ENT4162-Polymer Materials

Eng. J.W. Achini

B.Sc. Eng.(Moratuwa),AMIE (SL), A.Eng.(SL)
Lecturer,
Department of Engineering
Technology, Faculty of Technology,
University of Ruhuna.
TOPICS
Module Introduction
• Course Unit Code : ENT 4162
• Course Unit Title : Polymer Materials
• Credits :2
• Lecture Hours : 30 hours
• Grading Percentage for final grade :
Continuous Assessment (CA) : 40%
End Semester Examination: 60%
Eligibility to sit for the End Semester Examination
1. Minimum 80% attendance for lecture participation
2. Minimum 50% marks from continuous assessments

•Continuous Assessment (CA) ….40%

Tutorial / Assignment Submission : 10%

Quizzes: 10%
Mid Semester Examination : 20%
Course Unit Objectives

This lesson intends to provide the rationale for the following;

•Demonstrate their understanding of the fundamental concepts of the range of

commonly used polymer processing methods and the associated polymeric
materials.
•Demonstrate the understanding of the basic theories of polymer product
manufacturing processes and inform on their limitations.
•Introducing the techniques and providing skills to select appropriate polymer
materials, machines and process equipment for manufacture
Course Unit Learning Outcomes

After completing this course Unit, students would be able to,

1.LO1: Demonstrate good understanding of different range of commonly used polymer
processing methods.
2.LO2: Describe the physical properties of the associated polymeric materials, different
behaviours of the polymer under different temperatures.
3.LO3: Ability to use the methods of analysing the industrial problems through polymer
engineering fundamentals & suggest solution for them.
4.LO4: Explain the basic theories of polymer product manufacturing processes and inform
on their limitations and environmental issues of them
5.LO5: Demonstrate good understanding of techniques and providing skills to select
appropriate polymer materials, machines and process equipment for manufacturing.
 Module will Cover
• Introduction to polymer science: Classification of polymers: Thermoplastics, Thermosets and Elastomers. Polymer
Structure: Copolymers, Tacticity
• The Synthesis of High Polymers: Polymerization Mechanisms: Step-Growth, Chain-Growth. Polymerization
Techniques: Bulk, Solution, Suspension and Emulsion
• The Solid-State Properties of Polymers : Amorphous & Crystalline states, Solubility, Electrical Property, Optical
Property, barrier properties and Mechanical Property
• Commodity Thermoplastics, Fibres, thermosets and Elastomers: Polyolefins, Vinyl polymers, Thermoplastic
polyesters, Synthetic fibres, Epoxies, Formaldehyde Resins, Diene Elastomers, Nondiene Elastomers,
Thermoplastic Elastomers
• Polymer Processing and Rheology: Extrusion: Pipe, Blown, Film , Flat Film, Injection Moulding, Blow Moulding :
Extrusion, Injection and Stretched, Calendaring, Thermoforming, Introduction to Polymer Rheology
• Introduction to Polymer Engineering: Rubber Elasticity, Viscoelasticity, Rheology of Plymers, Morphology of
Polymers, Yield and Fracture
• Rubber Technology: Compounding Ingredients, Rubber Compounds, Mixing Extrusion, Calendaring, Injection
Moulding, Compression Moulding, Transfer Moulding, Vulcanization, Rubber-Textile Composites
• Surface Engineering
• Design and Fabrication of Polymer Products
• Degradation, Stability and Environmental Issues: Polymer Degradation and stability , The management of plastics
in environment
Recommended Books
• Mills NJ , Plastics, Butterworth-Heinemann, 2004
• Joel R. Fried, Polymer Science and Technology, Prentice Hall, 1995
• Patton, William J, Plastic Technology
• Nutt, Merle C, Metallurgy and Plastic for Engineers Newman, Thelma R,
Plastics
What is a Polymer?
The word polymer is derived from classical
Greek

poly
meaning “many” and
meres
meaning “parts.”
The unit in square brackets is called
Thus, a polymer is a large molecule the
(macromolecule) built up by the repetition of repeating unit.
small chemical units.
Molecular Arrangement of Polymers
 Most polymers are large linear macro-
molecules.
 This chain is called the backbone.
 Normally, some of these atoms in the
chain will have small chains of atoms
attached to them. These small chains are
called pendant groups.
 Pendant chains normally have just a few
atoms, but the backbone chain usually has
hundreds of thousands of atoms.
Polymers have a Repeating Structure
 We like to think that the atoms that
make up the backbone of a polymer
chain come in a regular order, and this
order repeats itself all along the length
of the polymer chain.
 For example, in polypropylene, the
backbone chain is made up of just two
carbon atoms repeated over and over
again.
The Structure of Polymers
 Below is a diagram of polyethylene, the simplest polymer
structure

