POLYMERS

An Introduction
Definition
• Polymer literally means “many parts.”
• A polymeric solid material may be considered
to be one that contains many chemically
bonded parts or units which themselves are
bonded together to form a solid.
• Polymers comprise a large class of natural and
synthetic materials with variety of properties
and purposes.
Natural polymers are found in many forms
such as horns of animals, tortoise shell, shellac
(from the lac beetle), rosin (from pine trees),
and tar from distillation of organic material.
 Types of Polymers
Two industrially important polymeric materials are
rubbers and plastics.
As engineering materials, it is appropriate to divide
them into the following three categories:

1. Elastomers
2. Thermoplastic Polymers
3. Thermosetting Polymers

Where (1) are rubbers and (2) and (3) are plastics
 Elastomers

Elastomers or rubbers can be elastically

deformed a large amount when force is
applied to them and can return to their
original shape when the force is released.
 RUBBER, A Natural Polymer
• One of the most useful natural polymers was rubber,
obtained from the sap of the hevea tree.

• It has only limited use as it became brittle in the cold

and melted when warmed.

• The development of vulcanization later in the

nineteenth century improved the durability of the
natural polymer rubber, signifying the first
popularized semi-synthetic polymer. The properties
were changed making the rubber more flexible and
temperature stable.
• The first wholly synthetic polymer,
BAKELITE, was introduced in 1909.

• Its original use was to make billiard balls.

 Plastics

Plastics are a large and varied group of synthetic

materials which are processed by forming or
molding into shape.

– Plastics can be divided into two classes,

thermoplastics and thermosetting plastics,
depending on how they are structurally and
chemically bonded.
 Thermoplastics vs. Thermosets
• Thermoplastics • Thermosets

-little cross linking -large cross linking

-ductile -hard and brittle
-soften when heated -do not soften with
-polyethylene, heating
polypropylene, -vulcanized rubber,
polycarbonate, epoxies, polyester resin,
polystyrene phenolic resin
 Reason Why Polymers are Important

• Plastics can be formed by molding into

intricate part shapes, usually with no further
processing required
• Cost competitive with metals
• Generally require less energy to produce than
metal
• Certain plastics are translucent/ transparent
which makes them competitive with glass in
some applications
 Polymers as Engineering Materials
• Advantages
• Low density relative to metals and ceramics
• Good strength-to-weight ratios for certain polymers
• High corrosion resistance
• Low electrical and thermal conductivity

• Limitations
• Low strength relative to metal and ceramics
• Low modulus of elasticity
• Service temperatures are limited to only few hundred degrees
• Viscoelastic properties, which can be distinct limitation in load bearing
applications
• Some polymers degrade when subjected to sunlight and other forms of
radiation
• The technology to mass produce polymers was not
developed until World War II, when there was a need
to develop synthetic rubber for tires and other
wartime applications and nylon for parachutes.
• Today, polymers are commonly used in thousands of
products as plastics, elastomers, coatings, adhesives,
as well as structural components for products
ranging from children’s toys to aircraft.
• They make up 80% of the organic chemical industry,
since most of them are based on carbon, with
products produced at approximately 150 kg of
polymers per person annually in US.
 Glass Transition Temperature

The temperature at which, upon cooling, a

non-crystalline ceramics or polymer
transforms from a super cooled liquid to a
rigid/inflexible glass.
 POLYMER SCIENCE

POLYMER CHEMISTRY
3.1.1 Polymers & Macromolecules
3.1.2 Polymer Synthesis
3.1.3 Physical Polymer Chemistry

POLYMER PHYSICS
 POLYMER SCIENCE
• Most polymer research may be categorized as
polymer science, a sub-discipline of materials science
which includes researchers in chemistry (especially
organic chemistry), physics, and engineering.
Polymer science may be roughly divided into two
subdisciplines:

• Polymer chemistry or macromolecular chemistry,

concerned with the chemical synthesis and chemical
properties of polymers.
 Basic concepts in polymer chemistry
• Polymers and macromolecules
In chemistry, the terms "polymer molecule" and
"macromolecule" are used interchangeably.
A polymer molecule has a high molecular mass and
is comprised of many smaller, repeating subunits or
monomers.
Polymers may be found in nature, such as the DNA
and proteins found in living cells, or created in
laboratories or factories.
Polymer molecule may be a long chain of a single
monomer repeated over and over again or a
complex network containing dozens of different
types of monomers. The identity, variety, and
arrangement of monomers in a polymer molecule
affect the chemical and physical properties of the
polymer molecule.
-Sample of polymers & macromolecules
 Polymer synthesis

An important area of research in polymer chemistry is

finding new or better ways to prepare a polymer
molecule from a stock of smaller monomers. In most
cases, polymers are prepared using principles of
organic chemistry.
Polymer chemists are also investigating polymerization
methods outside the scope of organic chemistry.
One area of interest involves preparing polymers by
imitating the biological processes used to create
biopolymers such as proteins or cellulose.
Other areas of study involve using plasma or electricity
to initiate polymerization reactions.
Physical polymer chemistry is the study of how a
polymer molecule's structure relates to the behavior of
the bulk substance.
Physical polymer chemistry is closely related to the field
of polymer physics and also overlaps with polymer
research in materials science.
Physical polymer chemists use analytical techniques
such as light scattering and spectroscopy* to
characterize the size and structure of polymers.
Other areas of interest in physical polymer chemistry
include the study of polymers in solution, the
mechanical properties of polymers, and understanding
phase transitions in polymer substances.
There are also many researchers using principles of
theoretical chemistry to better understand the
structure and properties of polymer molecules.
 Polymer physics
Concerned with the bulk properties of polymer materials and
engineering applications. The field of polymer science is
generally concerned with synthetic polymers, such as
plastics, or chemical treatment and modification of natural
polymers.

• Polymer physics is the field of physics associated to the

study of polymers, their fluctuations, mechanical properties,
as well as the kinetics of reactions involving degradation and
polymerisation of polymers and monomers respectively.
While it focuses on an aspect of the study of condensed
matter physics, the field of polymer physics has developed as
a branch of statistical physics. Polymer physics and polymer
chemistry are part of the wider field of polymer science.
 Disordered polymers are too complex to be described
using a deterministic method. However statistical
approaches can yield results and are often pertinent since
large polymers (that is to say, polymers which contain a
large number of monomers) can be described efficiently
as systems at the thermodynamic limit.
Thermal fluctuations continuously affect the shape of
polymers in liquid solutions, and modelling their effect
requires a recourse to the principles of statistical
mechanics. As a corollary temperature strongly affects the
physical behavior of polymers in solution.
The statistical approach to polymer physics is based
on an analogy between a polymer and either a brownian
motion, or some other type of random walk. The simplest
possible polymer model is presented by the ideal chain,
corresponds to homogeneous random walk.
 The study of biological polymers, their structure,
function, and method of synthesis is generally the
purview of biology, biochemistry, and biophysics.
These disciplines share some of the terminology
familiar to polymer science, especially when
describing the synthesis of biopolymers such as DNA
or polysaccharides. However, usage differences
persist, such as the practice of using the term
macromolecule to describe large non-polymer
molecules and complexes of multiple molecular
components, such as hemoglobin. Substances with
distinct biological function are rarely described in the
terminology of polymer science. For example, a
protein is rarely referred to as a copolymer.
Chemical Properties of Polymers
The attractive forces between chains play a
large part in determining a polymer’s properties.

Because polymer chains are so long, these

interchain forces are amplified far beyond the
attractions between conventional molecules.

Different side groups o the polymer can lend the

polymer to ionic bonding or hydrogen bonding
between its own chains. These stronger forces
typically result in higher tensile
strength and melting point.
The intermolecular forces in polymers can be affected by
dipoles in the monomer units. Polymers containing amide or
carbonyl groups can form hydrogen bonds between adjacent
chains; the partially positively charged hydrogen atoms in N-
H groups of one chain are strongly attracted to the partially
negatively charged oxygen atoms in C=O groups on
another. The strong hydrogen bonds, for example, result in
the high tensile strength and melting point of polymers
containing urethane or urea linkages.

