Unit Polymesr Nad Elastomers

Q.1. What is Glass transition temperature? Mention the factors

which affecting the Tg of a polymer 6 Marks
When an amorphous polymer is heated, it gets converted from hard brittle state
(glassy state) to a soft flexible state (rubbery state). The temperature at which a polymer
transforms from a hard glassy state to soft rubbery state is called glass transition temperature.
Glass State viscoelastic state Viscofluid state
(Hard & brittle) (Rubbery) (Polymer melt)
Tg Tm
Significance of Tg :
It is used as a measure for evaluating the flexibility of a polymer and the type of
response the polymeric material would exhibit to
Tg is very useful in choosing the right processing temperature for fabrication
(moulding, calendaring and extrusion )
Tg is very useful in determining the coefficient of thermal expansion, heat resistant,
refractive index, electrical property, etc.,

Factors affecting glass transition temperature

1. Chain Flexibility: Linear polymer chains have high degree of freedom for rotation ie.,
more chain flexibility and low Tg.
Aromatic or cyclic groups on the back bone of carbon atoms hinder the freedom of rotation
ie., chain flexibility decreases and causes an increase in Tg.

2. Cross-linking and branching: A small amount of branching will tend to lower Tg and a
high density of branching reduces chain mobility and elevates the Tg.

The cross linking brings the polymer chain closer, lowers free volume and restricts
molecular motion and hence rises Tg.
3. Intermolecular forces: The presence of large number of polar groups in the molecules
lead to strong intermolecular cohesive forces which restrict the segmental motion. As a result
Tg increases.
4. Molecular mass: Higher the molecular mass more is the restriction in the molecular
freedom. However, Tg is not significantly affected by molecular masses if the degree of
polymerization is above 25o;
5. Presence of plasticizers: Addition of plasticizers reduces the Tg vale; for example,
addition of di-isooctyl phthalate to pvc reduces its Tg from
o
80 C to below room temperature.
5. Stereo regularity of the polymer: A syndiotactic polymer has a higher Tg than atactic
polymer, which in turn has higher Tg than its isotactic stereoisomer.

Q.2.Explain compounding of resin. 6 Marks

The process of mechanical mixing of various additives to resins and converting resins in to
plastics is called as compounding of resin. The important additives used in compounding are
as follows
i) Fillers
ii) Plasticizers
iii) Stabilizers
iv) Colorants

i) Fillers: These are organic or inorganic compounds added during compounding to increase
the bulk of the polymer. The fillers also enhance the tensile strength, impact resistance and
abrasion resistance.
Ex: Wood, mica, clay, silica, talk, fabric scraps, glass fibers, carbon

ii) Plasticizers
Plasticizers are the substances, which are added during compounding to increase the
plasticity of a polymer. These decrease the Tg and helps in converting a hard, brittle polymer
into a soft, flexible polymer.
Ex: Tricrysyl phosphate, Tri phenyl phosphate, dioctyl phthalate, fatty acids etc,

iii) Stabilizers
Polymers have tendency to undergo degradation by air and light. The Stabilizers are added to
minimize the degradation of polymers.
Ex: Phenyl salicylate, aryl and alkyl phosphates, tri phenyl phosphates.

iv) Colorants
These are added to impart required color to the polymer. These increases the attractive and
decorativeness of a polymer. The colorants include organic and inorganic pigments.

Ex: Titanium oxide, lead chromate, BaSo4, carbon black, azo dyes etc,

Q.3.Give the manufacture and applications of Poly methyl

methacrylate PMMA (Plexi Glass) 4 Marks

Plexi glass is the trade name of polymethyl methacrylate. The monomers used for the
preparation of plexi glass are methyl methacrylate. Plexi glass is prepared by emulsion
polymerization method at 60 to 70c in presence of trace of H 2O2 or Acetyl peroxide as
initiator.

Properties:
i. Plexi glass is a white transparent thermoplastic
ii. It has got high optical clarity
iii. It is resistant to chemical action
Applications
i. It is used in the preparation of aircraft windows.
ii. Attractive sign boards.
iii. Manufacturing of transparent moulded articles & tubes.
iv. Lenses for automobiles, artificial eyes etc.,

Q.4.Give the manufacture and applications of Polyurethanes.

4 Marks
Ployurethanes are produced by the polymerization of disocyanate and diol or triol
(or the addition reaction between 2, 4-tolylene diisocyanate with glycol). In the production
of polyurethanes foams, glycol, toylene diisocyanate, catalyst tertiary amines), water and
surfactants are mixed together and heated.

Properties:
i. These can be obtained in the form of foams, fibers, Elastomers, Coatings etc.

ii. The foams are available in both rigid & flexible forms.
Uses:
i. Flexible foams are used for cushions in automobiles & furniture.
ii. Rigid foams are used to reinforce hallow structural units.
iii. Fibers of Polyurethanes are used in lightweight garments and swim suits because of
their stretching property.
iv. These are used to coat gymnasium floor and dance floor.
v. These are used in tyre treads and industrial wheels.

Q.5.Give the manufacture and applications of Phenol Formaldehyde Resins.

6 Marks
Phenol formaldehyde resins are prepared from condensation reaction between phenol
& formaldehyde. Commercially these are available into two forms nova lacks & resols..

i) Nova lacks.