 There are polymers that contain only carbon and

hydrogen.
 These are referred to as hydrocarbons-exs.
Polypropylene, polybutylene, polystyrene, and
polymethylpentene
The Structure of Polymers
 Even though the basic makeup of many polymers is carbon and hydrogen,
other elements can also be involved.
 Oxygen, chorine, fluorine, nitrogen, silicon, phosphorous, and sulfur are other
elements found in the molecular makeup of polymers.
 Polyvinyl chloride (PVC) contains chlorine.
 Nylon contains nitrogen.
 Teflon contains fluorine.
 Polyester and polycarbonates contain oxygen.
 There are also some polymers that, instead of having a carbon backbone, have
a silicon or phosphorous backbone.
 These are considered inorganic polymers.
 Polysiloxanes (Silicones) and Polyphosphazenes
Polyethylene
 Homopolymer

Vinyl Polymers  If X=H then polyethylene

 If X = CH3 then polypropylene

 Vinyl polymers are polymers made from  If X = Cl then polyvinylchloride

vinyl monomers; that is, small molecules  If X = Benzene ring then

polystyrene
containing carbon-carbon double bonds.
H H
 They make up largest family of polymers.
-C–C-
H X

polypropylene

polyvinylchloride polymethylmethacrylate
PTFE

polytetraflouroethylene
Chemical Structure of Some Common
Polymers

Poly(methylmethacrylate) Poly(vinylacetate) “PAVc”

“PMMA”

Poly(acrylate) “PAA”
Poly(vinylchloride) “PVC”
Chemical Structure of Some Common
Polymers

Poly(vinylidene Poly(ethylene oxide)“PEO”

chloride)“PAVc”

Poly(hexamethylene adipamide) Poly(caprolactam) “Nylon”

“Nylon 6,6”
Chemical Structure of Some Common
Polymers

Poly(ethylene terephthalate)“PET” Poly(carbonate)

Poly(dimethyl siloxane) Poly(methyl styrene)

 Assignment 1

1.Select 8 polymers of your choice.

2.Draw both the monomer and polymer structures for each polymer.
3.Write key applications for each polymer.
4.State specific reasons why the polymer is ideal for those applications

Submission: Neatly hand-written, Maximum two A4 pages(Write on both

sides), due by [3rd February 2025 – Bring to next lecture]. Write your index
number in the top write corner of the first page
Degree of polymerization (DP)
• The subscript designation, n, indicates the
number of repeating units in the polymer chain
(molecule). This is known as the

Degree of polymerization (DP).

• It specifies the length of the polymer molecule.
Basics of Polymer Structure
 What distinguishes polymers from other organic compounds is molecular
weight and dimension?
Polymerization Process
•Sequential Reactions: Monomers react in sequence to form larger molecules.
• Monomer → Dimer → Trimer → ….........→ Polymer.
• Reactions can occur between monomers, dimers, trimers, or other molecular species.
•Polymer Chain:
• Formed by linking repeating units, resembling links in a chain.
•Oligomers:
• Low-molecular-weight products (e.g., dimers, trimers, tetramers).
• Exhibit undesirable thermal and mechanical properties.
•Degree of Polymerization (DP):
• High DP is essential for useful material properties.
• Example:
• Polystyrene with DP = 7 → Viscous liquid (not useful).
• Commercial-grade polystyrene (DP > 1000) → Solid with desirable properties.
•Key Note:
• No clear boundary exists between oligomers and polymers.
Molecular weight (MW).
The degree of polymerization represents one way of quantifying
the molecular length or size of a polymer. This can also be done
by use of the term molecular weight (MW).

MW(Polymer) =DP X MW(Repeat Unit).

Unit =g/mol
Atomic mass of common elements List
H=1
C=12
N=14
O=16
F=19
​Cl=35.5
Molecular Weight Distribution in
Polymers •Polymer Samples: Comprise millions of molecules with

varying chain lengths due to random polymerization.

•Molecular Weight Averages:

•Number-average (Mn): Counts the number of molecules.

•Weight-average (Mw): Weighs contribution by molecule size.

•Polydispersity (Mw/Mn):

•Indicates heterogeneity in chain lengths.

