:

Close and orderly arrangement of chains leads to crystallinity in a polymer.When

chains are close (as in crystalline solid) intermolecular force of attraction (Vaander Walls
force) will be more. So more energy is required to initiate segmental motion which leads to
high Tg. (Higher crystallinity is expected if the chains are linear without branching).

6. Stereoregularity of the polymer:

Isotactic polymer is more symmetric than syndiotactic, which is more symmetric than
atactic polymer. When the structure is symmetric, chains can come closer which leads to
increase in crystallinity and thereby increasing Tg of the polymer. Thus, Tg of these polymers
is in the order of isotactic˃syndiotactic˃atactic polymer.

Eg: Three different confirmations of PVC are as follows.

Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl

Isotactic PVC Cl Cl Cl Cl
Syndiotactic PVC Atactic PVC
THERMO PLASTIC POLYMERS:

Some polymers soften on heating and can be converted into any shape that they can
retain on cooling. The process of heating, reshaping and retaining the same on cooling can be
repeated several times. Such polymers, that soften on heating and stiffen on cooling, are
termed ‘thermoplastics’. These are the linear or slightly branched long chain molecules
capable of repeatedly softening on heating and hardening on cooling. These polymers possess
intermolecular forces of attraction intermediate between elastomers and fibres. Polyethylene,
PVC, nylon and sealing wax are examples of thermoplastic polymers.

Poly carbonate:
Polycarbonates are the polyesters of unstable carboxylic acids. They contain [-O-CO-
O-] linkage through the chain.

Polycarbonates are prepared by condensation of

(i) Posgene and sodium salt of Bis-phenol-A

(ii) Diphenyl carbonate and Bis-phenol-A

Method(i): From Posgene and sodium salt of Bis-phenol-A

CH3 NaOH CH3

HO C OH NaO C ONa
CH3 CH3
Sodium salt of Bis-Phenol-A
Bis-Phenol-A

CH3 O CH3 O
n NaO C ONa n Cl C Cl O C O C O nNaCl
CH3 Posgene CH3
Sodium salt of Bis-Phenol-A n

Method (ii): From Diphenyl carbonate and Bis-phenol-A

CH3 O
nHO C OH n O C O
CH3
Bis-Phenol-A Diphenyl carbonate

Ester exchange reaction

CH3 O
O C O C O 2n C6H5OH
CH3
n
Properties:

1. It has high tensile strength and impact resistance.

2. It is white transparent thermoplastic polymer.

3. Highly soluble in alkalies and acids

4. Got very high melting point.

Applications:

1. Used in the manufacture of many useful articles such as telephone parts, unbreackable
glazing appliences, etc due to its high tensile strength.

2. Used in the manufacture of safety goggles, automobile lenses, DVD, CD etc due to its
transparent nature.

Acrylonitrile butadiene styrene (ABS):

The monomers used in the synthesis of ABS are, acrylonitrile, butadiene and styrene.
CH CH2

x H2C CH CN y H2C CH CH CH2 z

Acrylonitrile Butadiene Styrene

Polymerisation

CN
H2C CH CH2 CH CH CH2 CH CH2

x y z

Acrylonitryiebutadienestyrene

x,y,z depends on blending percentages of starting materials

Properties:

(i) Very strong having very high impact resistance

(ii) High thermal and chemical resistance.

(iii) Provides glossy surface.

(iv) Got wide range of operating temperature (-40̊ C to +90̊ C).

Applications:
THERMOSETTING POLYMERS:
Some polymers, on the other hand, undergo some chemical change on heating and
convert themselves into an infusible mass. They are like the yolk of egg, which on heating
sets into a mass, and, once set, cannot be reshaped. Such polymers, that become infusible and
insoluble mass on heating, are called ‘thermosetting” polymers. These polymers are cross
linked or heavily branched molecules, which on heating undergo extensive cross linking in
moulds and again become infusible. These cannot be reused. Some common examples are
epoxy resins, bakelite, urea-formaldelyde resins, etc.

