Molecular Weight of Polymers

As the chain termination is a random process, all the polymeric chains formed are of different
lengths. Under such a situation, it becomes difficult to express the molecular weight of the
polymer.
Hence, the molecular weight can be expressed as average of the molecular weights contributed
by individual molecules present in the sample.
The molecular weight of a polymer is expressed in two ways.

(i) Number average molecular weight Mn

If n1, n2, n3, … are the numbers of molecules with molecular masses M1, M2, M3, …,
respectively, then the number average molecular weight is
Difference between thermoplastics and thermosets:

Properties of Polymers
The properties of a polymer largely depend on their structural characteristics. Properties like
tensile strength, elasticity, crystallinity, chemical reactivity and electrical properties depend upon
various structural characteristics like chemical composition, sequence of monomer units, spatial
arrangement of side groups, nature of packing, molecular weight, etc.
The various properties of polymers in light of their structural variations are discussed below
Mechanical properties Properties like strength, elasticity and hardness depend on the
crystallinity of the polymer, whereas tensile strength and impact resistance are related to the
molecular weight of the polymer.
(i) Strength Strength of a polymer depends upon the magnitude and distribution of
intermolecular forces of attraction between the polymeric chains. Branched and straight chain
polymers are held together by weak intermolecular forces of attraction. The magnitude of these
forces increases with increase in length of the polymeric chain or the degree of polymerisation.
Higher the degree of polymerisation greater is the strength of
the polymer. Polymers with nearly 150–200 monomeric units show appreciable strength.

Polymers with low molecular weights are soft and gummy. High molecular weight and long
chain polymers are hard, tough and more heat-resistant. Strength of a polymer can be controlled
by making necessary changes in its structure. Polymers with polar groups like carboxyl,
hydroxyl, chlorine, fluorine and nitrile are strong for example, nylon, polyester, etc. Nylon and
terylene are strong due to the presence of hydrogen bonding between the polymeric chains.
Similarly, teflon is the toughest known polymer because the fluorine atom is highly polar. Cross-
linking also enhances the strength of the polymer. For example, natural rubber is soft.

Introduction of sulphur cross-linkages (vulcanisation) greatly improves the strength of natural

rubber.
Shape of a polymer also affects its strength. On comparing PE and PVC it is found that PVC is
tougher. This is because the presence of chloride groups restricts the chain movement and
increases van der Waals forces of attraction. Consequently, the chains cannot slip over each other
and the strength of the polymer increases. Bakelite is a crosslinked polymer. All structural units
are connected by strong covalent forces resulting
in a giant solid three-dimensional molecule. Hence, they are strong and tough as the movement
of chains is totally restricted.

Thermal behavior of polymers

Glass transition temperature (Tg) is defined as the temperature below which an

amorphous polymer (sometimes crystalline polymer) becomes hard, brittle and breaks like glass.
Above this temperature it is soft, flexible and rubbery. The hard and the brittle state is called the
glassy state because random arrangement of polymeric chains is similar to the random molecular
arrangement found in glass. The soft, flexible state is the rubbery or viscoelastic state. On
heating beyond Tg the polymer first changes into soft, flexible rubbery state and then converts
into the highly viscous liquid and starts flowing. This is called as viscofluid state and the
temperature at which this occurs is called the flow temperature Tf.
Importance of Tg
The Tg value gives information whether the polymer could be used as rubber or plastic. The
materials having low Tg are usually sticky in nature.
Hence if the Tg of the material is increased by addition of substance having high Tg values then
the product would not be sticky.
It becomes hard and easy to process for industrial use. In glassy state, the substance is tough and
has good strength.
Glass transition temperature can be used to modify physical properties of solids.
By altering Tg of the polymer or drug they can be maintained in an amorphous solid form at
ambient or body temperature. Improvement in handling characteristics, solubility and
reproducibility in dissolution of solids can be achieved by increasing the Tg of solids.

Degradation of Polymer:
The term ‘degradation’ means reduction in the molecular weight of the polymer. A polymer
suffers degradation or degeneration gradually. Mechanical stress, radiation, oxygen and other
environmental factors are generally responsible for the degradation of a polymer. Polymers also
degrade during fabrication process when they are subjected to high temperatures.

Types of polymer degradation

Polymer degradation is generally of two types.
(i) Chain end degradation In this type, the degradation starts from the chain end releasing the
monomeric units. This phenomenon is the reverse of chain propagation and is also termed as
‘depolymerisation’.

(ii) Random degradation: This type of degradation takes place from any point on the polymeric
chain.

In this type, low molecular weight fragments are formed, but monomeric units are not released.

