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 word 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 [1]. 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 certain additives. Later on, Charles Goodyear improved the properties of natural
rubber through vulcanization process with sulphur. 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 behaviour,
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. 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 Properties Rubber, Plastic, Fibers
Tacticity Isotactic, Syndiotactic, Atactic
Non crystalline(amorphous), Semi-crystalline,
Crystalline
Crystallinity
Polarity Polar, Non polar
Chain Hetro, Homo-chain

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.

1.3.2 Thermal Response

On the basis of thermal response, polymers can be classified into two groups
A. Thermoplastic
Polymers that flow when heated; thus, easily reshaped and recycled. This property is due to presence of
long chains with limited or no crosslinks. In a thermoplastic material the very long chain-like molecules are
held together by relatively weak Vander Waals forces. When the material is heated the intermolecular
forces are weakened so that it becomes soft and flexible and eventually, at high temperatures, it is a viscous
melt (it flows). When the material is allowed to cool it solidifies again. E.g., polyethylene (PE),
polypropylene (PP), poly(vinyl chloride) (PVC), polystyrene (PS), poly(ethylene terephthalate) (PET),
nylon (polyamide), unvulcanized natural rubber (polyisoprene).

B. Thermosetting
Decompose when heated; thus, cannot be reformed or recycled. Presence of extensive crosslinks between
long chains induces decomposition upon heating and renders thermosetting polymers brittle. A
thermosetting polymer is produced by a chemical reaction which has two stages. The first stage results in
the formation of long chain-like molecules similar to those present in thermoplastics, but still capable of
further reaction. The second stage of the reaction (crosslinking of chains) takes place during moulding,
usually under the application of heat and pressure. During the second stage, the long molecular chains have
been interlinked by strong covalent bonds so that the material cannot be softened again by the application of
heat. If excess
heat is applied to these materials they will char and degrade.

E.g., epoxy, unsaturated polyesters, phenol-formaldehyde resins, vulcanized rubber.

Characteristics of Thermoplastic and Thermosetting Polymers
Thermoplastics Thermosets
Good elasticity but depends on the type Very poor elasticity
Highly intractable crosslink i.e cannot be
Easily reshaped on heating
remoulded
Weak attractive forces between chains Stronger attractive forces between chains
They are soluble in organic solvents Not soluble in organic compounds
Super abrasion and dimensional stability Better flexural and input resistance
They are not flexible but rigid because of network
They are flexible and not rigid
structure formed by cross-linking
Undergoes irreversible change which causes it to
Softens without chemical change when heated
harden or set

Industrially Important Thermosetting Polymers

Polymer Property Application
High chemical and corrosive resistance,
outstanding adhesive properties, low Protective coatings, composite
Epoxides
shrinkage upon cure, and good electrical matrices, and adhesives.
properties.
High impact resistance, low crosslink Construction and marine
Polyester resins
density. applications, adhesives
Lacquers and varnishes, molding
Formaldehyde resins compounds, (e.g., wall panels
Good chemical, electrical, temperature
(phenoplast and and table tops), decorative plastic
and moisture resistance.
aminoplast) dinnerware. Reinforcing fillers
and electrical fittings.
+

Polythene(polyethelene): The monomer of polythene is ethylene. Polythene is prepared by the addition

polymerization of monomer ethylene in presence of heat catalyst produce either linear or branch or semi
branch polymer. Depending up on the density ethylene polymer is divided into -
1) Low density polythene (LDPE)
2) High density polythene (HDPE)
3) Linear low density polythene (LLDPE)
4) Ultrahigh molecular weight polythene (UHMWPE)

Low Density Polythene (LDPE)

Low density polythene is prepared by a number of methods. The common method for the preparation of
LDPE is polymerization of ethylene monomer at high pressure (1000 - 4000 atm) and temperature (2500C)
in presence of oxygen peroxide hydro peroxide (free radical generator). In this process huge branched
chains are formed through out every long back bone chain. The presence of branches repel each other and
the long chains are not well fltted to each other having some gap produce low density (0.91 to 0.925 gm/cc)
polymer.