Epoxy resins: (Araldite)

These are the polymers contain epoxy group on both the ends. The most common
epoxy resin is obtained by condensation reaction of epichlorohydrin and Bis-phenol-A in the
presence of NaOH as catalyst.
CH3 NaOH CH3
HO C OH NaO C ONa
CH3 CH3
Bis-Phenol-A Sodium salt of Bis-Phenol-A

CH3 O
NaO C ONa H2C C CH2 Cl
CH3 H

O H2 CH3 H2 O
H2C C C O C O C HC CH2
H
CH3

Polymerisation

O H2 CH3 OH
H2C C C O C O CH2 CH CH2
H
CH3
n

Properties:

1. Epoxy resins possess good electrical insulating properties.

2. Epoxy resins are resistant to water, acids, alkalis and various organic solvents.

3. They offer very good wearing and abrasion resistance.

4. The polar nature of the resins makes them excellent adhesives.

5. Cross linked polymers have high toughness and heat resistant properties.

Applications:

1. It is used as an adhesive to bind wood, glass, concrete, ceramic, metallic and leather
materials.

2. Epoxy resins are applied over cotton, rayon and bleached fabrics to impart grease
resistance and shrinkage control.

3. Used in manufacture of skid resistant industrial floorings and highway surfacing.

4. Used as laminating materials for electrical equipments.

5. Moulds which are made from epoxy resins are used in the production of aircraft and
automobile components.

Note: Curing of epoxy resins

Epoxy resins are converted in to three dimensional cross linked polymers by reaction with
curing agents such as polyamides, polyamines, dicarboxylic acids, acid anhydrides, etc. The
process is called curing of epoxy resins. On curing epoxy resins show outstanding properties
of toughfness, chemical inertness, flexibility and strong adhesion.

Phenol Formaldehyde resins:

Phenol-Formaldehede (PF) resins are formed by the poly condensation between
phenol and formaldehyde. The polycondensation reaction can be catalysed either acids or
bases.

Synthesis:

Aqueous solution of formaldehyde with phenol is heated to 70-75 C. The monomers

like monomethylol phenol, dimethylol phenol, trimethylol phenol are formed. These
monomers condense to give a polymer. The nature of the reaction depends on the ratio of
phenol to formaldehyde in the solution.

Phenol reacts with formaldehyde forms methylol phenols as below.

OH OH OH OH
CH2OH HOH2C CH2OH HOH2C CH2OH
HCHO

CH2OH
Mono Di Tri
The type of methylol phenol formed will depend on the ratio of phenol to formaldehyde in
solution.

Case (i) If the phenol to formaldehyde ratio is is greater than one (P/F˃1), the monomethylol
phenol is expected in higher percentage. This monomethylol phenol undergoes
polymerisation in presence of acidic catalyst forms a polymer called Novolac.
OH OH OH H OH
2
CH2OH HOH2C C
H+

n
Novolac

Case (ii) If the phenol to formaldehyde ratio is less than one (P/F<1), the di and trimethylol
phenol are expected in higher percentage. This di and trimethylol phenols undergo
polymerisation in presence of base catalyst forms a polymer called Resol.

OH OH OH H H2 OH
2
HOH2C CH2OH HOH2C CH2OH OH- H2C C O C CH2

n
Resol

Novolac or resol undergo curing when mixed with hexamine (Hexamethylene

tetramine). Hexamine helps in the cross linking of the chains. The highly cross linked product
is called Bakelite.

OH H OH OH OH
2 H2 H2
C H2C C O C CH2

H2C H2C H2C H2C

C H2C C O C CH2
H2 H2 H2
OH OH OH OH

Bakelite from Novolac Bakelite from Resol

Note:

1. Novolac or resol resins when mixed with drying oil are used as varnishes.

2. Both novolac and resol are linear polymers therefore thermoplastic in nature.

3. Resol is characterised by ether linkage where as novolac is characterised by methylene

linkage.
4. The curing agent, hexamine acts as a source of formaldehyde when it reacts with water.