Polyester have dipole-dipole bonding between the oxygen

atoms in C=O groups and the hydrogen bonding, so a
polyester’s melting point and strength are lower than
Kevlar's, but polyesters have greater flexibility.
 Ethene, however, has no permanent dipole. The
attractive forces between polyethylene chains arise
from weak van der Waals forces. Molecules can be
thought of as being surrounded by a cloud of negative
electrons.
As two polymer chains approach, their electron clouds
repel one another. This has the effect of lowering the
electron density on one side of a polymer chain,
creating a slight positive dipole on this side.
This charge is enough to actually attract the second
polymer chain. Van der Waals forces are quite weak,
however, so polyethene can have a lower melting
temperature compared to other polymers.
 Cracking of polymers
Cracking is the process by which a polymer is
divided into its subcomponents or monomers.
The resulting subcomponents are more
viscous than the original polymer.
 Polymer Degradation
• Change in properties of a polymer
• Polymer based product under the influence of one or
more environmental factors
• It is often due to the hydrolysis of the bonds
connecting the polymer chain, which in turn leads to
decrease in the molecular mass of the polymer.
• Changes may be undesirable or desirable
 Cont…

• Degradation of polymers to form smaller

molecules may proceed:
- by random scission
- by specific scission
• Degradation process can be useful to prevent
environmental pollution
- Polylactic acid and Polyglycolic, acidused for
biomedical application
 The characterization of a polymer
requires several parameters which need to be
specified. This is because a polymer actually
consists of a statistical distribution of chains of
varying lengths, and each chain consists of
monometer residues which affect its
properties.
 A variety of lab techniques are used to
determine the properties of polymers.
Techniques such as wide angle X-ray scattering,
small angle X-ray scattering, and small angle
neutron scattering are used to determine the
crystalline structure of polymers. Gel
permeation chromatography is used to
determine the number average molecular
weight, weight average molecular weight, and
polydispersity.
 Thermal properties such as the glass transition
temperature and melting point can be determined
by differential scanning calorimetry and dynamic
mechanical analysis. Pyrolysis followed by
analysis of the fragments is one more technique
for determining the possible structure of the
polymer.
 Morphological Properties
Crystallinity
 The state where in a periodic and repeating
atomic arrangement is achieved by molecular
chain alignment or ordered atomic array.
 It may exist in polymeric materials.
 Its atomic arrangements will be more complex
for polymers.
 When applied to polymers, the term
crystalline has a somewhat
ambiguous/unclear usage.
 Its crystals structure may be specified in terms
of unit cells which are quite complex.
 In addition to being entirely amorphous
polymers may also exhibit varying degrees of
crystallinity.

Amorphous having a non-crystal line structure.

Interdispersed / bury dissolved within
amorphous areas.

Polymers single crystals may be grown from

dilute solutions as thin platelets and having
chain-folded structures.
Many semi-crystalline polymers form
spherulites; each spherulites consists of a
collection of ribbon-like chain-folded
(lamellar) crystallites that radiate outward
from its center.
Bulk Properties/Mechanical Properties

The bulk properties of a polymer are those

most often of end-use interest.
These are the properties that dictate how
polymer actually behaves on a
macroscopic scale.
Mechanical Characteristics of Polymers

Highly sensitive to:

1. Rate of deformation (strain rate)
2. Temperature
3. Chemical Nature of the environment
(presence of water, oxygen, organic solvent
etc.)
 Young Modulus of Elasticity
The parameter quantifies the elasticity of the
polymers.
The ratio of stress (stress it is instantaneous
load applied to a specimen divided by cross
sectional area before any deformation) to
strain when a deformation is totally elastic.
It is also a measure of the stiffness of a
material.
 Transport Properties

Diffusivity relate to how rapidly molecules move

through the polymer matrix.
 Pure Component Phase Behavior
Diffusivity relate to how rapidly molecules
move through the polymer matrix.

Melting point
The term melting point when applied to
polymers suggests not a solid liquid phase
transition but a transition from a CRYSTALLINE
OR SEMI-CRYSTALLINE PHASE to a SOLID
AMORPHOUS PHASE.
It is also known as crystalline melting
temperature.
Ex. Among synthetic polymers, crystalline
melting is only discussed with regards to
thermoplastics, as thermosetting polymers
will decompose at high temperature rather
than melt.