•Ideal Polymers (e.g., Proteins): Mw = Mn (Monodisperse).

•Synthetic Polymers: Mw > Mn, broader distribution.

 Classification of Polymers
Polymers can be classified in many ways, Some of them are,

A. Natural vs. Synthetic

B. Polymer Structure
1. Linear, Branched, or Cross-Linked
2. Amorphous or Crystalline
3. Homopolymer or Copolymer
4. Thermoplastics, Thermosets and Elastomers
C. Polymerization Mechanism
D. Thermal Behaviour
E. Preparative Technique
F. End Use
 A) Natural vs. Synthetic Polymers
• Synthetic • Natural polymers occur in nature and
polymers are man made
polymers can be extracted.
• Examples • They are often water-based.
of synthetic polymers include
nylon, polyethylene, polyester, Teflon, • Examples of naturally occurring
and epoxy. polymers are silk, wool, DNA,
cellulose and proteins.
Classification- B. Polymer Structure
1. Linear, Branched, or Cross-Linked
Linear
Many thermoplastic polymers are built so their

molecules consist of many thousands of atoms

arranged into long linear chains. But they don't have
to be long straight chains.
Also we know that each such carbon to carbon

bond allows full rotation in both molecules, so that in

reality the chains are seldom extended to their full
contour length but are present in many different
shapes, or conformations.
Branched Polymers
 Not all polymers are linear in this way. Sometimes there are chains attached to the
backbone chain which are comparable in length to that backbone chain.
 Some thermoplastic polymers, like polyethylene, can be made in linear or branched
versions.
 This gives them a 2-D quality.

LDPE

HDPE

The branching increases the volume and thus reduces the density of the polymer.
Star Polymers
 Sometimes the ends of several
polymer chains are joined
together at a common center.
 Polymers like this are called star
polymers.
 They're often used as additives
or as coating materials.
Dendrimer
 Sometimes there is no backbone chain
at all.
 Sometimes a polymer is built in such a
way that branches just keep growing
out of branches and more branches
grow out of those branches.
 These are called dendrimers, from the
ancient Greek word for "tree".
Cross-linked Polymers
 Sometimes, both ends of the branch
chains are attached to the backbone
chains of separate polymer molecules.
 If enough branch chains are attached to
two polymer molecules, it can happen that
all of the polymer backbone chains in a
sample will be attached to each other in a
giant 3-D network.
 This is what happens in certain hydrogels,
polyelectrolytes, rubber, silicone and
certain polyurethanes.

secondary
bonding

Linear Branched Cross-Linked Network

Adapted from Fig. 14.7, Callister & Rethwisch 8e. 34
 2. Amorphous or Crystalline
The fundamental difference
between crystalline and amorphous
compounds is the arrangement of
their constituent atoms.

A crystalline solid has a long range

of ordered molecules and a sharp
melting point.

In contrast, an amorphous
compound has a short range of
ordered molecules and an irregular
arrangement of its atoms.
 Polymer Crystallinity (cont.)
Polymers rarely 100% crystalline
• Difficult for all regions of all chains to become aligned
crystalline
region

• Degree of crystallinity
expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase. amorphous
region
Adapted from Fig. 14.11, Callister 6e.
(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of
Materials, Vol. III, Mechanical Behavior, John Wiley
and Sons, Inc., 1965.) 36
3. Homopolymers & Copolymers
Polymers composed of only one repeating unit in the polymer
molecules are known as homopolymers.

Homopolymer
 If X=H then polyethylene H H
 If X = CH3 then polypropylene

 If X = Cl then polyvinylchloride -C–C-

 If X = Benzene ring then

polystyrene H X

n
Copolymers Adapted from Fig.
14.9, Callister &
Rethwisch 8e.

two or more monomers random

polymerized together
• random – A and B randomly
positioned along chain
• alternating – A and B
alternate in polymer chain alternating
• block – large blocks of A
units alternate with large block
blocks of B units
• graft – chains of B units
grafted onto A backbone

A– B–
graft
 4. Thermoplastics, Thermosets and
Elastomers
Thermoplastics:
Consist of flexible linear molecular chains that are tangled together like a
plate of spaghetti or bucket of worms. They soften when heated.
Thermosets:
Remain rigid when heated & usually consist of a highly cross-linked, 3D
network.
Elastomers:
Consist of linear polymer chains that are lightly cross-linked. Stretching an
elastomer causes chains to partially untangle but not deform permanently
(like the thermoplastics).