Properties of phenol-Formaldehyde resins:

1. Bakelite is resistant to water, acids, and organic solvents.

2. Due to the presence of phenolic –OH group it is attacked by alkalies.

3. Good electrical insulator and got excellent adhesive properties.

4. Rigid, hard and scratch resistant thermosetting polymer.

Applications:

1. Used in the manufacture of heater handles, TV and radio cabinets, because of it high
temperature resistance.

2. As Bakelite is good insulator, it is used for making electric insulator parts liks switches,
plugs, and switch boards.

3. For making brake linings, abrasive wheels and sand papers.

4. To seal electrical bulbs to their caps.

5. For making decorative laminates and wall papers.

6. In the production of ion exchange resins used in the purification of water.

BIODEGRADABLE POLYMERS:
It is observed that plastic bucket kept in sunlight and rain for long time loses its lustre
and strength. This deterioration in properties is due to a phenomenon called ‘polymer
degradation’, which is characterised by an uncontrolled change in the molecular weight or
constitution of the polymer. Conventionally, the degradation is a reduction in the molecular
weight of the polymer.

In developing countries, environmental pollution by synthetic polymers has assumed

dangerous proportions. Petroleum-derived plastics are not readily biodegradable and because
of their resistance to microbial degradation, they accumulate in the environment. In addition
in recent times oil prices have increased markedly. These facts have helped to stimulate
interest in biodegradable polymers. Biodegradable plastics and polymers were first
introduced in 1980s. Polymers from renewable resources have attracted an increasing amount
of attention over the last two decades, predominantly due to two major reasons: firstly
environmental concerns, and secondly the realization that our petroleum resources are finite.
There are many sources of biodegradable plastics, from synthetic to natural polymers. Natural
polymers are available in large quantities from renewable sources, while synthetic polymers
are produced from non-renewable petroleum resources. Biodegradation of polymeric
biomaterials involves cleavage of hydrolytically or enzymatically sensitive bonds in the
polymer leading to polymer erosion. A vast number of biodegradable polymers have been
synthesized recently and some microorganisms and enzymes capable of degrading them have
been identified.

“Thus the biodegradable polymers are the polymers which will degrade by the action
of naturally occurring microorganisms like bacteria, fungi or sunlight”.

Requirements of Biodegradable polymers:

1. Biodegradable polymers should have hydrolysable linkages like esters, amides or ether.

2. They should be hygroscopic in nature.

3. The product formed after degradation should act as compost.

Classification of biodegradable polymers:

The biodegradable polymers can be classified according to their chemical composition, origin
and synthesis method, processing method, economic importance, application, etc.

Poly Lactic acid (PLA):

The basic building block of PLA is the lactic acid (LA). It is a simple chiral molecule
which exists as two enantiomers, L- and D-lactic acid, optically active. It is can be produced
by fermentative or chemical synthesis. Today the most popular route is fermentation, in
which sugars and starches are converted into lactic acid by bacterial fermentation using an
optimized strain of Lactobacillus.

Properties: The PLA is a semi-crystalline polymer with glass transition temperature around
55 to 59°C and melting point 174-184 ° C. It shows a good mechanical strength, high
Young's modulus, thermal plasticity and has good processability. It is unstable in wet
conditions, which can undergo chain disruption in the human body and degrades into
nontoxic by products, lactic acid, carbon dioxide and water which are subsequently
eliminated through the Krebs cycle and in the urine.

Synthesis of Poly Lactic Acid:

There are two important methods for PLA synthesis:

(i) Direct polycondensation of lactic acid and

(ii) Ring opening polymerization of lactic acid cyclic dimmer, known as lactide.

Following reactions show the reaction mechanism for both of them.

CH3 O CH3 Chain coupling CH3 O CH3

O OH agents O OH
HO O HO O
O CH3 O O CH3 O
n n
Low molecular wt polymer Low molecular wt PLA
Mol Wt-2000-10,000 Mol Wt more than10,000
CH3
OH
HO Ring Opening
O Polymerisation
LA

CH3 O CH3 O O CH3

O OH Depolymerisation
HO O
H3C O O
O CH3 O
n
Lactide
Low molecular wt polymer
Mol Wt-2000-5,000

In direct condensation, solvent is used and higher reaction times are required. The
resulting polymer is a material of low to intermediate molecular weight.

