POLYMERS

1. POLYMERS

1.1 GENERAL INTRODUCTION AND ITS SCOPE

Polymers form a very important class of materials without which the life seems very difficult. They are all
around us in everyday use; in rubber, in plastic, in resins, and in adhesives and adhesives tapes. The word
polymer is derived from Greek words, “poly” (many) and “mers” (parts) or units of high molecular mass each
molecule of which consist of a very large number of single structural units joined together in a regular manner.
In other words polymers are giant molecules of high molecular weight, called macromolecules, which are build
up by linking together of a large number of small molecules, called monomers. The reaction by which the
monomers combine to form polymer is known as polymerization. The polymerization is a chemical reaction in
which two or more substances combine together with or without evolution of anything like water, heat or any
other solvents to form a molecule of high molecular weight. The product is called polymer and the starting
material is called monomer.

1.2 HISTORICAL DEVELOPMENT OF POLYMERS

Polymers have existed in natural form since life began and those such as DNA, RNA, proteins and
polysaccharides play crucial roles in plant and animal life. From the earliest times, man has exploited naturally-
occurring polymers as materials for providing clothing, decoration, shelter, tools, weapons, writing materials
and other requirements. However, the origin of today’s polymer industry is commonly accepted as being the
nineteenth century when important discoveries were made concerning the modification of certain natural
polymers. In eighteenth century, Thomas Hancock gave an idea of modification of natural rubber through
blending with ceatrain additives. Later on, Charles Goodyear improved the properties of natural rubber through
vulcanization process with sulfur. The Bakelite was the first synthetic polymer produced in 1909 and was soon
followed by the synthetic fiber, rayon, which was developed in 1911. The systematic study of polymer science
started only about a century back with the pioneering work of Herman Staudinger. Staudinger has given a new
definition of polymer. He in1919 first published this concept that high molecular mass compounds were
composed of long covalently bonded molecules.

1.3 CLASSIFICATION OF POLYMERS

Polymer is a generic name given to a vast number of materials of high molecular weight. These materials exist
in countless form and numbers because of very large number and type of atoms present in their molecule.
Polymer can have different chemical structure, physical properties, mechanical behavior, thermal
characteristics, etc., and on the basis of these properties polymer can be classified in different ways, which are
summarized in Table 1.1, whereas, important and broad classification of polymers are described in the next
section.

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Table1.1: Classification of Polymers

Basis of Classification Polymer Type

Origin - Natural, Semi synthetic, Synthetic

Thermal Response - Thermoplastic, Thermosetting

Mode of formation - Addition, Condensation

Line structure - Linear, Branched, Cross-linked

Application and Physical - Rubber, Plastic, Fibers

Properties

Tacticity - Isotactic, Syndiotactic, Atactic

1.3.1 Origin

On the basis of their occurrence in nature, polymers have been classified in three types:

A. Natural polymer: The polymers, which occur in nature are called natural polymer also known as
biopolymers. Examples of such polymers are natural rubber, natural silk, cellulose, starch, proteins, etc.

B. Semi synthetic polymer: They are the chemically modified natural polymers such as hydrogenated
natural rubber, cellulosic, cellulose nitrate, methyl cellulose, etc.

C. Synthetic polymer: The polymer which has been synthesized in the laboratory is known as synthetic
polymer. These are also known as manmade polymers. Examples of such polymers are polyvinyl alcohol,
polyethylene, polystyrene, polysulfone, etc..

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1.3.2 Thermal Response

On the basis of thermal response, polymers can be classified into two groups:

A. Thermoplastic polymers:- They can be softened or plasticized repeatedly on application of thermal

B. Thermosetting polymers:- Some polymers undergo certain chemical changes on heating and convert
themselves into an infusible mass. The curing or setting process involves chemical reaction leading to further
growth and cross linking of the polymer chain molecules and producing giant molecules. For example, Phenolic
resins, urea, epoxy resins, diene rubbers, etc.

1.3.3 Mode of Formation

On the basis of mode of formation, polymers can be classified as:

A. Addition polymers:- They are formed from olefinic, diolefinic, vinyl and related monomers. They are
formed from simple addition of monomer molecules to each other in a quick succession by a chain mechanism.
This process is called addition polymerization. Examples of such polymers are polyethylene, polypropylene,
polystyrene.

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B. Condensation polymer: They are formed from intermolecular reactions between bifunctional or
polyfunctional monomer molecules having reactive functional groups such as -OH, -COOH, -NH2, -NCO, etc.