Characteristics of low density polythene:

a) Low density polyethylene have density is low (0.91 to 0.925 gm/cc)
b) It is branched chain addition polymer.
c) Semi crystalline polymer having crystallinity 45-50 percent.
d) Chemically inert, nonpolar and having dielectric property zero.
e) Tough but flexible.
f) Melting point 105-1100C.
Uses of low-density polythene:
a) As LDPE is a good insulator they normally used for the preparation of electrical wires and cables.
b) Pouch pack, squeeze bottles, delivery pipes are prepared from LDPE.
c) Toys, refill for ball pen and ball pen also prepared from LDPE

High Density Polythene(HDPE)

The common method for the preparation of HDPE is by the polymerization of ethylene monomer at high
pressure (30 - 35 atm) and temperature (70 - 200 0C) in presence of metal oxide catalyst like CrO3 on silica
alumina. High density polythene can be prepared by the polymerization of ethylene monomer at low
pressure (5 - 7 atm) and temperature (60 - 70 0C) in presence of Zieglar Natta catalyst like triethyl aluminum
and titanium tetrachloride. In this process of polymerization as there is absence of branch through out the
long chain back bone, the chains are well fltted to each other which makes the polymer a high density (0.95
to 0.97 gm/cc) polymer
Characteristics of high density polythene:
a) High density polyethylene have high density (0.95 to 0.97 gm/cc).
b) It is less branched.
c) Highly crystalline polymer having crystallinity 80-90 percent.
d) Chemically inert, nonpolar and having dielectric property zero.
e) Highly tough but flexible.
f) Melting point 130 ¡ 1350C.
Uses of high density polythene:
a) As HDPE is a good insulator they normally used for the preparation of high performance electrical
cables.
b) Bucket, cup, toys are prepared from LDPE.
c) Due to inertness it is used for the storage of H2SO4, pipes for LPG gas and water reserver also

1.3.3 Mode of Formation

On the basis of mode of formation, polymers can be classified as
A. Addition (Chain-growth) Polymerization

Addition polymerization describes the method where monomers are added one by one to an active site on
the growing chain. This is characterized by self-addition of molecules to each other, very rapidly through
chain reaction. Monomer in this case retains its structural identity when it gets converted to polymer
(product has same elemental composition as the monomer). It can be represented with the chemical
equation:

Where n is the degree of polymerization.

In addition, polymerization, no by product is formed (i.e, no net loss of atom). The bifunctionality

is provided by the double bonds present in the monomer. The most common type of addition polymerization
involves Free radical chain reaction of molecule that have C=C bond. For olefins (CH2=CHR), vinyl
compounds (CH2=CHX), allyl compounds (CH2=CH-CH2X) and dienes (CH2=CR-CH=CH2), addition
reaction polymerization involves the opening of the bond with a free radical initiator. Under addition
polymerization, another process known as Ionic polymerization (i.e cationic chain growth and anionic chain
growth mechanism) can occur. All these polymerization processes follow three principal steps – Initiation
(birth), Propagation (growth), and Termination (death). Typical addition polymers are polystyrene,
poly(acrylic acid), polyethylene, poly(vinyl chloride), poly acrylonitrile, poly(vinyl fluoride) etc.

