CH

Natural Sciences Tripos Part IB
MATERIALS SCIENCE
Course C: Polymers
Name .................................... College .........................

Prof. R. E. Cameron
Lent Term 2011-12
IB
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Materials Science Part IB Course C : Polymers
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Polymers are very commonly used materials, but the relationships between their
chemical structure, molecular conformations, and functional properties are far from
simple.
The unique properties of polymers stem from the single fact that the small molecular
units within them are not separate but connected together to form large
macromolecules. The resulting chain like molecular structure leads to new phase
behaviour, unique entropy driven mechanics and distinctive processing properties.
The course aims to give an understanding of the relationships between macromolecular
structure and the characteristic behaviour of polymeric systems.
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Natural Sciences Tripos Part IB: Materials Science and Metallurgy

Lent Term 2012
Course C: Polymers
Professor Ruth Cameron
Key general texts
Practicals and Question Sheets
Online Resources
PART I: INTRODUCTION, DEFINITIONS, IDENTIFICATION
1. Introduction
1.1 Background
1.2 Polymer Basics
1.3 Characteristic Structural Features of Polymers
2. Polymer Identification
2.1 Always Read the Label
2.2 Carry Out Some Simple Identification Tests
2.3 Apply Some More Sophisticated Laboratory Techniques
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PART II: POLYMER MOLECULES

3. How Are Polymers Made?
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3.1 Additional Polymerisation
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3.2 Step Growth Polymerisation
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3.3 Molecular Weight: Definitions and Measurement
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3.4 Thermosetting Polymers and Gels
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3.5 Rubbers (or elastomers)
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4. Configuration and Conformation
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4.1 Configuration
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4.2 Conformation
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4.3 Thermodynamics of Chain Conformation
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4.4 Thermodynamics of a Freely Jointed Chain: the random walk (Gaussian) Chain Model CH24
PART III: POLYMER STATES
5. The Glassy State and the Glass Transition
5.1 The Behaviour of Polymer Chains under Stress
5.2 Time and Temperature Effects
5.3 Determination of Tg
5.4 Factors Which Influence Tg
6. Rubber and Rubber Elasticity
6.1 The Concept of the Entropy Spring
6.2 Classical Theory of Rubber Elasticity
7. Crystal Structure and Organisation
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7.1 Polymer Crystals

7.2 Polymer Crystal Morphology
7.3 Chain Alignment in Speherulites
7.4 Polymer Crystal Nucleation
7.5 Measuring Polymer Crystallinity
7.6 Factors Which Influence Tm and the Degree of Crystallinity
7.7 The Relationship between Tg and Tm
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PART IV: POLYMERS IN PRACTICE

8. Mechanical Properties of Polymers
8.1 The Effect of Transitions on Properties
8.2 Yield and Fracture
8.3 Chain Alignment and drawing
9. Polymer Processing
9.1 Forming Processes for Thermoplastics
10. Case Studies in Polymer Selection and Processing
10.1 The Carbonated Drinks Bottle
10.2 Polystyrene Coffee Cups
Glossary of Terms
Question Sheets
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CG
CQ1, CQ2, CQ3
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Key general texts

I. W. Hamley, Introduction to Soft Matter, Wiley, 2000 [Pf55, UL: 360:7.c.200.1] Chapter 2:
Polymers
P. C. Painter and M. M. Coleman, Fundamentals of polymer science: an introductory text,
Technomic, 1994 [AN6a.58 TRIPOS]
N.G. McCrum, C.P. Buckley and C.B. Bucknall, Principles of polymer engineering, 2nd ed., Oxford
Univ. Press, 1997 [AN6d.57, AN6d.57a TRIPOS]
R.J. Young and P.A. Lovell, Introduction to Polymers, Chapman and Hall, [AN6a.40, AN6a.40
TRIPOS]
Texts on more specific aspects of polymers

Sadtler Research Laboratories The Infrared Spectra Atlas of Monomers and Polymers, Heyden &
Son, 1980 [AN6b.73] Polymer Identification by IR Spectroscopy
D.I. Bower Introduction to Polymer Physics, CUP 2002 [An6c.127] Polymer Crystallization
N.J. Mills, Plastics: microstructure, properties and applications, 2nd ed., Arnold, 1993 [AN6c.126]
Polymer Processing
Practicals and Question Sheets
CP1
Polymer Characterisation and Identification
Beginning 24/1/12 (after L3)
CP2
Rubber Elasticity and the Entropic Spring
CP3
Polymer Alignment and Crystallinity
There will be three question sheets (CQ1, CQ2, CQ3) issued for this course, which are contained in
the handout after the glossary of terms. Answer sheets will be posted online every week, beginning
2/2/12.
Online resources
Course page at http://www.msm.cam.ac.uk/teaching/partIB/courseC.php
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All lecture materials (handout, practical book, question sheets and answers) will be posted here
during the course, along with links to data and analysis tools for practical and question sheets.
Teaching and Learning Packages (TLPs) available at http://www.doitpoms.ac.uk/tlplib

In particular, the following are of direct relevance to this course:
Optical Microscopy and Specimen

Preparation
Introduction to Mechanical Testing
Examination of an Artefact (Polymer

Identification) (CP1)
Crystallisation of Polymers (CP3)
Polymer Basics (Introduction)
X-Ray Diffraction
The Glass Transition in Polymers

(CP3)
The Stiffness of Rubber (CP2)
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PART I
INTRODUCTION, DEFINITIONS, IDENTIFICATION
1 INTRODUCTION
1.1
Background
What are polymers and why are they interesting to a Materials Scientist?
Polymers are very commonly used materials, but the relationships between their chemical
structure, molecular conformations, and functional properties are far from simple.
The unique properties of polymers stem from the single fact that the small molecular units
within them are not separate but connected together to form large macromolecules. The
resulting chain like molecular structure leads to new phase behaviour, unique entropy driven
mechanics and distinctive processing properties.
In some cases, polymer structures are described as self-organising or hierarchical, with

properties emerging from the bottom-up rather than being designed from top-down.
Recent approaches in materials science (e.g. nanotechnology) seek to control this process
Industrially, polymers are a major class of engineering material that are widely used due to
their low cost and ease of processing (mainly injection moulding). Total volume (although
not mass!) of plastics produced exceeds metals very significant in the world economy
Applications: clothing (fibres), packaging (bulk and film), coatings (paints), adhesives (glues)
car industry (10% vehicle mass interiors, tyres, paint, engine parts), consumer applications
(CDs/DVDs), medical applications (implants, drug delivery, gloves), rubbers
Some examples of polymers

Simple thermoplastic polymers
Majority of common artefacts made from just five polymers (PE, PP, PVC, PS or PET)
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(Updated figures in 2008 are HDPE 15%, LDPE 22%, PP 22%, PVC 15%, PS 10% and PET 8%,
Total 38 million tonnes)
Block copolymers
Can form complex morphologies (e.g. patterned surfaces) with a length scale determined by
their molecular architecture. Used in medicine, materials science and nanotechnology
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1.2
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Polymers Basics
What is a polymer?
Very long organic molecules formed from large number of identical units vast majority in
use are synthetic macromolecules (exceptions: cellulose, leather, silk, wool, chitin, rubber)
Greek - poly = many - mer = part, share.
Most of you will have encountered polymers before, and the following is only a brief summary of
some of the nomenclature and concepts required for this course. Rather than review this now, we will
refer back to it in the context of polymer identification (section 2.1)
Action: if this material is unfamiliar to you, review the Polymer Basics TLP (you can
skip the sections on Copolymers, Synthesis and Molecular Weight for now)
and check you can answer the Quick Questions
There is also a Glossary of terms at the back of this handout (and are usually italicized the first time
they occur in the handout), and a list of common polymer structures and thermophysical data in the
Part IB Data Book (beginning of entry for Course C)
1.3
Characteristic structural features of polymers
Backbone
very important because its stiffness (resistance to bending and bond rotation) has a strong
influence on the polymer properties
Side groups
Side groups affect:
- chain flexibility - impede rotation (PE, PS)
- regularity affects crystallisation
- interactions between chains and sections of chain H-bonding
Side branches
e.g. low density PE (LDPE) has some long branches and about 3 short branches (2-4 atoms
long) per 100 C in main chain. (density 0.91 g cm3)
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High density PE (HDPE) has no long chain branches and fewer short chain branches (< 1%
C). (density 0.96 g cm3). Side branches impede crystallisation.
Cross linking
Covalent links which form permanent joins between chains
Form a network by which every other chain is connected to every other