These are phenol formaldehyde resins obtained by condensation of phenol &

formaldehyde in presence of acid as catalyst when phenol to formaldehyde ratio is greater
than one

Properties:
i. Nova lacks are linear polymers.
ii. These have got good electric insulating property
Uses:
i. Used for sealing metal holders to the glass bulbs.
ii. Bounding sheets of paper, wood, card boards etc.,
ii Resol Resins.
 These are phenol formaldehyde resins obtained by the condensation of phenol &
formaldehyde. In presence of alkali as catalyst when phenol to formaldehyde ratio is less than
one.

Properties.
i. These are cross linked polymers
ii. These are non conductor of electricity
iii. Resols can be converted into bakelite by adding additives such as wood,
dies etc.,
Q.6.Mention the advantages of Synthetic Rubbers over natural rubber. 5 Marks

i. These are more resistance to heat & cold ( nitrile rubber)

ii. These are not easily attacked by sunlight & air ( neoprene and nitrile rubber)

iii. These have high abrasion and high tensile strength.

0 0
iv. Rubber property is retained at high temperatures (ex: silicon rubbers-90 - 316 c)
v. Do not age easily (ex; Polyurethane rubber)
vi. Do not swell and can hold organic solvent better than natural rubber (ex; polysulphide
rubber)
vii. Hold more air and water at high pressures (ex; butyl rubber)

viii.
ix.
x. What is Vulcanization of rubber
xi. Vulcanization or vulcanisation is a chemical process for converting rubber or related
polymers into more durable materials via the addition of sulfur or other equivalent
"curatives". These additives modify the polymer by forming crosslinks (bridges)
[1]
between individual polymer chains. The vulcanized material is less sticky and has
superior mechanical properties

Q.7.Give the manufacture and applications of Butyl rubber.

4 Marks
Butyl rubber is prepared by copolymerization of isoprene (2-methyl 1,3 – Butadiene)
0
Isobutylene by emulsion polymerization method at 90 C.

Uses.
i. Butyl rubber is widely used for preparation of inner tubes for tiers.

ii.It is also used for insulating high voltage wires & cables.
Silicone rubber:
Synthesis: Silicone rubber is a rubber-like material composed of silicone
— itself a polymer — containing silicon together with carbon, hydrogen, and oxygen. During
manufacture heat is required to vulcanize (set or cure) the silicone into its rubber-like form.
This is normally carried out in a two stage process at the point of manufacture into the
desired shape, and then in a prolonged post-cure process. It can also be injection molded.

Properties: Silicone rubber is generally non-reactive, stable, and resistant to extreme

environments and temperatures from -55°C to +300°C while still maintaining its useful
properties. Due to these properties and its ease of manufacturing and shaping, silicone rubber
can be found in a wide variety of products, including: automotive applications; cooking,
baking, and food storage products
Q.8.What are Conducting polymers? Give examples 2 Marks
These are the organic polymers having the conductivity band similar to that of
conductors with highly delocalized Pi electron system.
Ex: Polyaniline, Polypyrole, Polythiopene, Polyacetylene, etc Conducting polymers
are obtained by doping an oxidizing or
reducing agent into organic polymers. With the carbon backbone consisting of alternate
double bond & single bonds doping results in delocalization of electrons responsible for
conduction.

Q.9.Explain the mechanism of conduction in Poly acetylene.

6 Marks
The electron is removed from the top of the valence band of Polyacetylene creating a
vacancy or hole. The Polyacetylene molecule, now positively charged, is called a radical
cation, or polaron. The lone electron of the double bond, from which can electron was
removed, can move easily. Therefore, the electron successively moves along the polymer
chain.This are called delocalization of electrons. The positive charge, on the other hand, is
fixed by electrostatic attraction to the iodide ion; when I 2 added as dopant which does not
move so readily. If
Polyacetylene is heavily doped (heavily oxidized), polarons form pairs called Solitons.

The Solitons are delocalized over 12 carbon atoms. Due to the formation of Solitons,
a new localized electronic state appears in the middle of the energy gap. When doping is
high, several charged solution band. This band can later merge with edges of valence &
conduction bands thus exhibiting conductivity.

Q.10 Mention the structure & applications of conducting poly Aniline

 4 Marks

i) Used as conducting tracks on PCB’s (Printed Circuit Boards)

ii) Used as electrode materials for rechargeable batteries
iii) Used in humidity sensors.
iv) Used in electrochemical transducers.
v) Used in biosensors.
vi) Used in artificial nerves and optical computers etc.
vii) Used in smart windows which absorb sunlight.

Q.11.Explain the mechanism of conduction in Poly aniline 6 Marks

Partial oxidation Ammoniumperoxy

di sulphate (NH2 S2 O8)

Base form of
poly- aniline

Protonation
Aq. HCl ( 1 M)

Protonic acid doping:

The synthesis of conducting polyaniline is a typical example of this type of doping
technique. In this technique current carrying charged species (-/+) are created by the
protonation of imine nitrogen.
Polyaniline is partially oxidized, first using a suitable oxidizing agent into a base form
of aniline which contains alternating reduced and oxidized forms of aniline polymer
backbone. This base form of aniline when treated with aqueous HCl (1M) undergoes
protonation of imine nitrogen atom, creating current carrying charged sites (+ve) in the
-
polymer backbone. These charges are compensated by anions (Cl ) of the doping agent,
giving the corresponding salt.
 This type of protonic acid doping of polyaniline results in an increase of conductivity
by approximately 09-10 orders of magnitude.

Applications:
Conducting polymers are highly promising materials to be used in electric and electronic
applications, some of the applications are.
1) As electrode material for commercial rechargeable batteries, for higher power to weight
ratio (coin type of batteries)
2) As conductive tracks of on printed circuit boards