Initiation Reaction
The first step in producing polymers by free radical polymerization is initiation. This step begins when an
initiator decomposes into free radicals in the presence of monomers. The instability of carbon-carbon
double bonds in the monomer makes them susceptible to reaction with the unpaired electrons in the radical.
In this reaction, the active center of the radical "grabs" one of the electrons from the double bond of the
monomer, leaving an unpaired electron to appear as a new active center at the end of the chain. Addition
can occur at either end of the monomer. Example: Consider the polymerization of ethylene (CH2=CH2) to
polyethylene
A peroxide molecule breaks up into two reactive free radicals. Light or heat can provide the
energy needed for this process- first part of the initiation step: We can write an equation for this process:

peroxide free radical initiator

The second part of initiation occurs when the free radical initiator attacks and attaches to a monomer
molecule. This forms a new free radical, which is called the activated monomer.
An equation for the reaction is as thus:

free radical initiator ethylene activated monomer

One of the two Π- electrons in the ethylene has been used to form a single bond with the R–O˙ radical. The
other remains on the second carbon atom, leaving it as a seven-valence electron
atom that reacts with another ethylene molecule.
Propagation Reaction
After a synthesis reaction has been initiated, the propagation reaction takes over. In the propagation phase,
the newly formed activated monomer attacks and attaches to the double bond of another monomer
molecule. The process of electron transfer and consequent motion of the active center down the chain
proceeds. In this diagram, (chain) refers to a chain of connected monomers, and X refers to hydrogen atom.
Hence the monomer would be ethylene and the polymer polyethylene.

In free radical polymerization, the entire propagation reaction usually takes place within a fraction of a
second. Thousands of monomers are added to the chain within this time. The entire process stops when the
termination reaction occurs.

Termination Reaction

This chain reaction cannot go on forever. The reaction must terminate, but how?. In theory, the propagation
reaction could continue until the supply of monomers is exhausted. However, this outcome is very unlikely.
Most often the growth of a polymer chain is halted by the termination reaction. Termination typically
occurs in two ways: combination and disproportionation.
Combination occurs when the polymer's growth is stopped by radical end groups on two growing chains
that join and form a single chain. The following diagram depicts combination, with the symbol (R)
representing the rest of the chain.

Disproportionation halts the propagation reaction when a free radical strip a hydrogen atom from an active
chain. A carbon-carbon double bond takes the place of the missing hydrogen. Termination by
disproportionation is shown in the diagram.

Disproportionation can also occur when the radical reacts with an impurity. This is why it is so important
that polymerization be carried out under very clean conditions.
NOTE: Chemists can control the way a polymer does each of these steps by varying the reactants, the
reaction times and the reaction condition. The physical properties of a polymer chain depend on the
polymer’s average length, the amount of branching, and the constituent monomers.

B. Condensation (Step) Polymerization.

This takes place between two bifunctional molecules to produce one larger polyfunctional molecule. The
bifunctional molecules (monomers) usually condense with one another, and in so doing repeatedly eliminate
a small molecule such as H2O, NH3, HCl, etc., as the reaction proceeds. The reaction continues until almost
or all of the reactants are used up. This polymerization takes place by series of steps. The type of end
product resulting from a condensation polymerization is dependent on the number of functional end groups
of the

monomer which can react. Monomers with only one reactive group terminate a growing chain, and thus
give end products with a lower molecular weight. Linear polymers are created using monomers with two
reactive end groups and monomers with more than two end groups give three dimensional polymers which
are crosslinked. The monomers that are involved in condensation polymerization are not the same as those
in addition polymerization. They have two main characteristics: Instead of double bonds, these monomers
have functional groups (like alcohol, amine, or carboxylic acid groups).

Each monomer has at least two reactive sites, which usually means two functional groups. Some monomers
have more than two reactive sites, allowing for branching between chains, as well as increasing the
molecular mass of the polymer. During the polymerization process, the monomers tend to form dimers (two
linked monomers) and trimers (three linked monomers) first. Then, these very short chains react with each
other and with monomers. It is only near the end of polymerization that very long chains are formed.
Example of condensation polymers are polyamides, polyacetals, polyesters, polycarbonates and
polyurethanes.

Distinction between Addition and condensation polymerization.

(a) Addition polymerization (chain-growth polymerization.)

(i) Monomers are unsaturated.
(ii) Nothing is eliminated as result of this type of polymerization.

(iii) High molecular weight polymer is attained at once.

