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POLYMER
ENGINEERING
PN SURIANA BINTI ISMAIL
POLYMER ENGINEERING
CHAPTER 1 : INTRODUCTION TO POLYMER
CHAPTER 2 : POLYMER SYNTHESIS
CHAPTER 3 : PROPERTIES OF POLYMER
CHAPTER 4 : POLYMER ADDITIVES AND REINFORCEMENT
CHAPTER 5 : POLYMER MATERIALS
CHAPTER 6 : POLYMER PROCESSING
CONTINUOUS ASSESSMENT
 TEST 2X 20%
 TEST 1 CHAPTER 2 & 3
 TEST 2 CHAPTER 4 & 5

 QUIZ 2X 10%
 QUIZ 1 CHAPTER 1 & 2
 QUIZ 2 CHAPTER 4 & 5

 PRESENTATION CHAPTER 6 1X 5%

 END OF CHAPTER 2X 15%

 EOC 1 CHAPTER 3 & 4

 EOC 1 CHAPTER 5 & 6

INTRODUCTION TO POLYMER
WHAT IS A POLYMER ?
 Polymers are a special kind of macromolecule
 The word polymer comes from the Greek words
 “poly” =“many”, and “meros” meaning “parts” or
“repeating units”
INTRODUCTION TO POLYMER
 Polymer have influenced our life style in such away
that it would not be wrong to say that we are in
polymer age.
 These are so frequently use by people that a common
man calls them by names like plastics, fibres, rubbers
resins etc.
TODAY IT IS VERY DIFFECULT
TO CONSIDER A WORLD
WITHOUT POLYMERS!!!!
HISTORY OF PLASTICS
 1839

Charles Goodyear

Discovered the process for vulcanizing natural rubber

 1868

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licensed under CC BY-SA
Celluloid was invented by John Wesley Hyatt. This is considered to be the first
plastic, because it was made by substantially modifying a natural polymer and
then molding the resulting material into new shapes.
 1909

Dr. Leo Baekeland

Leo Hendrik Baekeland seems to have been the first person to use the term “plastic materials” to describe
products made from macromolecules (resins, elastomers and artificial fibers). That was in 1909. Two years earlier,
he had invented the first synthetic plastic: bakelite(first synthetic plastic)
 Bakelite

Radios, telephones and electrical insulators were made of

Bakelite in the past due to its insulating and heat-resistant
properties.
 1924
Hermann Staudinger

The polymer chain structure for synthetic polymers was proposed

by Hermann Staudinger
The main inventions in the world of plastics occurred between
the two World Wars: cellophane in 1913, then polyvinyl chloride
in 1927, polystyrene and nylon in 1938, and polyethylene in
1942.

A symbol of the “American way of life”, Tupperware first

appeared in 1946.
DEFINITION
Polymers
A polymer is a large molecule of high molecular weight
obtained by the chemical interaction of many small
molecules of low molecular weight of one or more type.
Monomers
Small molecules of low molecular weight, which
combine to give a polymer, are 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
Degree of polymerization (n): The number of monomers

used in the process is called degree of polymerization

DP affects properties of the polymer: higher DP increases

mechanical strength but also increases viscosity in the

fluid state, which makes processing more difficult

 Functionality: The functionality of a monomer is the
number of sites it has for bonding to other monomers
under the given conditions of the polymerization
reaction.
 Thus a bifunctional monomer, i.e., monomer with
functionality two, can link to two other molecules
under suitable condition
When the functionality of monomer is two bifunctional linear (or) straight

chain polymer is formed. Example : HDPE (high density polythene)

When the functionality of monomer is three (tri-functional), three-

dimensional net work polymer is formed. Examples : Urea formaldehyde,

phenol formaldehyde.

when a trifunctional monomer is mixed in small amounts with a

bifunctional branched chain polymer is formed. Example : LDPE (LOW

density polyethene)
EXAMPLE

Polyethene is a polymer formed- by linking together of a

large number of ethene (C2H4) molecules

n = degree of polymerization (DP).