Chemical cross-linking radically changes the nature of the polymer
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on heating, chains of a non-cross linked polymer can slide over each other; it becomes a
viscous melt which solidifies again on cooling called a thermoplastic
if cross-linked, the polymer chains cannot slide to form a melt; the polymer remains solid
until bonds actually break and it is decomposed get a thermoset or a rubber
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POLYMER IDENTIFICATION
Very often, we are confronted by artefacts containing polymers that we would like to identify
This may be because we are interested in why a particular material was chosen, or because
we are trying to find out more about how the artefact functions (in a commercial scenario,
this could include reverse-engineering a competitors product!)
Before resorting to more elaborate laboratory techniques, there are some simple tests that can be
applied to rapidly identify most of the commonly occurring polymers. You can find an interactive
online version of this procedure in the Polymer Basics TLP.
2.1
Always read the label
(PETE = PET, V = PVC)
Many common polymer artefacts are segregated for recycling purposes, and are marked with
an appropriate label
Even chemically similar polymers like LDPE and HDPE must be segregated because of their
different physical structure (degree of branching) which may give rise to immiscibility when
combined in the molten state
It is especially important to separate halogenated hydrocarbons, such as PVC, which are very
immiscible with pure hydrocarbons and often contains additives (plasticisers) to soften them
2.2
Carry out some simple identification tests
There are a number of simple identification tests that can be carried out without the need for
expensive equipment, a subset of which is summarized in the flow chart below
There is a more extensive identification chart in the Artefact Booklet, containing a wider
range of thermoplastic polymers, and a separate identification chart for thermosets
Warning: although these tests are simple and low-risk, some involve potentially
hazardous procedures and should not be attempted without appropriate measures
to mitigate any risk (e.g. use of fume cupboard for burning or solvent testing)
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Lets now review some of these tests, to see how they are related to some of the basic features
of polymer structure reviewed at the start of section 2. Many of the themes we will return to
in more detail throughout the rest of the course (follow links to pages in handout).
(i)
Water test why do polymers have different densities?

An obvious answer is that they might contain elements with different atomic masses
(e.g. PVC has a higher density than PE) or side groups (e.g. PS has higher density
than PE)
A somewhat less obvious answer is that the degree of chain order (crystallinity) in
polymers varies greatly depending on their degree of branching (e.g. PP < LDPE <
HDPE in increasing order of branching, and the reverse for density)
For vinyl polymers, tacticity also affects the ease of crystallization
Question: do you think that (non-expanded) atactic PS will sink or float in
water?
Remember to clean sample thoroughly and submerge fully to eliminate any surface
tension effects or adsorbed air bubbles
Beware of filled polymers or composites, i.e. those containing inorganic particles with
a higher density (e.g. calcite, carbon/glass fibre), which can cause misidentification.
Can use thermal analysis (see section (c) below) techniques to check this.
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(ii)
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Copper wire test why do chlorinated compounds burn with blue-green flame?
Chlorinated compounds form a hydrated complex of copper (II) chloride which emits
a blue-green colour in the optical region, whereas non-chlorinated compounds do not
Remember to clean sample thoroughly to get rid of surface impurities
(iii)
Scratch test why is PP harder than HDPE which is harder than LDPE?
PP generally has a higher crystallinity than highly branched HDPE which has some
branches in the chain. LDPE has even more branches and hence an even lower
crystallinity.
(iv)
Solvent test why does MEK dissolve PS and not non-aromatic polymers?
Methyl ethyl ketone (MEK), or butan-2-one, contains phenyl groups that interact
strongly with those in PS and other aromatic polymers, promoting miscibility.
(v)
Oven/heat tests why do some polymers melt or soften at lower temperatures than
others?
Similar factors influence both melting and softening (glass transition, see CH25)
temperature of crystalline and amorphous polymers due their effect on chain packing
and/or conformational rearrangements
Question: which has higher melting point, LDPE or HDPE?
2.3
Apply some more sophisticated laboratory techniques

(i)
X-ray diffraction (XRD)

Spacing between polymer chains in polymers corresponds roughly to wavelength of
X-rays from Cu K or synchrotron source, so can obtain information about the
packing arrangements and identify from known samples in database (cf. identification
by powder X-ray diffraction for inorganic materials)
Complicated in polymers by presence of both amorphous and crystalline phases (see
CH39) obtain different results for amorphous, fibrillar or fully crystalline samples
(ii)
Thermal analysis (DSC, TGA)

We will discuss differential scanning calorimetry (DSC) for determining melting and
glass transition temperatures later in the course (see CH29)
Thermogravimetric analysis (TGA) gives the mass loss of sample as a function of
temperature, which is a signature of polymer and its physical state, and can also reveal
the presence and amount (by mass) of inorganic filler as non-degradable residue
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(iii)
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Infrared (IR) spectroscopy

Infrared radiation in the 625 to 4000 cm1 (20 to 120 THz) region corresponds to the
separation between adjacent vibrational energy states in organic molecules (caveat:
not every vibrational mode is excited, for reasons we wont discuss here)
We can use a plot of relative IR absorbance or transmittance to identify functional
groups present in polymer molecules, and also their structural environment (for
purposes of identification, we are mostly just interested in the former)
A selection of the most diagnostically significant bands for polymers is given below
Structural unit (compounds)
CH (alkanes)
CH (alkenes, aromatic rings)
CH (substituted phenyls)
>CO (alcohols, ethers, esters,
carboxylic acids)
> NH (amines)
> NH (amines)
C=C (alkenes)
C=C (aromatic rings)
>C=O (aldehydes, ketones)
>C=O (carboxylic acids)
>C=O (esters)
>C=O (amides)
CN (nitriles)
CC (alkynes)
Frequency range [cm1]

2850-2950
3000-3100
680-840
1000-1200
3350-3500
1580-1650
1620-1680
1600, 1500 (weaker)
1710-1750
1700-1725
1730-1750
1680-1700
2240-2280
2100-2200
Excitation (peaks)
stretch (singlet)
stretch (singlet)
bend (singlet)
stretch (singlet)
stretch (singlet)
bend (singlet)
stretch (singlet)
stretch (doublet)
stretch (singlet)
stretch (singlet)
stretch (singlet)
stretch (singlet)
stretch (singlet)
stretch (singlet)
Can either match these bands by eye to a set of reference patterns (see The Infrared
Spectra Atlas of Monomers and Polymers in recommended reading list) or use
computer to match spectra to database of known polymers
Remember that band frequencies may vary by up to 10 cm1, and that the absence of
a particular band may be just as informative as its presence
Action: the above procedures should enable you to make a confident identification
of the polymers in your manufactured artefact, if any. Make sure you use them
judiciously, and discuss their interpretation with your supervisor if you are unsure.
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PART II
POLYMER MOLECULES
3.
HOW ARE POLYMERS MADE?
The chemical processes can be broadly classified according to the type of reaction involved.
These lead to different distributions of chain length and can be used in different ways to modify the
properties of the resulting polymer.
3.1
Addition Polymerisation (= chain polymerisation)
Growth process involves addition reactions is the normal method of synthesis for vinyl
polymers where monomer is CH2=CHX, e.g. vinyl chloride X=Cl, vinyl acetate X=CH3COO,
acrylonitrile X=CN, and polyolefins e.g. CH2=CH2, ethylene. Monomers all contain C=C
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Process involves 3 stages: initiation, propagation and termination of chain growth.