(iv) Only monomers and polymers are present during the course of the polymerization.
(v) Only monomers add to the growing chain.
(vi) Chain grows at active centers.
(vii) Molecular wt. of polymer = DPX Mol. wt. of monomer.
(viii) Involves opening of double bond by active species like free radical on in.
(ix) Example: Polyolefins, polygons, vinyl polymers and a cyclic polymers.
(x) Initiator orcatalyst generate active species that attacks the monomer (free radical,
anions, cantons). The process of polymerization is endothermic.
(xi) Can be done by bulk, solution, suspension and emulsion polymerization technique.
(xii) Can quickly lead to a polymer with very high molecular weight, cross-linking can be
achieved by using monomers with two double bonds i.e. divinely benzene.

(b) Condensation polymerization (Step-growth polymerization.)

(i) Monomers contain two or more functions groups.
(ii) Usually the molecules like H2O, Alcohols, HX, and NH3 etc. are eliminated during the process of
polymerization.

(iii) High molecular weight polymer is attained only at very high conversions.

(iv) All possible molecular weight species i.e.dimmers, trimmers, tetramers and mutineers etc. are present.

(v) All species are reactive.

(vi) Stepwise intermolecular conversation.

(vii) Not so, because some small molecules often get eliminated during the course of polymerization.

(viii) Involves the reaction between the functional groups.

(ix) Example: Polyesters, polyamides, and polycarbonates.

(x) Most of the reaction has higher value of activation energy and hence usually heating is required.
Unanalyzed and catalyzed process are possible.

(xi) Poly condensation can be achieved in melt, solution as well as at the interfacial boundary between two
liquids in which the respective monomers are dissolved.

(xii) Slow stepwise addition process, molecular weight is <1,00,000 highly dependent on monomer
stoichiometry, little amount of the on multi-functional monomers develop extensive cross-linking.

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. Examples: Polyethylene, poly (vinyl chloride) (PVC), polystyrene, polymethyl methacrylate
(plexiglass), nylon, fluorocarbons (teflon)

Linear Homopolymer Linear Copolymer

B. Branched polymer:- When monomer units are joined in branched manner, it is called branched
polymer. Examples: Many elastomers or rubbers.
 Branched Homopolymer Branched Copolymer

C. Cross linked polymer:- A polymer is said to be a cross linked polymer, if the monomer units are
joined together in a chain fashion. Examples: Thermosetting polymers, many elastomers or rubbers are
also cross-linked (vulcanized).

Cross linked Homopolymer Cross linked Copolymer

Application and Physical Properties

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

A. Rubber (Elastomers):- Rubber is high molecular weight polymer with long flexible chains
and weak intermolecular forces. They exhibits tensile strength in the range of 300-3000 psi and
elongation at break ranging between 300-1000%. If the inter- chain forces are very weak, then
the polymer is elastic, flexible and soft in nature and is known as rubber. The molecular chains
are stretched on pulling but the inter chain forces not being strong enough to keep it in the
oriented position, then the chains regain their original position after removal of the deforming
forces. Examples: are natural and synthetic rubber.
 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. These are the substances of high polymer class which can be molded into articles
by heat and pressure. These are mostly synthetic in nature and are called synthetic resins. They possess
high modulus of elasticity in the range of 10 to 100 kg/ cm 2. Examples: polyethylene, polypropylene,
PVC, polystyrene, etc.

Fibers: Fibers are long- chain polymers characterized by highly crystalline regions resulting
mainly from secondary forces. They have a much lower elasticity than plastics and elastomers.
They also have high tensile strength ranging between 20,000- 150,000 psi., are light weight and
possess moisture absorption properties. If the inter -chain force of attraction in a polymer is very
strong, then it must be hard and durable and is known as fiber. In fiber, the chains are oriented
along the direction of the pull and the inter- chain forces keep these very strong enough.
Tacticity:-

It may be defined as the geometric arrangement (orientation) of the characteristic group of 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.