Factors responsible for degradation:

(a) Thermal degradation: Degradation under the influence of heat is termed as thermal
degradation. Thermal degradation occurs by both chain end degradation, leading to the formation
of monomer units, or by random degradation. Besides the above two types of degradation, non-
chain scisions also occur, which involve the pendant (substituent) groups without affecting the
main chain. For example, PVC degrades at about 200 °C releasing HCl.
As a result of this degradation, the color of PVC changes from white to black.

(b) Degradation by radiation: It is brought about by ultraviolet or visible light. Also called
photodegradation, it is responsible for the yellowing and gradual embrittlement of plastic
material on storage. Ultraviolet or visible light causes 1,1-disubstituted polymers to degrade to
monomers almost exclusively at room temperatures. Polymethylmethacrylate gives a quantitative
yield of the monomer in the presence of ultraviolet rays. Generally, photostabilisers like ‘salol’
are added to protect the polymers from deteriorating in the presence of light.

(c) Oxidative degradation: It leads to the hardening, discoloration and surface changes in the
polymer. Saturated polymers degrade very slowly by oxygen, whereas unsaturated polymers are
easily attacked by oxygen. It is believed that oxidative degradation proceeds by the formation of
hydroperoxide radical, which is mainly responsible for chain incission.
Mechanical degradation: Some polymers degrade under mechanical stress.
Polystyrene dissolved in a solvent when stirred vigorously undergoes molecular degradation or
fragmentation. Similarly, rubber on being subjected to mechanical stress called mastication
undergoes chain scission, leading to the formation of low-molecular-weight fragments. Polymers
also undergo degradation by ultrasonic waves, X-rays, gamma rays, alpha rays, beta rays and
other high-energy radiations.

Polymer Composites
A composite material is a hybrid material formed by the combination of two or more dissimilar
materials to produce a new material, having the advantageous properties of the different
components.
A composite material is better suited for a particular application than either of the original
materials alone.
Modern technologies require materials of unusual combination of properties that cannot be
met by the conventional polymeric materials, alloys, ceramics and cements. These materials can
be combined in composite material to produce unique characteristics such as stiffness, toughness,
high temperature strength. These types of materials find use particularly in aerospace,
underwater and transportation applications. The composite materials comprise of two phases
‘matrix’, which is the continuous phase and the ‘dispersed phase’ or the reinforcing material.
The most common example of a composite material is the fibre-glass reinforced plastic. The
plastic acts as the matrix and fibre glass is the dispersed phase. Plastic alone is relatively weak
and has a low elastic modulus, that is, it bends and stretches easily. The glass fibres provide it
strength and stiffness, and their modulus of elasticity may be 50 times greater than that of plastic
alone. Glass fibres take most of the load when the composite is stressed.

Fibre-reinforced plastic (FRP) They are composites that contain fibre in the dispersed phase.
The design goals of fibre reinforced composites often include high-strength and stiffness on a
weight basis.
Glass-reinforced plastics (GRP) Glass-reinforced plastic is popularly known as ‘fibreglass’. It
is a composite material made of plastic material reinforced by fine glass fibres in the dispersed
phase.
Properties
Dimensional stability Glass fibre exhibits dimensional stability. It does not stretch or shrink on
exposure to extremely high or low temperatures.
Moisture resistance Glass fibres do not absorb moisture.
High strength They have high strength-to-weight ratio. This property makes them useful for
applications in areas where high strength and minimum weight is required.
Fire resistance Being inorganic in nature, glass fibre does not burn or support combustion.
Chemical resistance They are chemically inert. However, they are affected by hydrofluoric
acid, hot phosphoric acids and strong alkaline substances.
Electrical properties They have low dielectric constant. Glass fibres are excellent materials for
electrical insulation.

Uses
The combination of properties such as low moisture absorption, high strength, heat resistance,
chemical inertness and low dielectric constant makes glass fibres ideal polymers for a variety of
end uses. They are mainly used in the aerospace industry for making high-performance aircraft
(gliders), boats, automobiles, hot tubs, water tanks, baths, pipes, etc. They are used for making
mats and fabrics for thermal insulation, electrical insulation, sound insulation, high-strength
fabrics, heatand corrosion-resistant fabrics. They are also used to reinforce various materials like
translucent roofing panels and automobile bodies. GRP pipe systems are used over and under the
ground for firewater system, drinking water system, gas system, waste water or sewage system.
GRPs are also used in construction of buildings and for producing chimneys. GRPs can be used
to construct panels with appropriate insulation, which reduces heat loss.
Owing to their light weight characteristics, they are used for making helmets, sports use articles
like goal tender masks or catches masks. Fibre glass also finds use in the telecommunication
industry.