MSE 355 POLYMER PROCESSING

• Reference Books
• The Elements of Polymer Science and Engineering by
Alfred Rudin
• Principles of Polymer Processing by Z. Tadmor & C.G.
Gogos
• Materials Science & Engineering, An introduction by
William Callister Jr
• Introduction to Materials Science & Engineering by J.F.
Shackelford
• Plastics Engineering by R.J. Crawford; Pergamon Press

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 COURSE OBJECTIVE

To enable students;
• Classify polymeric materials
• Conversant with polymer processing
techniques

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 MARKS

• 70% exams
• 15% Midsem
• 10% coursework
• 5% Quiz

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 Polymer Science
• Polymer Technology always precedes Polymer
Science
• Mastication of rubber (to spread on cloth) in
1820
• Patents on vulcanization 20 years later
• Structure of natural rubber determined 100
years later

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 Definitions in Polymer Science
• Polymer: The word means ‘‘many parts’’.
• Designates a large molecule made up of small
repeating units
• Structure of polystyrene

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 Definitions
• Macromolecule is a synonym for polymer.
Have molecular weight greater than 5000

• Monomer: a molecule which combines with

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 Definitions
• Oligomer: oligomer is a low-molecular-weight
polymer.
• Will contain at least two monomer units.
• Hexatriacontone (n-CH3-(CH2)29-CH3) –
oligomer of polyethylene
• ~CH2-CH2- CH2- CH2~
• Oligomeric articles do not have practically
useful strength

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 Definitions
• Greek roots of these terms
• Meros part;
• Oligo few
• Poly many
• Mono one

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 Repeating Unit
• Repeating Units: portion of the
macromolecule such that the complete
polymer except for the ends might be
produced by linking together a sufficiently
large number of these units

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 Repeating Unit
• Comprises a single identifiable precursor e.g.
polystyrene

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 Repeating Unit
• Or composed of the residues of several
smaller molecules e.g. poly(hexamethylene
adipamide) – Nylon 6,6

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 Repeating Unit
• The repeating unit may not be necessarily
generated from molecules whose structures
are essentially those being repeated e.g
polyvinyl alcohol

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 Repeating Unit
• Expected starting material is

• Rather starting material is vinyl acetate

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Repeating Unit

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Repeating Unit

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 Repeating Unit
• End Groups
• The exact nature of the end group is
frequently unknown

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 Degree of Polymerization
• The degree of polymerization indicates the
average number of mers or repeating units in
the polymer molecule.
• Relation between degree of polymerization
and molecular weight M is given by
• M = (DP) Mo
• Mo= formula weight of the repeating unit

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 Degree of Polymerization
• Polymerization: a chemical reaction in which
the product molecules are able to grow
indefinitely in size so long as reactants are
supplied

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 Functionality
• The functionality of a molecule is the number
of sites available for bonding to other
molecules under the specific conditions of the
polymerization reaction
– Bifunctional monomer

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 Functionality
• Polyfunctional monomer can react with more
than two other molecule e.g. Divinyl benzene

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 Functionality
• a-functional monomer reacts with a b-
functional monomer in a nonchain reaction to
yield product molecule with functionality of
a+b-2
• bi – or polyfunctionality is a necessary, but not
sufficient condition for polymerization to
occur

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 Functionality
• E.g. propylene has a functionality of 2 in
reactions involving the double-bond
• Free radical reactions do not produce
macromolecules
• But polymerization in heptane at 70˚C with
Al(CH2CH3)2Cl/ TiCl3 catalyst yields high
polymers

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 Latent Functionality
• Latent Functionality: functional groups that
react under different conditions e.g
vulcanization
• Latent functionality allows chemical reactions
on polymers after they have been shaped into
desired forms

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 Latent Functionality
• E.g of Latent functionality
• Isoprene can be polymerized at about 50˚C in
n – pentane with either
– butyl lithium or
– titanium tetrachloride/ triisobutyl aluminum
catalysts

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 Latent Functionality
• Product is cis form of 1,4 – polyisoprene

• Double bond reacts with sulfur during

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 Latent Functionality
• Vulcanized rubber

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 Epoxy
• Epoxies
• Epoxy polymers are used mainly as
– adhesives,
– surface coatings and
– in combination with glass fibres or cloth, as light
weight, rigid structural material
• The conversion of an epoxy polymer to an
interconnected network structure is formally similar
to the vulcanization of rubber