Boiling Point
The boiling point of a polymer substance
is never defined due to the fact that
polymers will decompose before reaching
theoretical boiling temperatures.
The Three Primary Methods of
Polymer Synthesis
Polymers are synthesized by three primary
methods:
a. organic synthesis in a laboratory or factory,
b. biological synthesis in living cells and
organisms, or,
c. chemical modification of naturally occurring
polymers.
 a. Organic synthesis

• In 1907, Leo Baekeland created the first completely

synthetic polymer, Bakelite, by reacting phenol and
formaldehyde at precisely controlled temperature
and pressure. Subsequent work by Wallace Carothers
in the 1920s demonstrated that polymers could be
synthesized rationally from their constituent
monomers. The intervening years have shown
significant developments in rational polymer
synthesis. Most commercially important polymers
today are entirely synthetic and produced in high
volume, on appropriately scaled organic synthetic
techniques.
• Laboratory synthetic methods are generally
divided into two categories, condensation
polymerization and addition polymerization.
However, some newer methods such as
plasma polymerization do not fit neatly into
either category.

• Synthetic polymerization reactions may be

carried out with or without a catalyst.
 b. Biological synthesis

• Natural polymers and biopolymers formed in living

cells may be synthesized by enzyme-mediated
processes, such as the formation of DNA catalyzed by
DNA polymerase. The synthesis of proteins involves
multiple enzyme-mediated processes to transcribe
genetic information from the DNA and subsequently
translate that information to synthesize the specified
protein. The protein may be modified further
following translation in order to provide appropriate
structure and function.
 c. Chemical Modification

Many commercially important polymers are

synthesized by chemical modification of
naturally occurring polymers.
Prominent examples include the reaction of
nitric acid and cellulose to form nitrocellulose
and the formation of vulcanized rubber by
heating natural rubber in the presence of
sulfur.
 Polymer Structure and Properties

Types of polymer 'properties' can be broadly

divided into several categories based upon scale.

At the nano-micro scale are properties that

directly describe the chain itself. These can be
thought of as polymer structure.

At an intermediate mesoscopic level are

properties that describe the morphology of the
polymer matrix in space.

At the macroscopic level are p roperties that

describe the bulk behavior of the polymer.
 Structure
The structural properties of a polymer relate to the physical
arrangement of monomers along the backbone of the chain.
Structure has a strong influence on the other properties of a
polymer. For example, a linear chain polymer may be soluble
or insoluble in water depending on whether it is composed of
polar monomers (such as ethylene oxide) or nonpolar
monomers (such as styrene). On the other hand, two samples
of natural rubber may exhibit different durability even though
their molecules comprise the same monomers. Polymer
scientists have developed terminology to precisely describe
both the nature of the monomers as well as their relative
arrangement:
Monomer identity

The identity of the monomers comprising the polymer is

generally the first and most important attribute of a polymer.
Polymer nomenclature is generally based upon the type of
monomers comprising the polymer. Polymers that contain only a
single type of monomer are known as homopolymers, while
polymers containing a mixture of monomers are known as
copolymers. Poly(styrene), for example, is composed only of
styrene monomers, and is therefore is classifed as a
homopolymer. Ethylene-vinyl acetate, on the other hand,
contains more than one variety of monomer and is thus a
copolymer. Some biological polymers are composed of a variety
of different but structurally related monomers, such as
polynucleotides composed of nucleotide subunits.
A polymer molecule containing ionizable subunits is known as a
polyelectrolyte. An ionomer is a subclass of polyelectrolyte with a
low fraction of ionizable subunits.
Chain linearity