Isotactic Polypropene

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

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

Atactic Polypropene

BIOCOMPOSITES
Composite 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 [4-6].
Fiber-reinforced plastic composites began with cellulose fiber in phenolics in 1908, later
extending to urea and melamine, and reaching commodity status in the 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 fiber (natural/biofiber) and
crop/bioderived plastic (biopolymer/bioplastic) are likely to be more ecofriendly, and such
biocomposites are sometimes termed “green composites”

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 Brazil 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.
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 (nonwood and wood fibers) of natural fibers is represented schematically in
Fig. 1.1.
Currently several nonwood 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
nonwood fibers.

Figure 1.1 Schematic representation of reinforcing natural/biofibers classification.

CHARACTERIZATION OF POLYMERS

It is comparable to the synthesis of organic compound, composites, biocomposites without a subsequent

characterization of its various properties Synthesized material characterization is therefore of very great
importance. Some of the important aspects related to characterizations have been described in this section.

Molecular Weight and its Distribution

The molecular weight of a polymer is of prime importance in the polymer’s synthesis and application. It is
important because it determines many physical properties. The term molecular weight is a ratio of the
average mass per formula unit of substance to 1/12 th of an atom of 12C. Molecular weight (MW) and its
distribution (MWD) has a considerable effect on macroscopic properties of polymer such as toughness,
tensile strength, adherence and environmental resistance, etc. [10]. A simple chemical has fixed molecular
weight but when we discuss about the molecular weight of polymer, we mean something different from that
which applies to small sized compounds. Since polymers are mixture of molecules of different molecular
weight, the molecular weight is expressed in the term of “average” value. This average molecular weight is
basically based on either average number of repeating units, known as number average molecular weight, or
average weight, known as weight average molecular weight. The number average molecular weight is
obtained from the number ni of macromolecules for each degree of polymerization Pi by taking for each
degree of polymerization the product of the number of polymer molecules and their degree of
polymerization ni pi and dividing the sum of these product by the total number of monomers No

The weight average molecular weight M w is obtained in a similar manner from mass mi of each degree of
polymerization Pi according to the following equation:

When the molecular weight distribution is very narrow, the number average and weight average molecular
weights are essentially equal. When the distribution is broad, the weight average molecular weight is
greater than the number average molecular weight and broader the distribution, the greater the difference
between them as shown in Figure 1.2. From these molecular averages the molecular
distribution is represented by their ratio:

Crystallization
Crystallization in polymer has always been the subject of great scientific and academic interest, since
polymers are known to exhibit a variety of structures at various length scales, such as unit cell, lamella, and
spherulites. It is an interesting property related to phase transition which determines the final properties of
many technologically relevant and scientifically exciting systems. Polymer crystallization controls the
structural formation process of polymeric materials and thereby dominates the properties of final polymer
product. Polymer crystallization is usually divided into two separate processes primary nucleation and
crystal growth. In general, a crystalline phase must primarily nucleate. The fundamental kinetics of
nucleation are often complicated to determine because the rate of heterogeneous nucleation at defects,
impurities, and surfaces is much faster than the homogeneous rate of nucleation within the pure bulk liquid.
After a nucleus forms, the kinetics of crystal growth determines the overall rate of the phase transformation.
For growth from solid or liquid solutions, the rate limiting step in the kinetics is often mass diffusion. For
crystal growth from a melt, heat transfer plays an important role for metals, ceramics, and semiconductors,
but for large molecules and polymers, the microscopic kinetics associated with attaching a large molecule or
polymer segment to the growing crystal are typically the most important consideration. The crystalline and
amorphous components influence polymer properties. Actually, crystallinity of a polymer sample is
expressed in terms of that fraction of the sample which is crystalline. The definition of degree of
crystallinity is, of course, based on the premise that crystalline and non-crystalline components of a polymer
can coexist''. The highest crystallinity is generally associated with polymers which have a simple unit cell
structure and a relatively high degree of molecular order. The overall property (Q) of a partially crystalline
polymer can be expressed as a sum of its two components as:

where Qc and Qa are contributions of the crystalline and amorphous components of the sample, respectively.
A number of methods can be used to detect crystallinity and estimate its degree: X-ray diffraction, infrared-
absorption spectroscopy, polarized light microscopy, density, differential thermal analysis and nuclear
magnetic resonance spectroscopy, etc. Accurate and undisputed measurement of the volume fraction of
crystallinity in a polymer is not easily accomplished because each of the method of measurement mentioned
above is concerned with a different physical aspect of material. Nevertheless, the great practical
consequences of crystallinity and orientation on mechanical properties dictate that at least relative changes
in these factors be observed by whatever means are applicable, and that these be correlated with changes in
processing and fabrication methods and with end-use behaviour. It was found that the preparation method of
samples influence the morphology and crystallization behaviour of blends.

Glass Transition Temperature

In the study of polymers and their applications, it is important to understand the concept of the glass
transition temperature Tg. The glass transition is a phenomenon observed in linear amorphous polymer. It
occurs at fairly well-defined temperature when the bulk material ceases to be brittle and glassy in character
and become less rigid and more rubbery. The knowledge of Tg is essential in the selection of materials for
various applications.

Many Physical properties change profoundly at the glass transition temperature, including mechanical
properties and electrical properties. All of these are dependent on the relative degree of freedom for
molecular motion within a given polymeric material and each can be used to monitor the point at which the
glass transition occurs.

An ordinary rubber ball if cooled below – 70 oC, it becomes so hard and brittle that it will break
into pieces like a glass ball falling on a hard surface. Why this happens below -70 oC. This is

because there is a temperature boundary for almost all amorphous polymer and many crystalline

polymers only above which the substance remains soft, flexible and rubbery and below which it

becomes hard, brittle and glassy. The temperature below which a polymer is hard and above which it is soft
is called the Glass transition temperature. The hard, brittle state is known as the glassy state and the soft,

flexible state is known as rubbery on Viscoelasticity state. On further heating the polymer (without cross-
linked) becomes a highly viscous liquid and starts flowing, which is known as viscous fluid state.

Definition: The temperature at which the internal energy of the molecules of the polymer increases to such
an extent that the chain segment of the polymer just gets over its frozen state to a mobile state, capable of
leaving the lattice sites is known as glass transition temperature.

One property associated with the glassy state is a low volume coefficient of expansion. This low coefficient
occurs as the result of a change in slope of the curve of volume Vs temp. at the point called glass transition
temperature (Tg). This behavior is shown by natural rubber. Another general phenomenon i.e. the
amorphous regions of partially crystalline polymers are also assuming a glassy state. i.e. Tg being
independent of degree of crystalline to first approximation. The magnitude of the phenomena associated
with Tg decreases with decreasing amorphous content. Hence Tg is sometimes difficult to defect in highly
crystalline polymer.

SUMMARY
MECHANICAL PROPERTIES OF POLYMERS

To study the necessary set of valuable properties, polymers differing from one another by their chemical
structure and properties are usually mixed together, either homogeneously or heterogeneously. The
mechanical properties of inhomogeneous mixture are worse than those of individual polymers, while the
mechanical properties of homogeneous mixture are good.

Polymers can exhibit the features of glassy, brittle solid or an elastic rubber, or that of a viscous liquid,
depending on the temperature and time scale of measurement. The studies on mechanical properties of
polymer can, therefore, be carried out by subjecting them to some form of mechanical stress either
continuous or in a periodic manner at different rate. Some of the important properties of polymers with
regard to their use as engineering material are tensile strength, compressive and flexural strength, hardness,
creep, fatigue resistance and impact resistance.