Ring-opening polymerization (ROP) of the lactide needs catalyst (Stannous octoate

(Sn(Oct)2)) but results in PLA with controlled molecular weight. Depending on monomer
used and controlling reactions conditions, it is possible to control the ratio and sequence of
Dand L-lactic acid units in the final polymer.

Poly caprolactam: (Nylon-6):

The monomer used in the synthesis of polycaprolactam is caprolactam, a seven
membered cyclic amide.
Properties:
Polycaprolactam (Nylon 6) fibres are tough, possessing high tensile strength, as well
as elasticity and lustre. They are wrinkle proof and highly resistant to abrasion and chemicals
such as acids and alkalis. The fibres can absorb up to 2.4% of water, although this lowers
tensile strength. The glass transition temperature of Nylon 6 is 47 °C.

As a synthetic fiber, Nylon 6 is generally white but can be dyed to in a solution bath
prior to production for different color results. Its tenacity is between 6 and 8.5 gm/den with a
density of 1.14 gm/cc. Its melting point is at 215°C and can protect heat up to 150°C on
average.

Synthesis of Poly caprolactam:

The starting material used for the synthesis is caprolactam  Caprolactam has 6 carbons, hence
'Nylon 6'. When caprolactam is heated at about 533 K in an inert atmosphere of nitrogen for
about 4-5 hours, the ring breaks and undergoes polymerization.
H O O
N 553K, N2 H
N
n N
H
O

Applications of biodegradable polymers:

 Polycaprolactum can be used as micropsheres for drug delivery systems.

 Polycaprolactum can be used as medical implants.
 Ultrahigh-strength PLA are used to make bone nails and screws
 PLA are used in Fracture fixation and Ligament augmentation

Medical Applications
 Wound management
 Sutures
 Staples
 Clips
 Adhesives
 Surgical meshes

 Orthopedic devices
 Pins
 Rods
 Screws
 Tacks
 Ligaments
CONDUCTING POLYMERS

Polymers who conductivity is comparable to that of metals are called conducting polymers.
Requirements for conducting polymers
1. Linear structure with rigid chains
2. Extensive conjugation in polymeric backbone
These materials in pure form are not conducting but on doping their dconductivity increases
enormously
Examples:
1. Polyacetylene
2. Polypyrrole
3. Polyaniline
On doping (p-type- Removing electrons from valence band) or n-type (adding electrons to
conduction band) generates charge carriers (positive charges or holes & electrons) which move in
electric field.

POLY ANILINE

It is the oldest conducting polymer known. It has conjugated p-bond system due to carbon p
orbitals. Nitrogen p orbitals are also a part of conjugated system. The electrons can be easily
delocalized making the polymer conductive
It is prepared by redox polymerization of aniline using APS ( Ammonium Peroxydisulfate)
NH4S2O8 as oxidant. Distilled aniline(0.2M) is dissolved in 300cm3 of 1M Hcl. APS
(0.5M) is dissolved in 200ml Hcl (1M)and added to the aniline solution maintaining the
temoerature 0-5 oC.
It results in formation of dark green precipitate which is polyaniline Emeraldine salt
Only the emeraldine salt is conducting in nature. It can be converted into emaraldine base
(violet) by treatment with ammonia solution.

Synthesis of polyaniline:
NH2
(NH4)2S2O8 / HCl H H
N N
0-5C
n
Leucoemaraldine
(non Conducting form)

N N N N

n
Emaraldine form
conducting form
POLYPYRROLE

Poly-pyrrole films are formed by casting a pyrrole derivative in an organic solvent on an

air-water interface where the water sub phase contains an oxidant (FeCl3). Free pyrrole as
the vapor is added to cause polymerization. They are excellent conductors.