The simplest form of polymer molecule is a straight chain or

linear polymer, composed of a single main chain. The flexibility
of an unbranched chain polymer is characterized by its
persistence length. A branched polymer molecule is composed
of a main chain with one or more substituent side chains or
branches. Special types of branched polymers include star
polymers, comb polymers, and brush polymers. If the polymer
contains a side chain that has a different composition or
configuration than the main chain the polymer is called a graft or
grafted polymer. A cross-link suggests a branch point from which
four or more distinct chains emanate. A polymer molecule with a
high degree of crosslinking is referred to as a polymer network.
Sufficiently high crosslink concentrations may lead to the
formation of an 'infinite network', also known as a 'gel', in which
networks of chains are of unlimited extend.
 Chain size
Polymer bulk properties may be strongly dependent on the
size of the polymer chain.
Like any molecule, a polymer molecule's size may be
described in terms of molecular weight or mass. In polymers,
however, the molecular mass may be expressed in terms of
degree of polymerization, essentially the number of monomer
units which comprise the polymer. For synthetic polymers, the
molecular weight is expressed statistically to describe the
distribution of molecular weights in the sample. This is
because of the fact that almost all industrial processes
produce a distribution of polymer chain sizes. Examples of
such statistics include the number average molecular weight
and weight average molecular weight. The ratio of these two
values is the polydispersity index, commonly used to express
the "width" of the molecular weight.
Monomer arrangement in copolymers

Monomers within a copolymer may be organized along the

backbone in a variety of ways.
Alternating copolymers possess regularly alternating monomer
residues ,
Periodic copolymers have monomer residue types arranged in a
repeating sequence,
Random copolymers have a random sequence of monomer
residue types ,
Statistical copolymers have monomer residues arranged
according to a known statistical rule,
Block copolymers have two or more homopolymer subunits
linked by covalent bonds. Block copolymers with two or three
distinct blocks are called diblock copolymers and triblock
copolymers, respectively.
Tacticity in polymers

This property describes the relative

stereochemistry in neighboring structural units
within a macromolecule.
There are three types: isotactic, atactic, and
syndiotactic
 Industry
Today there are primarily six commodity polymers in
use, namely polyethylene, polypropylene, polyvinyl
chloride, polyethylene terephthalate, polystyrene
and polycarbonate. These make up nearly 98% of all
polymers and plastics encountered in daily life.
Each of these polymers has its own characteristic
modes of degradation and resistances to heat, light
and chemicals.
 Polyethylene
Polyethylene (IUPAC name polyethene) is a
thermoplastic commodity heavily used in
consumer products.
Over 60 million tons of the material are
produced worldwide every year.
 Polypropylene
• Polypropylene or polypropene (PP) is a
thermoplastic polymer, made by the chemical
industry
 applications
Used in a wide variety of applications,
including food packaging, ropes, textiles,
plastic parts and reusable containers of
various types, laboratory equipment,
loudspeakers, automotive components, and
polymer banknotes. Additionally it is used
commonly in New Zealand and by the US
Military as Thermal Underwear.
 Polyvinyl chloride
Polyvinyl chloride, (IUPAC Polychloroethene)
commonly abbreviated PVC, is a widely used
thermoplastic polymer.
 applications
There are many uses for PVC. As a hard plastic, it is
used as vinyl siding, magnetic stripe cards, window
profiles, gramophone records (which is the source of
the name for vinyl records), pipe, plumbing and
conduit fixtures.
The material is often used in Plastic Pressure Pipe
Systems for pipelines in the water and sewer
industries because of its inexpensive nature and
flexibility
 Polyethylene terephthalate
• Polyethylene terephthalate (aka PET, PETE or
the obsolete PETP or PET-P) is a thermoplastic
polymer resin of the polyester family.
 applications
used in synthetic fibers; beverage, food and
other liquid containers; thermoforming
applications; and engineering resins often in
combination with glass fiber. It is one of the
most important raw materials used in man-
made fibers.
 Polystyrene
Polystyrene is a polymer made from the
monomer styrene, a liquid hydrocarbon that is
commercially manufactured from petroleum
by the chemical industry.
At room temperature, polystyrene is normally a
solid thermoplastic, but can be melted at
higher temperature for molding or extrusion,
then re-solidified.
 Polycarbonate

• Polycarbonates are a particular group of

thermoplastic polymers. They are easily
worked, molded, and thermoformed;
 applications
• these plastics are very widely used in the
modern chemical industry. Their interesting
features (temperature resistance, impact
resistance and optical properties) position
them between commodity plastics and
engineering