(i)
Initiation: the creation of an active centre, often a free radical centre with an unpaired
electron.
Initiation by heat or UV light or commonly by decomposition of a suitable initiator
molecule e.g. peroxide:
(ii)
Propagation: Initiator radical I reacts with a monomer molecule:
This step is exothermic (here H is 105 kJ mol1) which represents the difference in
energy between the C=C and the CC bonds. This is the main driving force for the
reaction, outweighing the entropy change.
Propagation occurs very fast therefore high concentration of monomer molecules and
the chain grows very rapidly. Typically 103 to 106 monomer units per second.
(iii)
Termination: Occurs when two reactive molecules combine to destroy their active
centres
e.g. mutual termination:
or disproportionation:
Growing chains can also form side branches (e.g. in polyolefins) by a backbiting reaction. The
unpaired radical at the end of the chain transfers to a backbone atom further down the chain, causing
a branch to propagate away from the main chain.
The chance of a growing chain meeting another is quite small. It is much more likely to meet a
monomer molecule. The reaction mixture consists predominantly of monomer and long dead chains.
The rate-controlling step is the initiation of the reaction.
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3.2
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Step Growth Polymerisation

Here the chain forms by the repetition of an elementary reaction which creates a single
linkage.
e.g. an ester linkage:
This is an example of a condensation reaction removal of a small molecule, in this case

water.
The reactive groups here:
are known as functional groups, defined as the sites in the monomer molecule at which bonds
form to other molecules during polymerisation. For chain growth, the monomers must each
have at least 2 functional groups (> 2 leads to cross linking and branching)
The number of functional groups is referred to as the functionality: e.g. bifunctional,

trifunctional etc.
Generally, the molecules involved in step growth are more complex than chain growth.
Typical linkages are:
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e.g. PET formed by condensation of terephthalic acid and ethylene glycol. (PET terelene
fibres, PET film).
In step growth, all polymer chains and monomer molecules have reactive groups present.
Their reactivity is independent of chain length (principle of equal reactivities), so we have
many possible reactions for monomers A and B.
A + B AB (with elimination of water)
AB + AB ABAB
or
AB + A ABA
ABAB + ABAB ABABABAB,
etc.
The distribution of chain lengths will be very different from chain growth, with many more
short chains and few long ones.
The Carothers theory relates the average chain length to the extent of reaction.
If
then:
p = extent of reaction = (no. of functional groups reacted) / (no. present initially),

p = probability that any given group has reacted.
no. groups reacted = (initial number) (final number) = N0 N
p = 1 N / N0
Mean chain length
= number average degree of polymerisation xn

= initial number of groups / final number of groups
= N0/N, since groups are eliminated by the reaction process.
So, xn = 1 / (1 p) i.e. as p 1, then xn
In any polymer there will be a distribution of chain lengths and hence molar masses typically
appears like a log-normal distribution.
3.3
Molecular Weight: Definitions and Measurement

Many different methods available to determine MW distribution (or average MW), all
indirect. Three of the most important are:
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(i)
Viscometry - measure viscosity of a solution of the polymer. Polymer chains are much
longer that the solvent molecules and increase the viscosity of solution. With suitable
calibration, viscometry can provides an average MW (not full distribution). Easy to carry out,
but crude method.
(ii)
Gel Permeation Chromatography (GPC) polymer solution flows along a column
packed with porous beads (often gel). Polymer molecules are trapped in the pores and the
time taken to pass through the column depends on the chain length. (Small molecules get
trapped travel slower due to more convoluted path).
Gives full MW distribution. Requires specialised equipment, but still moderately
straightforward.
(iii) Mass spectrometry (MS) polymer molecules are ionised and separated according to
their mass-to-charge (m/z) ratios. Ionisation can be achieved either through electro-spraying
(ESI) or using a laser (MALDI), and separation by magnetic field or time-of-flight (TOF)
measurements.
Gives very accurate MW distribution, but requires highly specialised equipment.
M N is the number average molecular weight, or mean of the number distribution:
where Ni is the number of molecules with molar mass Mi. M N is the sum of the products of
molar mass of each fraction with its mole fraction xi.
MW
is the weight average molecular weight, or mean of weight distribution:
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is the sum of the products of molar mass of each fraction with its weight fraction wi.
This gives a different distribution the relative importance of large molecules increased.
The ratio M W / M N is a measure of the spread of molecular weights called polydispersity
index.
MW
3.4
Thermosetting polymers and Gels

So far we have been looking at linear polymers without cross-links thermoplastics. But
some very important polymers are cross-linked thermosets and rubbers.
The very first commercial polymer was heavily cross-linked produced by reacting phenol
with formaldehyde. The presence of the OH group leads to high reactivity of phenol at the
ortho/para (2/6 and 4) positions.
After the first reaction, phenol can react further (2 more sites per molecule).
The phenol is trifunctional so reaction leads to a 3D network of phenol formaldehyde resin

(phenolic resin). Heavily cross-linked, very hard, dense stiff and brittle.
When partially reacted can be dissolved in solvent basis for lacquers.
Other thermosets based on condensation with formaldehyde are urea formaldehyde and
melamine formaldehyde. Used for electrical fittings, plastic tableware and foam insulation for
buildings.
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An important modern class of thermoset is epoxy resins e.g. Araldite.
Reaction between epoxy terminated chains and

polyfunctional hardener molecules (e.g. amines).
Starting reagents may have quite long chains

leads to good control over cross-link density and
properties. Used in adhesives and composites.
3.5
Rubbers (or elastomers)
Rubbers generally have much lower cross-link density than thermosets (discussed later)
Cross-links at intervals of 500-1000 monomers, prevent gross chain sliding. Process of

vulcanisation involves the production of cross-links by reaction of e.g. sulphur with polymer
chains.
polyisoprene (natural rubber)

[X = H]
polybutadiene (synthetic rubber)

[X = CH3]
Can have several S in linking chain. Other methods can involve C atoms as units, e.g.
peroxide activation. Can also get environmental attack of rubber by UV light or O3, causing
extra cross-linking.
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4.
CONFIGURATION AND CONFORMATION
4.1
Configuration
Molecular configuration is fixed at the time of synthesis.

The configurational isomerism concerns the arrangement of side groups in two ways:
(i)
Sequence
e.g. for simplest vinyl polymers:
(ii)
chain growth can be head-to-tail (most common):
or head-to-head:
Tacticity
This concerns the arrangement of side groups on the backbone

e.g. for PVC:
isotactic
(same side)
syndiotactic
(alternating sides)
atactic
(random)
Tacticity affects the ease of crystallisation. Regular chains (iso- and syndiotactic) can
crystallise, but randomness (atacticity) generally prevents it.
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For example, the bacterially-synthesized polymer PHB is perfectly isotactic, due to its
biological origin, which is one of the reasons why it crystallises so readily.
Tg = 4C
Tm = 195C
Tacticity is fixed by chain synthesis. No amount of chain rotation (i.e. change in

conformation) can alter it.
4.2
Conformation
The chain also can rotate around the CC bonds, producing a 3D structure.
The 3D arrangement of a polymer molecule is called its conformation, and can be represented
by a Newman projection - a diagram showing orientation of the chains and side groups
attached to one CC bond.
Circle represents one bond. Projection shows the view along bond.
e.g. we can represent isotactic PVC in all-trans conformation using a Newman diagram as:
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4.3
Thermodynamics of chain conformation
Amorphous polymer chains are not extended zigzags, as in crystalline lamellae with all bonds
in the trans conformation, but twisted and convoluted with a relatively large number of
gauche conformations at non-zero temperature.
The trans conformation is energetically favoured, but a disordered chain has higher entropy.
Angle of rotation from trans called the torsion angle.
The number of bonds in each state depends on the energy difference between each state and
the temperature of the molecule.
Consider the energy needed to twist one link: E = Eg Et 3 kJ mol1 (for PE).
Then, we expect the populations in the two states to be given by a Boltzmann distribution:
= 2 exp
, remembering to include the degeneracy factor of 2 for gauche states.
e.g. at 300 K, ng = 0.6 nt. Hence, at high temperatures, the chain conformation will be random.
We need to treat the overall length of the chain from end-to-end, statistically.
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4.4
Thermodynamics of a freely jointed chain: the random walk (Gaussian) chain model
You have seen a version of this analysis before in IA (BH19)
Consider a chain of n links each of length a. If it is a random walk, then the probability
density function of end-to-end distance, r:
3
b
2 2
P(r )
=
exp b r