PPy can be prepared by oxidation of pyrrole, which can be achieved using ferric chloride in
methanol:
n C4H4NH + 2 FeCl3 → (C4H2NH)n + 2 FeCl2 + 2 HCl
Polymerization is thought to occur via the formation of the pi-radical cation C4H4NH+. This
electrophile attacks the C-2 carbon of an unoxidized molecule of pyrrole to give a dimeric
cation (C4H4NH)2]++. The process repeats itself many times.
Conductive forms of PPy are prepared by oxidation ("p-doping") of the polymer:
(C4H2NH)n + x FeCl3 → (C4H2NH)nClx + x FeCl2

The polymer’s conductivity can be varied over several orders of magnitude, covering a range that is
suitable for microwave absorption
Polypyrrole (PPy) can be formed chemically or electrochemically through oxidative polymerization of
pyrrole monomer,
Oxidative polymerisation of pyrrole to polypyrrole proceeds via a one electron oxidation of pyrrole to
a radical cation, which subsequently couples with another radical cation to form the 2,2’-bipyrrole.
This process is then repeated to form longer chains.
The final form of polypyrrole is that of a long conjugated backbone as shown below. The polymer has
resonance structures that resemble the aromatic or quinoid forms. In this neutral state the polymer is
not conducting and only becomes conducting when it is oxidized. The charge associated with the
oxidized state is typically delocalised over several pyrrole units and can form a radical cation
(polaron) or a dication (bipolaron). The physical form of polypyrrole is usually an intractable powder
resulting from chemical polymerization and an insoluble film resulting from electropolymerization.

Bipolaron
Chemical structures of polypyrrole in neutral aromatic and quinoid forms and in
oxidized polaron and bipolaron forms
Use of Conducting Polymers in

1. Energy Harvesting

 Polypyrrole can be used as catalyst support for fuel cells and to sensitize cathode
electrocatalysts.
 Inexpensive microporous polyaniline (PANI) is used as a substitute for platinum to
construct the counter electrode in dye-sensitized solar cells (DSSCs).
 Nano Polypyrrole incorporated graphene oxide can be used as an efficient counter
electrode for platinum-free dye-sensitized solar cells.
 Biocompatible polypyrrole cathode (PPyDS) and a Mg alloy anode in Mg/air battery.
These batteries are sufficient to drive some implantable devices requiring low power
densities such as a pacemaker or biomonitoring systems.

2. Sensing applications

 Polypyrrole nanowire doped FeCl3, assessed for chemical sensing application,

specifically pH monitoring.
 Bovine serum albumin (BSA), a protein incorporated polypyrrole film can be used
for detection of Urea.
 Single Polypyrrole nanowires-based sensors showed good limit of detection and
sensitivity and excellent selectivity for gaseous ammonia.
 Polyaniline can be used in conductometric sensors.
 PANI/CuCl2 as a hydrogen sulphide sensor
 PANI nanofiber reinforced nanocomposite crystal microbalance sensor as HCl sensor

3. Defence applications

 Conducting PANI and Polypyrrole can be used in Radar Absorbing materials

Materials that absorb incident electromagnetic energy and convert that energy
to other forms—typically heat.
  Conducting polymers, such as polypyrrole (PPY), polyaniline (PAni), and
polyethylenedioxythiophene (PEDOT) have been deposited onto various textiles in
the forms of woven fabrics, knit fabrics, felts, other nonwoven structures, and fibers.
Potential property of any conductive fabric is its ability to shield against
electromagnetic radiation.
 Conformable Polypyrrole Antennae for soldiers.

Photo conducting polymers:

Photo conductive polymers conduct electricity only in the presence of light. They

are insulators or partially conductive in darkness. This property of photoconductivity
is due to the ability to create free charge carriers(electron holes) by absorption of
radiation and subsequent transport of these carriers to the electrode.  The compound
is used in the photoreceptors of photocopiers.

Eg: Polyvinyl Carbazole

Synthesis of Polyvinyl Carbazole

Benzoyl Peroxide

Vinyl Carbazole Polyvinyl Carbazole

In dark it behaves as an insulator but on exposure to UV radiations, it becomes

conductive. Photoconductive response to visible & IR region can be extended by
incorporating sensitising dyes or electron acceptors.

Applications of photo-conducting polymers in printing.