Toughness of a polymer is the ability to absorb mechanical energy without fracturing. The property such as
tensile strength is the maximum amount of tensile load per unit area a material can withstand, while the
tensile elongation gives the measure of increase in length in response to a tensile load expressed as a
percent of the original length. Elongation at break is the maximum elongation the plastic can undergo.

Engineering applications of polymers are governed to a great extent by strain hardening

considerations. The designer using polymeric materials must, therefore, understand their mechanical
behaviour with respect to the maximum permissible strains to avoid failure. As for most materials, a simple
tensile stress-strain curve provides a good start towards understanding the mechanical behaviour of a
particular polymer. This curve is usually established by continuously measuring the force developed as the
sample is elongated at constant rate of extension until it breaks. Portions of the curve in Fig.1.3 represent the
stress-strain behaviour of any polymer and are used to define several useful quantities. The initial slope
provides a value for Young's modulus (or the modulus of elasticity) which is a measure of stiffness. The
curve also gives yield stress, strength and elongation at break. The area under the curve or work to break is a
rough indication of the toughness of the polymeric material. The stress at the knee in the curve (known as
the yield point) is a measure of the strength of the material and resistance to permanent deformation. The
stress at the breaking point, commonly known as ultimate strength, is a measure of the force required to
fracture the material completely.

A hard, brittle material such as an amorphous polymer far below its Tg, usually has an initial slope
indicative of very high modulus, moderate strength, a low elongation at break, and a low area under the
stress-strain curve (Fig. 1.4). Polymeric materials showing hard brittle behaviour at room temperature or
below are polystyrene, poly (methyl methacrylate) and many phenol-formaldehyde resins.
 Hard and strong polymers have high modulus of elasticity, high strength, and elongation at break of
approximately 5 percent. The shape of the curve often suggests that the material has broken where a yield
point might be expected. This type of curve is characteristic of some rigid poly(vinyl chloride) formulations
and polystyrene polyblends. Hard, tough behaviour is shown by polymers such as cellulose acetate,
cellulose nitrate and nylons; they have high yield points and high modulus, high strengths and large
elongations. Most polymers of this group show cold-drawing or "necking" during the stretching process.
Cold-drawing is important in synthetic fiber technology, and is used to develop strength. Polymeric
materials that are soft and tough show low modulus and yield values, moderate strength at break, and very
high elongation ranging from 20 to 100 per cent. This type of stress-strain curve is characteristic of
plasticized PVC and rubbers (elastomers).

The two mechanical performances creep and stress relaxation are related to each other. In creep, elongation
takes place under the application of constant stress, while in stress relaxation, decrease in stress occur when
a specimen is held at constant and essentially instantaneously induced strain. The varying stress or strain is
measured as a function of time. Repeated flexing of a sample through a given distance often causes a sample
to fail at a lower stress than it could for a single flexure. This feature is referred to as fatigue.

Figure 1.3: Generalized tensile stress-strain curve for some polymeric materials
Figure 1.4: Tensile stress-strain curves for four types of polymeric material.

Fatigue testing may be carried out by subjecting the sample to alternating tensile and compressive stress.
The fatigue resistance usually decreases with increase in rigidity.

Impact strength is a measure of toughness or resistance to breakage under high velocity impact conditions.
From this point of view, polymeric materials under normal conditions of use are thought to be either brittle
or tough. For example, polystyrene, poly(methyl methacrylate) and unmodified, non plasticized PVC are
usually rated as brittle, breaking with a sharp fracture; plasticized PVC's are considered to be tough. In
general, polymeric materials are either brittle or tough, depending on the temperature and rate of impact, i.e.
rate of deformation. Impact strength of polymers and derived plastics depends on the position of the glass
transition temperature (Tg) with respect to room temperature and ease of crystallization. Far below the glass-
transition, amorphous polymers break with a brittle fracture, but they become tougher as the service
temperature approaches Tg.. Above Tg, amorphous polymers are in a rubbery state so that the term impact
ceases to have any significance.