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3
2na 2
where b =
Hence, probability of chain end being some distance r to r + dr from the origin is given by:
3
b
P=
(r )4
rd r
exp

2
( b r 4
)
2 2
rd2 r
1/2
Thus, r.m.s. length = r 2 P(r ) 4 r 2 dr

0
a n which is a standard result.

=
However, this model assumes that linkages are perfectly flexible. In fact they can only take
up specific conformations (trans and gauche). Also, the function predicts finite probability
for chains greater than the actual chain length.
Nevertheless, the general conclusion that r.m.s. length is proportional to n is still valid,
provided n is relatively large (n > 100, depending on stiffness of the monomer units)
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PART III
POLYMER STATES
THE GLASSY STATE AND THE GLASS TRANSITION
When we extend or compress a polymer we try to move the chain ends apart or together. For a
polymer chain to change its conformation, individual links must twist from trans to gauche or vice
versa. This requires energy and is a thermally activated process.
At a sufficiently low temperature, the conformation becomes frozen in. This is the glass transition
temperature (or Tg) and is very important as it leads to major changes in the polymer properties.
The glass transition is thus the temperature above which changes in chain conformation become
thermally activated by rotation of backbone segments about single bonds.
An activation energy is required for conformation change. Changes in conformation clearly depend
on T, but also on timescale.
5.1
The behaviour of polymer chains under stress
Below Tg, an amorphous polymer can change shape only by locally stretching, bending or
twisting intermolecular bonds. It is a glass and has a high elastic modulus determined by
intermolecular van der Waals forces. (E = 23.5 GPa).
Above Tg, shape changes can be accommodated by coiling and uncoiling of chains. The
material is rubbery, with a much lower elastic modulus (perhaps 0.1% of the value below Tg)
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Well away from Tg (above or below) the response to applied stress is rapid, but around Tg the
behaviour is sluggish. Conformations can change, but only slowly. There is a significant time
delay in responding to applied force and mechanical energy is dissipated as heat rather than
stored as elastic strain energy.
So, a polymer ball will bounce well, above or below Tg but not close to Tg.
So an amorphous polymer below Tg is glassy. Several polymers are used in this state we
call them glassy polymers.
e.g.
PS
PVC
Tg = 100 C
Tg = 80 C
Other amorphous polymers are used well above Tg in the rubbery state we call them
elastomers.
e.g.
polyisoprene (natural rubber) Tg = 75 C

polybutadiene (a synthetic rubber) Tg = 85 C
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5.2
Time and Temperature Effects
Amorphous materials above Tg show rubbery behaviour that depends on T and timescale,
since both influence twisting.
-
At very short loading times they can still be glassy (insufficient time for chains to move in
response to stress).
At intermediate times they may be rubbery very low elastic modulus and very large
recoverable elastic strains.
At very long times, the chains can move permanently past each other (chain sliding) like a
viscous liquid because activation energy for conformational changes is similar to energy for
chain sliding.
For a useful rubbery material (elastomer), we must suppress chain sliding, extending the
rubbery region. This is achieved by cross-linking, which is an irreversible chemical process.
5.3
Determination of Tg
(i)
Mechanical methods
Measure elastic modulus as a function of T, e.g. by torsion pendulum. Timescale

(frequency) of pendulum oscillation is important because Tg depends on time allowed
for chain segments to rotate.
Measure energy absorbed when specimen is deformed cyclically, plot energy loss per
cycle versus T (this quantity is also known as tan ).
CH28
These methods are the basis of DMTA (dynamic mechanical thermal analysis)
techniques.
(ii)
Volume methods
Changes in conformation require more volume.
CH28
The actual volume of the molecules stays the same through Tg, but the free volume
the volume through which they can move increases and so see an increase expansion
coefficient above Tg.
CH29
CH29
(iii)
Thermal methods
Since link motion requires extra energy, there is a change in enthalpy and specific
heat at Tg. Note that specific heat is larger above Tg due to the additional conformation
degrees of freedom that are activated.
This transition can be measured directly by calorimetry (DSC differential scanning

calorimetry). A small amount (e.g. mg) of polymer sample is encased in a thermally
conductive metallic sample holder (called a pan).
By making the polymer sample heat at the same rate as an empty reference pan, the
difference in thermal energy required to keep the two pans heating at the same rate
gives the heat flux, Q.
DSC measures the heat flux (Q = q/t [J/s]) in or out of a sample pan at a fixed heating
rate (T/t [K/s]).
q/t
q
= = Cp
Ratio of Q to heating rate gives:
T / t T
For a glassy polymer heated through Tg, we see change in the heat flux into polymer
sample as the torsional modes are activated. An increased heat input is required to
achieve a given rise in temperature above Tg.
Schematic DSC curve for
archetypical polymer.
We can also detect the crystallisation temperature Tc as an exothermic peak in the

graph of Q versus T. Crystallisation occurs as temperature increases because the
chains have enough thermal energy to rearrange into a regular lattice.
CH30
Similarly, melting will show up as an endothermic peak at Tm.
Notice difference between glass transition and melting/crystallisation peaks this is

because the latter are thermodynamically first order and involve a latent heat. The
area under DSC peak is related to the latent heat of transformation.
This is an extremely schematic picture, as the finer details such as position, intensity,
presence or absence, and number of Tg, Tc and Tm peaks depend very much on the
chemistry and structure of the polymer, as well as the heating/cooling rate.
5.5
Factors which influence Tg
Chain flexibility
Tg decreases with increasing flexibility
e.g.
PEEK Tg = 416 K
(less flexible)
PET Tg = 345 K
PE Tg = 153 K
(more flexible)
Side groups
Side groups hinder rotation and therefore increase Tg.
The increase is greater with bulky or polar side groups.
e.g.
PVC Tg = 353 K
CH30
PE Tg = 153 K
Chain length (or equivalently degree of polymerization or molecular weight)