Laser printing

A laser beam (typically, an aluminium gallium arsenide (AlGaAs) semiconductor laser)

projects an image of the page to be printed onto an electrically charged, selenium-coated,
rotating, cylindrical drum (Drum- Organic photoconductor made of  polyvinylcarbazole).
Photoconductivity allows the charged electrons to fall away from the areas exposed to light.
Powdered ink (toner) particles are then electrostatically attracted to the charged areas of the
drum that have not been laser-beamed. The drum then transfers the image onto paper (which
is passed through the machine) by direct contact. Finally the paper is passed onto a finisher,
which uses intense heat to instantly fuse the toner/image onto the paper.

Synthetic Fibres: Synthesis of carbon fibre from PAN, applications of carbon fibre in
polymer composites.

SYNTHETIC FIBRES
CARBON FIBERS
Carbon fibers are novel high-performance materials. They could be described as fibers
containing at least 90 % carbon obtained by the controlled pyrolysis of appropriate fibers.
Carbon atoms are bonded together in a crystal that are aligned parallel to the axis of fibre..
This alignment gives fibre high strength to volume ratio.Several thousand carbon fibres are
bundled together which are then woven into fabric.
Edison in 1879 found that carbon fibers can be used as carbon filaments in electric lamps.
Since the early work of Edison, the carbon fibers have been investigated and used intensively
because they generally have excellent tensile properties, low densities, high thermal and
chemical stabilities in the absence of oxidizing agents, good thermal and electrical
conductivities, and excellent creep resistance.
In recent years, the carbon fiber industry has been growing steadily to meet the demands
arising from different applications such as aerospace (aircraft and space systems), military,
turbine blades, construction, lightweight cylinders and pressure vessels, medical, automobile,
and sporting goods. Furthermore, in the case of the carbon fibers, the range of their
applications would depend on the type of precursors used to produce the carbon fibers.
Consequently, many types of precursors have been studied to produce the carbon fibers.
Carbon fibre from Poly Acrylo Nitrile (PAN)
PAN-based polymers are the optimum precursors for the carbon fibers owing to a
combination of tensile and compressive properties as well as the carbon yield. The PAN-
based fibers were first developed by Dupont in the 1940s for use in the textile fiber. The

PAN
thermal stability of PAN-based fibers was an important factor in expanding the application of
fibers.

Synthesis

Step-1 Oxidative stabilization- Stretching & Oxidation

Thermoplastic PAN 2000C-3000C Non plastic PAN

Non Cyclic Cyclic

Step-II- Carbonization

Inert Atmosphere
Nonplastic PAN PAN ( 50%) + Volatiles
0 0
400 C-600 C

Step-III-Graphatization ( -N2)

The fibres are treated at temperature between 6000C- 13000C to improve order and
orientation of crystallites in direction of fibre axis.
Properties of Carbon fibre

 Carbon fibre has tensile strength 3 times greater than steel & 4.5 times lighter.

 Exceptional Impact properties- Good energy dissipation mechanism

 Low coefficient of thermal expansion compared to metals

 Better corrosion resistance

 High chemical inertness

Application of carbon fibres in composites

Applications in Sports:

 Ice Hockey Sticks

 rack Spikes
 Bicycle Frames
 Helmets
 Motor Racing
 Tennis Rackets
 Golf Clubs
 Cricket Bats
 Gliders
 Surfboards
 Rowing Shells
Application in the Automotive Industry:

 Racing car chassis

 Hoods
 Car emblems
 Mufflers
  Interior panels of a car
 Steering wheels
Application in Civil Engineering

 Carbon Fiber Reinforced Polymer is can be applied to reinforce concrete structures

 The high strength of carbon fiber enables it to be used as a prestresser
 High corrosion resistance allows for use in offshore environments
 Used in PCCP (Prestressed Concrete Cylinder Pipe ) lines to reinforce the pipes
Applications in Aerospace Engineering

 Aircraft: main wings, Tail units, Rudders, Elevators, Floor panel, Beams, Lavatory
units, Seats
 Rockets: Nozzle cones, Motor cases
 Satellites: Antennas, Solar battery panels