CHEMICAL PROPERTIES – DEGRADATION:

POLYMER ADDITIVES:
Polymers obtained from manufacturing plants after isolation and purification are called virgin
polymers. The bulk properties of virgin polymers can be altered by incorporating additives.
The process of incorporation of additives into virgin polymers to get desired properties is
known as compounding of polymers.

PROCESSING ADDITIVES:
These additives enable easy processing of polymers.
Additive Function Example
Plasticiser Lower the Tg of polymers and make them easily processable. Tricresyl phosphate
They get intercalated between polymer chains and decrease
intermolecular forces and hence lower the Tg of polymers. Dioctyl phthalate

R is octyl group
Thermal Prevent thermal degradation of polymers during processing. Lead soaps, organo
stabilisers For example PVC degrades with the elimination of HCl tin compounds
during moulding, leading to discoloration.
The additives aid in removing the degradation products. Calcium and barium
salts

Lubricants Prevent the fabricated polymer article from sticking to the Waxes, oils, soaps
equipment. They are also called mould release agent. They
also impart a flawless and glossy finish.
Blowing These additives decompose at any stage during the Sodium bicarbonate
agents processing of polymers giving out gases. These gases NaHCO3 gives CO2
evolved cause the formation of pores in the polymers and Azocarbonamide
hence are used in the production of foamed plastics. gives N2, CO2 and
CO
Coloring They give the desired color. Dyes and Pigments.
agents
Antistatic They prevent static charge build up. They are compounds Eg., Long chain
agents containing polar groups. aliphatic amines,
quaternary ammonium
salts.

PROTECTIVE ADDITIVES (ANTIAGING)

  Generally polymer aging or degradation is initiated by the formation free radicals due action
of UV light action of oxygen or ozone, or due to mechanical forces.
 Free radicals can be generated in the polymer itself or any other molecules in the polymer
sample like any impurity present in the polymer.
 Once free radicals are formed they are further attacked by oxygen to form peroxy radicals and
hydroperoxides. The decomposition products of hydroperoxides generate free radicals which
further attack other polymer molecules and degrade them and this process can continue like a
chain reaction.

where P is a polymer chain

 This degradation leads to chain scission in the polymer and reduction in molecular
weight.
 Such degradation lead to loss of mechanical strength in the polymer, discoloration, loss of
transparency, loss in dielectric strength etc.
UV stabilisers or photostabilisers:
Absorb UV light and dissipate the energy as heat. Eg., TiO2 (make the polymer opaque)
Example o-hydroxybenzophenone(suitable for neutral or transparent applications). It undergoes
isomerization by absorbing UV light and dissipates the energy as heat while it goes back to its
original form.

Antioxidants
Kinetic chain-breaking antioxidants (chain terminators, radical scavengers). They have the
capability to scavenge some of even all available low molecular radicals (R•, RO•, ROO•, HO•, etc)
and polymeric radicals (P•, PO•, POO•)
They have reactive OH or NH groups (hindered phenols and secondary aromatic amines). Inhibition
occurs via a transfer of a proton to the free radical species.
Examples:
Hindered phenols

Secondary amines:
The following shows how phenylnaphthylamine help in removing free radical sites on polymer chains
and itself forms resonance stabilized free radical which is not available to further attack other
polymer chains.
Secondary antioxidants
Secondary antioxidants, frequently referred to as hydroperoxide decomposers, act by converting
hydroperoxides into non-radical, non-reactive, and thermally stable products. They are often used in
combination with primary antioxidants to yield synergistic stabilization effects. Hydroperoxide
decomposers prevent the split of hydroperoxides into extremely reactive alkoxy and hydroxy radicals.

Examples: organophosphorous compounds:

Thioethers or dialkylsulfoxides:

FUNCTIONAL ADDITIVES
Impact Modifiers
PVC has been toughened by the addition of small amounts of acrylonitrile rubber (NBR) and other
elastomeric materials. The traditional purpose of impact modifiers is to absorb the impact energy by
inducing plastic deformation before crack initiation and propagation can happen. The general
characteristics of such additives can be summarized as follows:
- Low Tg;
- Effectiveness with minimum amount;
- Optimum particle size and particle size distribution;
- Good adhesion to the thermoplastic matrix.