Each chain end has some free volume associated with it, so shorter chains have more free
volume and hence a lower Tg.
Tg' for shorter chains will be lower
than for infinite chains
CH31
CH31
Branches
May either reduce Tg (since add chain end free volume) or hinder rotation (like large side
groups) and so increase Tg.
Plasticisers
Small molecules (typically esters) added to the polymer increase chain mobility, space out
chains, and hence reduce Tg.
e.g.
PVC cling film (plasticised) Tg << room temp

uPVC unplasticised Tg = 80 C
Crosslinking
Cross links reduce chain mobility and so increase Tg.
Crosslinking also suppresses chain sliding, extending the rubbery region. Cross-links at intervals of
500-1000 monomers, prevent gross chain sliding.
CH32
6.
RUBBER AND RUBBER ELASTICITY
6.1
The Concept of the Entropy Spring
CH32
Once above the glass transition, as we extend a polymeric material, the chains respond by twisting
the links between units, changing the overall chain conformations.
The extended chains now exist in a less probably conformation and there is an increasing retractive
force with extension.
When the load is removed, the chains will retract (on average) not to the same conformation, but to
roughly the same original length.
Extension of a rubber does not, therefore, involve stretching bonds the links are simply twisting
and untwisting. The internal energy of the bonds stays essentially the same. Instead, we are
changing the entropy of the chain by moving it from a more probable (high entropy) state to a less
probable (lower entropy) state.
The rubbery polymer behaves as an entropy spring.
6.2
Classical theory of rubber elasticity
We can describe quantitatively the origin of the rubber modulus using the random walk chain model
introduced in section 4.4, together with concept of conformational entropy of chain.
The conformational entropy is related to the number of different ways of arranging chain with
the same end-to-end distance, r, i.e.:
S=
kB ln , where is the total number of conformations with same r.
conf
But
P(r ) ,
which we assume takes the Gaussian form (CH24) at equilibrium.
Imagine that the chain trajectory between cross-links is random (i.e. not too many cross-links,
so n is still large between each cross-link point), then we model the affine deformation of the
whole network by considering what happens for just a single cross-link segment.
CH33
CH33
For a single cross-link segment, the change in conformational entropy S (dropping subscript
for clarity) between the equilibrium and extended conformations can be written as:
p

=
=
S kB ln
kB ln , where primed quantities refer to extended segment.
p
Now, if the deformation is small, then, defining the start of segment as the origin, the end of
segment translates from point ( x, y, z ) to ( x, y, z ) , and associated entropy change is:
} {( y) y } + {( z) z }
p
2
S =kB ln =kBb 2 ( x ) x 2 +
= kBb 2 ( 2x 1) x 2 + ( 2y 1) y 2 + ( 2z 1) z 2
where x, y and x are the extension ratios in the x, y and z-directions.
Since we assumed the original conformation was isotropic, then on average:

=
x2
=
y2
r 2 / 3 , but r 2 = na 2 as shown in CH24, and so following from above:
=
z2
2
3 r
S = kB
2x + 2y + 2z 3)
(
2
2
3
na
kB 2
= ( x + 2y + 2z 3)
2
Provided the deformation is uniformly distributed across the whole network, then the total
change in entropy is given by multiplying by the number of chain segments (or, equivalently,
cross-links) per unit volume, nseg:
nseg kB 2
2
2
S =
( x + y + z 3) ,
2
which is the general case, valid for small affine 3D deformations. Note that it is always
negative in sign i.e. deforming rubber away from random coil decreases its entropy.
Uniaxial deformation of rubber (for biaxial case, see CP2)
In the special case of uniaxial extension by a factor x, then y = z =1

to be incompressible (true to a good approximation for rubbers).
The entropy change thus becomes S =
nseg kB 2 2
3 .
x +
x
2
x for the material
CH34
CH34
To obtain the mechanical work required to deform the rubber, we calculate the change in the
free energy:
G =H T S
nseg kBT 2 2
x + 3 per unit volume,

2
x
since H is quite small compared to S (no bonds are being strained, only conformational
changes are required).
To obtain the force required to deform a sample of volume V, we take the gradient of the free
energy density with respect to the extension and multiply by volume:
nsegVkBT
G nsegVkBT 2 2
3
=
F V =
=
x +
2
x0
x
x
x
1
1
nseg AkBT x 2
x =
2
x
x
where x0 is the original length and A is the cross-sectional area of the sample.
This gives a formula for nominal stress of =
F
1
= nseg kBT x 2
A
x
Erubber nseg kBT
which agrees reasonably well with experiment for small extension ratios (x < 4).
The deviation occurs either when extensions become too large (chain conformation between
cross-links no longer random) or degree of cross-linking is too high (not enough monomers
between cross-links for random walk model to apply). It is not due to the full extension of
segments between cross-links (this would require much higher extension ratios)
It can be seen that, for modest extension ratios, the elastic response of the rubber is almost
Hookean, with Youngs modulus:
Erubber nseg kBT .
This is what is meant by the term entropic spring.
Notice that that the rubber modulus increases with temperature, as opposed to that for an
enthalpic spring in a conventional elastic solid (which decreases with temperature due to
anharmonicity of the interatomic potential), and is proportional to cross-link density.
CH35
CH35
7.
CRYSTAL STRUCTURE AND ORGANISATION
7.1
Polymer crystals
Many polymers are at least partially crystalline.
Crystalline regions contain regular packings of chains giving lower entropy but increased
inter-chain bonding compared with the amorphous fraction.
Formation of polymer crystals is largely dominated by kinetic considerations (fastest growth

rate, not lowest free energy).
e.g. PE crystallises in an orthorhombic P cell containing 2 chains parallel to the z-axis per
unit cell.
Bonding in the unit cell is highly anisotropic weak van der Waals to the chain but stiff
covalent to the chains
The chains need not be planar zigzags, e.g. isotactic PP and PTFE can form helices.
Cannot pack single molecules into single crystals over their whole length crystalline
polymers consist of relatively small crystallites separated by amorphous regions.
e.g. a typical polymer chain of 104 carbon atoms may crystallise only over lengths of ~100
atoms. Each chain wanders over lengths of several crystalline regions.
CH36
CH36
7.2
Polymer crystal morphology
Often crystalline regions are lamellar (= sheet-like).
Lamellae are separated by disordered amorphous regions.
Crystalline lamellae grow from the melt radially outwards from a nucleating site to form
spherulites.
Spherulites are roughly spherical regions containing radial crystalline lamellae and
amorphous material, originating from a common nucleating point (few microns to hundreds
of microns in size).
CH37
CH37
Lamellar ribbons may twist regularly leading to rings of birefringence when thin sections are
observed between crossed polars.
7.3
Chain alignment in speherulites
Polymer spherulites viewed between crossed polars show a Maltese cross pattern due to
radial alignment of lamellae with fast axes parallel to lamellar planes. When the lamellar axis
is parallel to one of the polarisers, one of the permitted vibration directions (PVDs) must be
normal, and hence there is extinction.
The lamellar ribbons twist regularly (rotating around the radial axis) as they emanate from the
centre of the spherulites, leading to rings of varying birefringence (known as banding): at
certain orientations one of the PVDs will be perpendicular to vibration direction of light.
CH38
CH38
7.4
Polymer crystal nucleation
As is also seen in metals, the number of nucleating events is greater at a higher undercooling,
giving a finer microstructure, with larger number of smaller spherulites.
At very high undercooling, solidification can occur before crystallite growth, leading to a
completely amorphous polymer.
CH39
CH39
Control of crystallinity and crystallite size is important as they influence: mechanical

properties, optical properties (transparency), gas permeability; etc.
e.g. in injection moulding, see a range
of microstructures close to the mould
wall.
7.5
Measuring polymer crystallinity
The degree of crystallinity of a polymer is never 100%.