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 Epoxy
• Termed “curing”
• More polar and more highly hydrogen-bonded
molecules form stronger articles at lower
degrees of polymerization as shown in
following figure
• Polyamide
• Epoxy

• Olefins
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 Epoxy
• Polymeric articles and molecular weight,
– A – Polyamides B – Epoxy and phenoxy
polymers C – Olefin polymers
A crude, but useful, generalization
of this concept can be seen in Fig.
1-1,
where a mechanical property is
plotted against the average number
of repeating
units in the polymer. The property
could be the force needed to break
a standard
specimen or any of a number of
other convenient characteristics.
The intercepts
on the abscissa correspond to In general, the more polar and more highly
molecular sizes at which zero hydrogen-bonded molecules
strength would be form stronger articles at lower degrees of polymerization
detected by test methods normally
used to assess such properties of
polymers.
(Finite strengths may, of course,
exist at lower degrees of
polymerization, but
they would not be measurable
without techniques which are too
sensitive to be
useful with practical polymeric
materials.) "Zero-strength"
molecular sizes will
be inversely related to the strength
of intermolecular attractive forces,
as shown in
the figure
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 Copolymers
• Homopolymer is a macromolecule derived
from a single monomer

• Copolymer contains structural units of two or

• Random Copolymer one in which the

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 Copolymers
• Alternating Copolymer
• Each monomer of one type is joined to
monomers of a second kind e.g. polymer
made from styrene and maleic anhydride
(SAN). ---ABABABABABAB---

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 Copolymers
• Graft Copolymer: Formed by growing one
polymer as branches on another preformed
macromolecule.
• E.g. graft copolymer is impact – resistant
polystyrenes

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 Copolymers
• Block Copolymers: comprise 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
• For example, polystyrene-b-poly(methyl
methacrylate) or PS-b-PMMA (where b =
block)

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 Copolymers
• Usually made by first polymerizing styrene,
and then subsequently polymerizing methyl
methacrylate (MMA) from the reactive end of
the polystyrene chains.

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 Classification of Polymers
• Many possible ways to classify polymers
according to
a) Source of the product such as
– Naturally-occurring polymers.
– Entirely synthetic macromolecules.
– Those derived by chemical modification of
naturally-occurring polymers.
b) Chemical structure
– Polyolific – alkenes
– Polyamide

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 Classification of Polymers
c) Polymer texture during use
– Rubbery
– Glassy
– Partially crystalline
d) Area of application
– Adhesive
– Fiber etc.
e) Method of production
– Addition
– Condensation polymers

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 Polymers
• Pure polymeric materials are the polymers
• Three polymer types
– Thermoplastics
– Thermosets
– Elastomers
• Additives to turn polymers into plastics
• Two important classes of plastics;
– Thermoplastics materials
– Thermosetting plastic materials

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 Polymers
• Advantages of plastics:
– Lightness
– Resilience
– Resistance to corrosion
– Colour fastness
– Transparency
– Ease of processing, etc

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 Polymers
• Natural polymers
– Silk
– Shellac
– Bitumen
– Rubber
– Cellulose
• Have long chain-like molecules
• 2 classes of plastics
• Thermoplastics and Thermosets
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 Thermoplastics
• Undergo cycles of heating and cooling
• (1) Polyethylene(PE)
• (2) Polyvinyl chloride (PVC)
• (3) Polystyrene (PS)
• (4) Nylon
• (5) Cellulose acetate
• (6) Acetal
• (7) Polycarbonate
• (8) Polymethyl methacrylate (PMMA)
• (9) Polypropylene (PP)
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 Thermoplastics
• 2 classes of Thermoplastics
• Crystalline (ordered), e.g polyethylene, nylon.
• Amorphous (random), e.g acrylic, polystyrene
• Degree of crystallinity is dependent on the
thermal history
• Characteristics of crystalline plastics
– Always opaque and
– Exhibit a relatively large shrinkage during
moulding

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 Thermoplastics
• Some advantages of high crystallinity
– High rigidity, especially at elevated temperatures.
– Low friction, hard wearing.
– High hardness.
– Increased resistance to environmental stress
cracking.
– Can be effectively reinforced.
– Ability to be stretched.
– Greater creep resistance

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