PLASTIC
 Polymer whose fundamental property is
plasticity (thermoplastic). It is deformed
plastically under the action of pressure and or
heat .
 Mixture (of a polymer with additives) that can be
transformed by flowing or moulding in liquid or
molten state.
 CLASSES OF POLYMER

THERMOPLASTI
THERMOSET ELASTOMER
C

CRYSTALLINE AMORPHOUS
CLASSES OF POLYMER
 Thermoplastic: a polymer that can be melted and
molded into a shape that is retained when it is
cooled
 Thermoset: a polymer that can be molded when it
is first prepared but, once it is cooled, (sometime
called “curing”) hardens irreversibly and cannot be
remelted
 Elastomers: These are rubber – like solids with elastic
properties.
 In these elastomeric polymers, the polymer chains are
held together by the weakest intermolecular forces.
 These weak binding forces permit the polymer to be
stretched.
 A few ‘crosslinks’ are introduced in between the chains,
which help the polymer to retract to its original position
after the force is released as in vulcanised rubber.
EXAMPLES OF POLYMERS
Thermoplastics:
Polyethylene, polyvinylchloride, polypropylene, polystyrene,
and nylon
Thermosets:
Phenolics, epoxies, and certain polyesters
Elastomers:
Natural rubber (vulcanized) Synthetic rubbers
CRYSTALLINE VS AMORPHOUS THERMOPLASTIC

Amorphous = The polymer chains are in

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random arrangement
The crystalline region (crystallite) has an
orderly arrangement of molecules. The
higher the crystallinity, the harder, stiffer, and
less flexible polymer
Both amorphous and crystalline areas can
exist in the same polymer
Density (crystalline polymer) > density
(amorphous polymer)
CHARACTERISTICS OF POLYMERS
 Polymers are semi-crystalline materials. They have both
amorphous and crystalline regions. In fact, polymers have
regions of crystallinity, called crystallites, embedded in
amorphous regions. Crystallites provide strength and
hardness and the amorphous regions provide flexibility to the
polymeric material.
 Combustible materials.
 Show excellent resistance to corrosion.
 Polymers are very light in weight with significant degrees of
strength
 Polymers can be very resistant to chemicals
 Polymers can be both thermal and electrical insulators
 Polymers can be processed in various ways to produce thin
fibers or intricate parts.
 Packaging

Entertainment Medical

USES OF
POLYMER
S

Recreationa
Housewares
l
APPLICATIONS FOR POLYMERS
Industrial

1. Building and Construction

2. Electrical, Electronics and Telecommunications

3. Engineering

4. Furniture

5. Medical

6. Packaging

7. Textiles

8. Transport
APPLICATIONS FOR POLYMERS

Agriculture
1. Water conservation and management
a. Reservoir and irrigation lining
b. Water tanks and containers
c. Mulching
d. Pipe for drip and sprinkler irrigation

2. Plastics covered tunnels

e. Plastics covered tunnels
f. b. Green house covers 3.

3. Production collection and packaging

4. Fertilizer, pesticides packaging, transport and distribution
5. Livestock
6. Machinery and Tools
 Polymer Polymerization
structure mechanism

Physical or
Sources of mechanical
polymer properties
CLASSIFICATION
OF
POLYMER
BASED ON THEIR SOURCES

Natural polymers
The polymers, which are obtained from natural sources such
as plants and animals, are called natural polymers.
also known as biopolymers
Examples Wood, cellulose, Jute, Cotton, Wool, Silk,
Proteins, Natural rubber etc.
BASED ON THEIR SOURCES

Natural polymers
BASED ON THEIR SOURCES

Semi synthetic polymer

They are the chemically modified natural polymers such as
hydrogenated, natural rubber, cellulosic, cellulose nitrate,
methyl cellulose, etc.
Synthetic polymers
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.
POLYMER STRUCTURE

a) A more important classification of polymers is based

on molecular structure.

b) According to this system, the polymer could be one

of the following:
Linear chain polymer
Branched chain polymer
Network or gel polymer
LINEAR POLYMERS
 These are the polymers in which the monomer units are
linked to one another to form long linear chains.
 Only bifunctional monomers can form linear polymers.
 They are generally thermoplastic polymers
(polyethylene, and polyvinyl chloride )
LINEAR POLYMERS
 These linear chains are closely packed in space.
 The close packing results in high densities, tensile
strength and high melting and boiling points.
 Example high density polyethene, nylon and
polyesters are linear polymers
BRANCHED CHAIN POLYMERS
 The monomer units are linked to form long chains with
some branched chains of different lengths with
source.
 As a result of branching, these polymers are not
closely packed in space.
 They have low densities, low tensile strength as well
as low melting and boiling points.
BRANCHED CHAIN POLYMERS
 Some common examples of such polymers are low
density polyethene, starch, glycogen etc.
 Branching may create several physical properties in a
polymer such as decrease of solubility in solvents,
rise in the softening point
EFFECT OF BRANCHING ON PROPERTIES