(i)
Measurement of density
Can determine degree of crystallinity from measurement of density, since amorphous regions
have lower density than crystalline.
= C + (1 ) A
where is the volume fraction of crystalline phase.
- Deduce density of perfect crystal, C, from unit cell parameters

- Measure density of purely amorphous phase, A, from quenched state
- Assume linear relationship between densities of different phases: rule of mixtures
If required as mass fraction, use specific volumes (1/density) rather than densities of
crystalline and amorphous phases
(ii)
X-ray Scattering
Can also calculate degree of crystallinity via X-ray scattering measure area fraction of
amorphous to crystalline scattering in the trace.
CH40
CH40
Some uncertainty can arise over separation of crystalline and amorphous peaks, and also the
elimination of any background fog due to incoherent scattering (could be linear or constant in
angle). Also, assumes random orientation of polymer crystallites can give inaccurate results
for drawn or oriented polymer samples.
(iii)
Calorimetry
Calorimetry can also be used to measure crystallinity find heat absorbed on melting, which
must be due to crystalline fraction only (CH29).
Note that methods used to measure crystallinity often give different results due to the implicit
assumption of two phase behaviour often better to speak of a relative index of crystallinity
specific to each method.
7.6
Factors which influence Tm and the degree of crystallinity
Crystalline polymers have a more or less well defined melting point Tm however variations
in lamellar thickness lead to some differences for a given polymer.
Chain flexibility
Tm decreases with increasing flexibility, since greater flexibility gives less stable crystals.
e.g.
PPS Tm = 560 K
(less flexible)
PE Tm = 413 K
PEO Tm = 340 K
(more flexible)
Side groups
Tm increases with bulky side groups which reduce chain flexibility.
However, side groups reduce the ability to crystallise (though if isotactic they can pack as
helical chains). For this reason, PS and PMMA naturally amorphous.
Polar side groups can stabilise crystals by increasing interchain forces and therefore increase
Tm (e.g. nylons)
CH41
CH41
H-bonding stabilises molecular

stacking sequence
Also increases affinity for H2O
(acts as plasticizer for nylons)
Tacticity
Crystallisation is favoured by a regular chain structure (i.e. isotactic or syndiotactic). Atactic
polymers are therefore very reluctant to crystallise since chains do not pack closely.
e.g.
PP
isotactic typically 70% crystalline
atactic fully amorphous.
Copolymerisation
Alternating (regular) copolymers can crystallise (subject to tacticity etc). But random
copolymers ABBBABBBAAA will not too irregular. With block and graft copolymers with
long homopolymer regions, can get local crystallisation.
Chain length (or equivalently degree of polymerization or molecular weight)

Chain length has little effect on Tm, since it is normally much larger than the lamellar
thickness.
Branches
Small number of branches (especially if flexible) increase chain end volume and so lower Tm.
Large number of branches (especially if bulky) act as side groups stiffen chain increase
Tm. In all cases, branches inhibit the ability to crystallise.
e.g.
LDPE many branches 4070% crystalline.

HDPE fewer shorter branches, 7090% crystalline.
CH42
CH42
7.7
The relationship between Tg and Tm
Since both Tg and Tm are influenced by similar factors, there is a broad relationship between
them.
For a wide range of polymers, Tg = 2 Tm
In a homopolymer, it is therefore hard to control Tg and Tm independently, but this can be

achieved in a copolymer.
e.g. random copolymerisation of nylon 6,6 and nylon 6,10.

Tg is little changed but Tm is reduced because the irregularity makes crystals less perfect.
CH43
CH43
PART IV
POLYMERS IN PRACTICE
8.
MECHANICAL PROPERTIES OF POLYMERS
8.1
The Effect of Transitions on Properties
In a semi-crystalline polymer we see contributions to stiffness from both crystalline and

amorphous regions and these show transitions at Tm and Tg respectively.
In a copolymer we can put more than one glass transition in different regions of the chain
powerful method of controlling Tg.
CH44
CH44
Tg PS = 95C (glassy at rt), PB 87C (rubbery at rt)
Can use random copolymerisation to get smooth variation in Tg eg SBR, or block and graft
to see 2 Tgs at the two homopolymer values.
CH45
8.2
CH45
Yield and Fracture
So far we have considered the elastic deformation of polymers. Further to this, stress-strain curves
from polymers may show brittle behaviour (elastic deformation then fracture), e.g. PS or PP, or some
plastic flow before failure, e.g. PE.
Typically, we investigate this behaviour via tensile testing on a dumbbell-shaped sample

made from an extruded polymer sheet the ends of the dumbbell help the jaws of tester to
grip the sample as it is stretched
We can modify a brittle polymer to toughen it e.g. by incorporating fine (0.05 10 m)

rubber particles into PS high impact PS (HIPS). This has a lower modulus and encourages
energy absorbing processes around the crack tip giving toughness.
A more ductile polymer may behave in various ways often observe necking (local reduction
in area) and cold drawing
Necking involves a balance between strain softening (load falls as areas falls) and strain
hardening (load increases as extension increases).
(i)
Morphological changes in the polymer e.g. shear zones, chain reorientation, which
make slip easier, and/or:
CH46
(ii)
CH46
Temperature rise due to energy dissipation (can be very significant). Will vary with
strain rate but (i) will not, so can separate by carrying out tests over a range of speeds
The strain hardening which limits the necking process (and allows stable necking) is due to
molecular alignment parallel to the draw direction. Gives a stiffer, stronger material and also
sometimes strain induced crystallisation. The shape of the curve is very sensitive to strain rate
and temperature.
Drawing of polymers is important in some manufacturing processes. The limit of drawing is

described by the natural draw ratio = (length of fully necked specimen) / (original length)
A heavily drawn polymer will be very anisotropic e.g. HIPS disposable coffee cups, hot
formed, split along chain alignment direction. Similarly for parcel strapping. In both
amorphous and semi-crystalline polymers, the anisotropy of chains means that orientation has
a large effect on mechanical properties.
8.3
Chain alignment and drawing
In both amorphous and crystalline polymers, the anisotropy of the chain means that
orientation has large effect on mechanical properties. This is exploited in many ways e.g.
polymer films usually oriented, either uniaxially or biaxially, by stretching the film as it is
formed.
Uniaxial orientation (e.g. polyester magnetic tape)
Biaxial orientation (chains parallel to plane of sheet)
Since such films will be exposed to tensile stresses in the plane during use, orientation leads
to valuable increase in strength and stiffness.
Chains are also aligned in fibres produced by extrusion of molten thermoplastic through a
die and then stretching.
Chains are aligned // to fibre axis. Processing carried out at T between Tg and Tm.
CH47
CH47
If, during processing, chains are aligned above the Tg and the sample cooled to below Tg
before they have had time to relax to a random conformation, the orientation may be frozen
in.
CH48
CH48
9.
POLYMER PROCESSING
9.1
Forming processes for thermoplastics
The dominant forming processes for thermoplastics are extrusion, injection moulding and film
blowing.
Both involve melting the polymer, shaping the molten polymer by flow, casting and
solidification. The products are often oriented to some extent.
Extrusion
Polymer granules are melted and fed along a heated barrel by a rotating screw. The melt is
then extruded through a shaped die and cooled. (Solid sections, pipes, wire insulation)
Film blowing
Used to make thin films. The melt is extruded and then inflated and stretched to produce
biaxially oriented film.
CH49
Injection Moulding
Melt is forced under high pressure into cool mould, giving precise detail in product.
CH49
CH50
CH50
10. CASE STUDIES IN POLYMER SELECTION AND PROCESSING

10.1
The carbonated drinks bottle
The specification requires a cheap, light, polymer bottle to contain a liquid under pressure of
CO2 about 4 bar (0.4 MPa) with shelf life of 12 weeks.
How does it achieve the performance?
Estimate stress in wall of cylinder (1A DH65)
Balance forces in the wall of a thin walled cylinder with forces due to internal pressure
For P = 0.4 MPa, r = 50mm (2 litre bottle), t = 0.3mm (typical) we have
= 67 MPa
z = 33 MPa
These are high stresses for a polymer.
CH51
CH51
Requirements are therefore

- high strength
- compatibility with contents
- minimum diffusion of CO2
- reasonably transparent
- cheap
Best compromise: PET
- CO2 loss is tolerable

- PVDC too expensive
- PAN contains CN in residual monomer toxic
Process route: blow moulding
(i)
Injection mould pre-form

Quickly quenched in the mould to keep the pre-form amorphous.
(ii)
Heat the perform to 95 C and expand in mould

95 C is slightly above the Tg of 76 C. This gives stress induced lamellar crystals
which are biaxially oriented. The oriented crystals result in lower gas permeability
and enchanced mechanical properties. The crystals are small and the polymer
therefore remains optically clear.
CH52
CH52
Pre-form is moulded above Tm from a viscous melt.