Examples: Butadiene based graft copolymers, ABS modifiers (acrylonitrile-butadiene-styrene

copolymer) MBS modifiers. The MBS (methacrylate-butadiene-styrene)

Fillers:
They modify the physical and mechanical properties. They increase the strength, weight and volume
of the final polymer products. They reduce the cost of polymer products.
(a) Particulate fillers :
Filler used in the form of particles
Eg., Carbon black added to rubber increases abrasion resistance.
Silica and carborundum impart hardness.
 (b) Fibrous fillers:
Used in the form of fibres and they increase the mechanical strength. They are called
reinforcing fibres
Polymers containing these fibres are called fibre-reinforced plastics
Eg., Glass fibres, aramid fibres, carbon fibres, cotton flock, wood flour.
Cross-linking agents
Used to form cross links between linear molecules to improve strength.
Eg., Vulcanisation of rubber.
Sulphur is used.

Also used to obtain thermosetting polymers.

Amines are used as crosslinking agents to prepare epoxy thermosets.
Flame retardants
Makes the polymer flame resistant.
For flames to propagate it requires fuel, heat and oxygen.

A flame retardant functions in such a way that it cuts of the access for fuel and/or reduces the heat
and/or cuts off the oxygen supply.

Eg., Halogen-based flame retardants(chlorinated or brominated organic compounds).

These compounds decompose to give non-combustiblke gases like HCl or HBr that interfere with free
radicals formed in the combustion reaction.
Phosphorus-based flame retardants These FRs are also known as char formers, because during the
burning process they produce phosphoric acids, that, reacting with the substrate produce a char that
acts as a protection of the substrate itself.
Metal hydrate flame retardants. This class of FRs include typically aluminium trihydrooxide
(Al(OH)3) and magnesium hydroxide (Mg(OH)2). These products provide FR protection by releasing
water upon heat decomposition, impacting the combustion process

Melamine functions in all three ways to stop the polymers from burning.
It decreases the heat by undergoing endothermic decomposition and gives nitrogen gas that cuts off
oxygen supply.
It also forms an intumescent char(a coating) on the surface of the polymer and hence also cuts off the
fuel supply.
Melamine
COMPOSITES
FIBRE-REINFORCED PLASTICS(FRP):

MATRIX MATERIALS:

Comparison between thermoplastic and thermosets as matrix materials

Thermoplastics Thermosetting plastics

They are linear or branched polymers and They are crosslinked polymers and their
hence their composites have the ability to composites have limited ability to undergo
undergo plastic deformation plastic deformation.
They have greater toughness Toughness is lesser
Higher coefficient of thermal expansion Thermal expansion is less
Properties vary with processing conditions Properties can be carefully controlled by the
because crystallinity varies with processing extent of crosslinking by controlling the
conditions. amount of cross-linking agent
Prepreg preparation is difficult. High Prepreg preparation is easier since it is
temperatures or solvents are required to prepared using a partially cured resin
disperse the fibres in the polymer
Manufacturing costs are high Less expensive
Shelf life of thermoplastic prepregs are long Shelf life is of thermoset prepregs are short
and does not require refrigeration for
storage.
FIBRES:

Glass fibres Carbon fibres Kevlar fibres

Obtained by passing molten glass Obtained by heating The polymer is
through small orifices polyacrylonitrile fibres under
tension to high temperatures in
the absence of air.
Graphitisation takes place giving
carbon fibres. They have a
graphitic structure.
The fibre is then obtained by
Easy production process spinning process.

Properties and applications: Properties and Applications: Properties and applications:

1. High tensile strength and high 1. Light weight with high tensile 1. Light weight, High strength
impact resistance – used to make strength and modulus. and modulus – so used to
composites for automotive parts. 2. Good chemical resistance make composites for aircraft,
2. Low modulus when compared 3. Electrical conductivity. helicopter parts like rotor
with carbon fibres and hence is [Link]-flammable and low blades and body.
more flexible. coefficient of thermal 2. Good toughness and hence
3. Good chemical resistance – so expansion. high impact resistance – so
used to make composites for 5. Expensive used to make composites for
chemical storage tanks and Due to High specific strength it light weight armour.
industrial floorings. is used to make composites for 3. Good heat resistance and
4. Low cost helicopter wings and body, abrasion resistance – due to
sports equipments like tennis the high strength and heat
racquets, golf clubs, surgical and abrasion resistance they
implants like hip replacements are used to make composites
for automotive brakes and
clutches
4. Good flame resistance.
Stress-strain graphs of polyethylene, carbon fibre and carbon fibre reinforced polyethylene:

Aspects of carbon fibres that are to be considered in the preparation of composites are;

- Aspect ratio – length to diameter

- Volume fraction of fibres
- Orientation of fibres – unidirectional or random
- Strength and modulus of fibres