 Thermoplastic polymers always possess linear or

branched structures, or a mixture of the two
 Branches increase entanglement among the
molecules, which makes the polymer:
Stronger in the solid state
More viscous at a given temperature in the plastic
or liquid state
CROSS-LINKED POLYMERS
 The monomer units are linked together to form three
dimensional network.
 The monomers contain strong covalent bonds as they
are composed of bi-functional and tri-functional in
nature
CROSS-LINKED POLYMERS
 These are expected to be quite hard, rigid and brittle.
 Examples of cross linked polymers are Bakelite (used
in electrical insulators), melamine-formaldehyde
polymer etc.
EFFECT OF CROSS-LINKING ON PROPERTIES
 Thermosets possess a high degree of cross-linking, while
elastomers possess a low degree of cross-linking
 Thermosets are hard and brittle, while elastomers are elastic
and resilient
 Cross-linking causes the polymer to become chemically set
The reaction cannot be reversed
The polymer structure is permanently changed; if heated,
it degrades or burns rather than melt
NETWORK POLYMERS
 Networked polymers are complex polymers that are heavily
linked to form a complex network of three-dimensional
linkages.
 These polymers are nearly impossible to soften when heating
without degrading the underlying polymer structure
 Example thermosetting polymers, such as epoxies and
phenolics
Direction of Increasing strength
 Polymers can be homopolymer or copolymer when the number of
monomers are one and two respectively.
 Polymers formed from the same type of monomers are called
homopolymers
 Polymers formed by combining different monomers are called
Copolymer

 The chains of co-polymer consist of repeating units derived from each

monomer. Following are some common types of co-polymers :

(a) Alternating co-polymers

(b) Block co-polymers

(c) Random co-polymers

(d) Graft co-polymers

Alternating co-polymers
 The different repeating units alternate in each
chain.
 If A and B represent two different units then an
alternating co-polymer will be represented as,

-ABABABAB-
Random Co-polymers
 In this type of copolymers, the different repeating units
are not arranged in a systematic manner but are
randomly arranged,
-ABAABABBAAABA-
 Eg; commercial copolymers of butadiene and
acrylonitrile
Block Co-polymers
 In such copolymers, block of repeating units of one
type alternate with block of another type, e.g. SBS
(styrene-butadiene-styrene)
-AAAABBBBAAAABBBB-
Graft Co-polymers
 In such co-polymers, blocks of one repeating
units are attached or grafted to a block of linear
polymer, e.g. High impact polystyrene
TACTICITY(Stereoisomerism)
 The orientation of monomeric units or functional groups
in a polymer molecule can take place in an orderly or
disorderly manner with respect to the main chain is
known as tacticity
 The difference in configuration (tacticity) do affect their
physical properties.
ISOTACTIC POLYMER
 If the groups attached to the carbon are arranged on the same
side of the main chain, the polymer is called Isotactic polymer.
 The best example is polypropylene.
 Isotactic polypropylene has excellent mechanical properties
ATACTIC POLYMER
 If the groups attached top the carbon chain are arranged
randomly, the polymer is called Atactic polymer.

Can’t Crystallize
SYNDIOTACTIC
 If the groups attached to the carbon chain are
arranged in an alternating side of the main chain,
the polymer is called Syndiotactic polymer.
POLYMERIZATION MECHANISM
Polymers can also be classified on the basis of
mode of polymerization into two sub groups.
 Addition polymers
 Condensation polymers
ADDITION POLYMERS

 The addition polymers are formed by the repeated addition of

monomer molecules possessing double or triple bonds, e.g, the
formation of polyethylene (polyethene) from ethene and
polypropene from propene.
 The addition polymers formed by the polymerization of a single
monomer species are known as homopolymers, e.g., polythene.
ADDITION POLYMERS

 The polymers made by addition polymerization

from two different monomers are termed as
copolymers, e.g., Buna-S, Buna-N, etc
CONDENSATION POLYMERS

 The condensation polymers are formed by repeated

condensation reaction between two different bi-
functional or tri-functional monomeric units.
 In these polymerization reactions, the elimination of
small molecules such as water, alcohol, hydrogen
chloride, etc. take place.
 The examples are terylene (dacron), nylon 6, 6, nylon
6,10 etc.