Blow moulding just above Tg to avoid spherulite growth and give low crystallisation
rate
Biaxial orientation achieves extension ratios of 2.5 along length of bottle and 3.5
around diameter so that material is anisotropic (practical CP3)
Cooling rate is critical

Faster cooling would result in a fully amorphous material which would be optically clear but
highly permeable to gases.
Slower cooling would give a highly crystalline material with large spherulites which would
be optically opaque and brittle.
Very cost effective container with weight about 2.5% of contents (50g for 2l bottle)
CH53
10.2
CH53
Polystyrene Coffee Cups
Specification cheap, light, able to hold liquids at temperatures close to 100 C for a few
minutes (before they cool down).
Use atactic polystyrene
Atacticity means that it cannot crystallise and is amorphous.

Tg therefore important. Tg of PS is about 97 C.
Three options
(i)
Thermoformed general purpose polystyrene(GPPS)
CH54
CH54
Polystyrene sheets are heated to above the Tg, and then shaped between a positive and
negative mould, sometimes with the aid of a vacuum.
Very high (40%) orientation in the vertical wall of the cup. Less orientation on the
base.
Because the PS is below Tg at room temperature, it is glassy and brittle. It is
particularly prone to failure in the vertical direction of the walls, since there are fewer
chains crossing this direction.
Very hot drinks will raise the cup above its Tg and it will soften if held there for any
length of time.
(ii)
Thermoformed High Impact Polystyrene (HIPS)
The problem of brittle failure in the cups can be reduced by using high impact
polystyrene (HIPS) rather than GPPS.
CH55
CH55
HIPS is made by combining PS with polybutadiene rubber. These polymers are

immiscible and the rubber forms separate, rubbery phases within the glassy PS
structure. There are also grafts of rubber onto the PS chains, forming graft
copolymers. These changes have the effect of increasing the toughness of the PS.
HIPS sheets can be thermoformed as GPPS. Same orientation effects, less
catastrophic failure.
Tg is about 90 C, so again very hot drinks cannot be held for any length of time.
(iii)
Expanded polystyrene foam
Closed cell lightweight, rigid foams can be made from polystyrene.

Start with beads of PS, impregnated with about 6% pentane.
CH56
CH56
Pre-expansion
hot air and steam is introduced. This increases the volume by
raising the beads above Tg and softens them
heating the pentane above its boiling point
Residence time, temperature, resin feed rate, etc. give different prepuff densities
Maturation
Allows pressure in the cells to reach equilibrium with the outisde
Removes residual moisture
Removes residual blowing agent
Molding
Heat the prepuff in mould cavity to above Tg by introducing steam
Cool and eject
The combination softening and expansion in an enclosed cavity allows the individual
particles to fuse together into a single solid foam part.
Little orientation in the tough rigid foam.
The thermal conductivity of the resulting cup is very low since it is a foam. This
means that much of the cup as a whole does not reach Tg even with very hot drinks.
CG1
CG1
Glossary of terms
The following are definitions of some terms used in this course. The list is intended for
reference and revision, and supplements the detailed discussion which can be found in
textbooks and lecture notes.
Terms are listed alphabetically. Words in italics provide cross-references to other entries in
the glossary.
___________________________________
Addition polymerisation Chain-growth by addition reaction in which monomer units are

sequentially added to the ends of a growing (homochain) polymer molecule. The ratecontrolling step is initiation of the reaction, usually by catalysed free radical
formation, which then proceeds rapidly (cf. step-growth polymerisation). Polymers
typically formed by addition polymerisation include polyolefins, polystyrene,
polyacrylics and poly(vinyl chloride).
Additive Material mixed with a polymer to modify its properties. Additives include:
antioxidants, usually organic compounds which are themselves readily oxidised;
colourants, organic or inorganic pigments; fillers, fibrous (sometimes themselves
polymeric) or particulate solids which can reduce overall cost and usually enhance
mechanical properties; plasticisers, usually organic compounds such as esters, which
are added to assist flow in processing and improve toughness of the product.
Affine deformation A type of deformation in which the extension between any two points
in the material is the same as the overall extension.
Agglomeration [also flocculation or coagulation] reversible aggregation of colloidal
particles.
Aggregation irreversible aggregation of colloidal particles.
Amorphous polymer lacking crystallinity.
Antioxidant see additive.
Architecture Spatial arrangement of groups in a molecule.
Arcing [on a 2D X-ray diffraction pattern] concentration of diffracted intensity at constant
Bragg angle on to particular axes in the diffraction pattern, usually perpendicular to
the direction of tensile drawing in the case of semi-crystalline polymers.
Atactic see tacticity.
Azimuth (n.), azimuthal (adj.) [on a 2D X-ray diffraction pattern] the angle, often denoted
, between the projection of the divergent scattered beam onto plane of X-ray pattern
and a reference direction (normally equator or meridian) in this plane.
Bifunctional see functionality.
Block copolymer see copolymer.
CG2
CG2
Bragg angle the angle, often denoted , which incoming and outgoing X-rays make with the
diffracting Bragg planes from a crystal, as defined from the Bragg equation.
Chi parameter see Flory-Huggins parameter.
Coagulation see agglomeration.
Cold drawing [during tensile deformation] the region between initial onset of necking and
the point at which limiting strain in the neck is reached.
Colourant see additive.
Colloid a fine dispersion of two or more phases. Originally, polymers were classified as a
type of colloid, but through the work of Staudinger, Carothers and other early
polymer scientists, they were shown in fact to be macromolecules.
Condensation polymerisation (see also step-growth polymerisation) Chain growth
involving elimination of a small by-product molecule (often water, hydrogen halides
or low molecular weight alcohols) from the monomers or ends of reacting chains.
Polymers typically formed by condensation polymerisation include polyesters (e.g.
polyethylene terephthalate) and polyamides (e.g. nylons).
Configuration Spatial arrangement of atoms and groups in a molecule as dictated by the
nature and orientation of the chemical bonds. Configuration cannot be altered without
breaking bonds (cf. conformation) and is thus fixed once the molecule is synthesized.
Configurational entropy The entropy of a system due to the number of possible ways of
rearranging its constituent parts, irrespective of their motion, orientation or
conformation (cf. conformational entropy).
Conformation Arrangement of bond orientations (both within the backbone and any sidegroups/branches) in a polymer molecule. Can be changed by rotation about (single)
bonds, which occurs only above the glass transition temperature (cf. configuration).
Conformational entropy The entropy due to the conformational disorder in a polymer chain.
Maximal for a random walk (or Gaussian) chain, and minimal for a fully chainextended crystal.
Considres construction a graphical method for determining whether plastic deformation
will occur by necking or cold drawing based on tangents to true stress/strain curve.
Copolymer Polymer composed of (at least) two types of monomer residues (cf.
homopolymer). Classified according to the monomer distribution: alternating, with
equimolecular proportions distributed alternately along the chain (equivalent to a
homopolymer with a larger repeat unit; block, in which each monomer residue is
clustered into short homopolymer lengths which alternate along the chain; graft in
which one monomer forms the chain backbone, with short chains of the other
monomer attached as side-branches at random points along the length; random, with
an irregular sequence of monomer residues along the chain length.
Cross-linking Formation of covalent bonds (which may involve linking chains of more than
one atom) between adjacent polymer chains to form a network.
CG3
CG3
Degree of crystallinity The proportion of polymer (either by volume or by mass) present as