1.3.4 Line Structure

On the basis of structure, polymers are of three types:

A. Linear Polymer: If the monomer units are joined in a linear fashion, polymer is said to be linear polymer.

B. Branched Polymer: When monomer units are joined in a branched manner it is called branched polymer.

C. Cross linked Polymer: A polymer is said to be a cross linked polymer, if the monomer unit are joined
together in a chain fashion.

1.3.5 Application and Physical Properties

Depending on its ultimate form and use a polymer can be classified as:

A. Rubber (Elastomer): Rubber is a high molecular weight polymer with long flexible chains and weak
intermolecular forces. They exhibit tensile strength in the range of 300-3000 psi and elongation at break
ranging between 300-1000%. Examples are natural and synthetic rubbers.

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B. Plastics: Plastics are relatively tough substances with high molecular weight that can be molded with (or
without) the application of heat. These are usually much stronger than rubbers. They exhibit tensile strength
ranging between 4000-15000 psi and elongation at break ranging usually from 20 to 200% or even higher.
The examples of plastics are, PET, PP, PVC, PS, etc.

C. Fibers: Fibers are long-chain polymers characterized by highly crystalline regions resulting mainly from
secondary forces. T hey have much lower elasticity than plastics and elastomers. They also have high tensile
strength ranging between 20,000 – 150,000 psi, are lightweight and possess moisture absorption properties.

1.3.6 Tacticity

It may be defined as the geometric arrangement (orientation) of the characteristic group monomer unit
with respect to the main chain (backbone) of the polymers. On the basis of structure, polymer may be
classified into three groups:

A. Isotactic polymer: It is the type of polymer in which the characteristic group are arranged on the same
side of the main chain.

B. Syndiotactic polymer: A polymer is said to be syndiotactic if the side group (characteristic group) are
arranged in alternate fashion.

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C. Atactic polymer: A polymer is said to be atactic, if the characteristic group (side group) are arranged in
irregular fashion (randomness) around the main chain. It has proper strength and more elasticity.

1.4. Biocomposites

Composites are attractive materials because they combine material properties in ways not found in
nature. Such materials often result in lightweight structures having high stiffness and tailored properties for
specific applications, thereby saving weight and reducing energy needs. Fiber-reinforced plastic composites
began with cellulose fiber in phenolics in 1908, later extending to urea and melamine, and reaching commodity
status in 1940s with glass fiber in unsaturated polyesters. From guitars, tennis racquets, and cars to microlight
aircrafts, electronic components, and artificial joints, composites are finding use in diverse fields.

Composite materials derived from biopolymer and synthetic fibers such as glass and carbon also come
under biocomposites. Biocomposites derived from plantderived fibers (natural/biofiber) and crop/bioderived
plastic (biopolymer/bioplastic) are likely to be more ecofriendly, and such biocomposites are sometimes termed
as “green composites”.

1.4.1 Natural/Biofibers as Reinforcements in Biocomposites

The world’s supply of natural resources is decreasing and the demand for sustainable and renewable
raw materials continues to rise. Biofiber-reinforced composites represent a potential nontraditional, value-
added source of income to the agricultural community.

Jute is from India and Bangladesh; coir is produced in the tropical countries of the world, with India
accounting for 20% of the total world production; sisal is also widely grown in tropical countries of Africa, the
West Indies, and the Far East, with Tanzania and Brail being the two main producing countries; kenaf is grown
commercially in the United States; flax is a commodity crop grown in the European Union as well as in many
diverse agricultural systems and environment throughout the world, including Canada, Argentina, India and
Russia. Flax fiber accounts for less than 2% of world consumption of apparel and industrial textiles, despite
the fact that it has a number of unique and beneficial properties. Hemp originated in Central Asia, from which
it spread to China, and is now cultivated in many countries in the temperate zone. Ramie fibers are the longest
and one of the strongest fine textile fibers mostly available and used in China, Japan and Malaysia.

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Jute Coir Sisal

Kenaf Flax Hemp

Ramie fibers

Most of the polymers by themselves are not suitable for load-bearing applications due to their lack of
sufficient strength, stiffness and dimensional stability. However, fibers possess high strength and stiffness.
Unfortunately, they are not suitable for use in load-bearing applications by themselves because of their fibrous
structure. In fiber-reinforced composites, the fibers serve as reinforcement by giving strength and stiffness to
the structure while the plastic matrix serves as the adhesive to hold the fibers in place so that suitable
structural components can be made. A broad classification (non-wood and wood fibers) of natural fibers is
represented schematically in the Figure below.

Currently , several non-wood fibers (e.g. hemp, kenaf, flax, and sisal) are being utilized commercially in
biocomposites in combination with polypropylene for automotive applications. Now from need of society and
research point of view, it is much important to work on leaf-based non-wood fibers.

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