crystals, usually chain-folded lamellae, relative to the total amount of crystalline and
amorphous chains. Assumes a simple two-phase model for polymer structure, with
sharp interfaces, and often varies systematically for the same polymer depending on
method of measurement (e.g. X-ray diffraction, DSC, densitometry).
Degree of polymerisation Number of repeat units in the polymer chain.
Differential scanning calorimetry (DSC) A thermal analysis technique used to characterize
the melting point of crystalline polymers and glass transition temperature of glassy or
semi-crystalline polymers. Can also measure heat capacities and crystallinity.
Dynamic mechanical thermal analysis (DMTA) A thermal analysis technique used to
characterize the mechanical energy loss in a sample as a function of the frequency of
applied driving force and temperature. Can detect the glass transition temperature as
a peak in the energy loss spectrum for a given frequency (see
Elastomer [q.v. rubber] an amorphous polymer above its glass transition temperature.
Uncross-linked elastomers can exhibit considerable plastic deformation by a process
of reptation, and are characterised by low elastic modulus and (very) high elastic
strain to failure.
Engineering stress/strain [cf. true stress/strain] or nominal stress/strain are the stresses and
strains during uniaxial deformation assuming that the cross-sectional area remains
constant. Although for most materials, the change in cross-sectional area for small
strains is negligible, for elastomers and other plastics, the change is significant and
true stress/strain should be used.
Entropic spring an informal way to describe the elastic behaviour of a cross-linked rubber
by analogy with a conventional (enthalpic) spring in which bond strain provides the
restoring force. By contrast, in an entropic spring, the restoring force is driven by
maximization of conformational entropy, and hence the elastic modulus rises with
temperature (and, as a result of this, a stretched entropic spring contracts when heated).
Equator (n.), equatorial (adj.) [on a 2D X-ray diffraction pattern] the horizontal axis of
diffraction pattern, perpendicular to both incoming X-rays and meridian.
Extension ratio The ratio of extended length to original length, denoted . Related to the
engineering strain by = + 1.
Filler see additive.
Flory-Huggins parameter a dimensionless quantity with magnitude related to the strength
of enthalpic interaction between two species, with positive values denoting repulsion
(a tendency to demix) and negative values denoting attraction (a tendency to mix).
Fringed micelle model an alternative, older model for semi-crystalline polymer morphology,
in which small crystalline regions are linked by fringes of amorphous polymer
chains. This model has been generally rejected in favour of the lamellar crystalline
model for most semi-crystalline thermoplastics, but may be relevant for some semicrystalline block copolymers.
CG4
CG4
Functionality Number of sites on a monomer molecule at which bonds form to other

molecules during polymerisation. Monomers must be at least bifunctional to
polymerise and trifunctional to cause cross-linking and branching.
Gauche Conformation (at a pair of backbone atoms) in which the two extensions of the
backbone chain are oriented at an angle of 60 when viewed along the axis of the
bond joining the pair (cf. trans).
Gaussian chain See random walk chain.
Gel point In polymerisation of a cross-linking system, the point at which just enough crosslinks have formed to join all molecules together into a single continuous tree; the
polymer is no longer soluble but forms a swollen gel in a solvent. Associated with a
sharp rise in viscosity.
Glass Amorphous (i.e. non-crystalline) solid; has no sharp melting point. If a glassy polymer
is not cross-linked it will flow under stress, with a progressive fall in viscosity with
increasing temperature, becoming a thermoplastic melt. A glassy polymer may also
be cross-linked (in which case it will become a rubber above its glass transition
temperature)
Glass transition temperature Tg Temperature above which changes in chain conformation
become thermally activated (by rotation of backbone segments about single bonds).
The glass transition is associated with important changes in the properties of
amorphous polymers (or the amorphous regions in semi-crystalline polymers), such
as stiffness (i.e. modulus), density and heat capacity.
Graft copolymer see copolymer.
Gyroid a periodic bicontinuous phase with cubic symmetry seen in block copolymers and
some other soft matter systems. Normally only stable over a narrow range of
temperatures and interaction strengths. An example of a minimal surface.
Hermans orientation parameter a quantitative measure of the degree of alignment chain in
an amorphous or semi-crystalline polymer (very similar to the order parameter for a
nematic liquid crystal) with a reference axis (e.g. tensile draw direction). Ranges from
0.5 for complete orientation in a plane perpendicular to the reference axis, to 1 for
perfect orientation parallel to the reference axis. Zero for an isotropic system.
Homopolymer Formed from a single type of monomer (cf. copolymer)
Infrared (IR) spectroscopy An analytical technique in which infrared radiation is used to
provide information about the functional groups present in a molecule. Can be used
for materials identification and for following the extent of chemical reaction.
Isotactic see tacticity.
Isotropic in context of a liquid crystal or polymer chain, refers to the absence of an unique
axis of orientation, i.e. a given molecule or monomer is equally likely to be oriented
in all directions; hence, bulk properties such as modulus or refractive index do not
depend on the measurement direction.
CG5
CG5
Lamella (n.), lamellar (adj.), lamellae (pl.) Structural element of a polymer crystal in which
chains are densely packed in an all-trans conformation into planar sheets, which are
very thin compared to the total length of polymer due to repeated folding of the chain.
Limiting strain in neck (q.v. natural draw ratio) The maximum strain which can be reached
in the necked region of sample under tensile draw.
Maltese cross a characteristic pattern often observed when viewing crystalline polymers
containing spherulites between crossed polarisers, demonstrating that the lamellae are
oriented radially from the centre.
Mer Term for monomer or monomer residue according to context; an n-mer is a chain
containing n mers.
Meridian (n.), meridional (adj.) [on a 2D X-ray diffraction pattern] the vertical axis of
diffraction pattern, perpendicular to both incoming X-rays and equator.
Minimal surface strictly, a surface with zero mean curvature. Can also be thought of as
surfaces that minimize surface area subject to some constraint, such as total volume
enclosed or a specified boundary. Examples: soap films, the gyroid and a plane.
Molecular weight the total mass of each individual polymer chain; for simple polymers
equal to the product of the degree of polymerization with the mass of the repeat unit.
Monomer Multifunctional molecule capable of reacting to form a polymer chain.
Monomer residue Feature added to a growing chain by incorporation of one monomer
molecule: may be the same as the monomer, but will be smaller if elimination of some
atoms occurs during chain growth (cf. repeat unit).
Natural draw ratio The length of a fully necked polymer specimen divided by its original
length, equal to one plus the limiting strain in neck. Characteristic of the materials
hardening behaviour rather than the way in which the tensile draw has been imposed.
Natural polymer formed in biological systems. Typical examples include cellulose and
starch from plants, alginates from sea-weeds, chitin from crustacean shells, collagen
from animals and various microbial gums such as gellan and xanthan. A notable
example are the polyhydroxyalkanoates, such as polyhydroxybutyrate, which are
synthesized by bacteria for energy storage and can be processed as thermoplastics.
Necking [of a polymer] the formation of a localized region of reduced cross-sectional area
during tensile draw, associated with an increase in local strain until either limiting
strain in neck is reached or failure occurs (depending on whether or not the material
exhibits stable cold drawing).
Newman projection View down the axis of the chain backbone showing the relative
orientation of successive sets of side-groups.
Nominal stress/strain see engineering stress/strain.
Olefin [alkene] Hydrocarbon of the homologous series CnH2n, containing a single C=C
double bond (e.g. ethene).
Order parameter see Hermans orientation parameter.
CG6
CG6
Packing fraction the ratio of solid volume of particles in a colloid to the overall volume
occupied.
Plasticiser see additive.
Plastics Organic polymer in which plastic strain can be induced.
Polydispersity Existence of a range of molecular masses. The polydispersity index is the
ratio of the weight average molecular mass to the number average molecular mass.
Polymer Long chain molecule.
Polyolefin [polyalkene] A polymer produced from an olefin [alkene] monomer, e.g.
polyethylene or polypropylene. Although polyalkene is the modern terminology, the
term polyolefin is still widely used.
Random walk chain A polymer conformation in which the probability density of the endto-end distance (or, equivalently, monomer density) follows a normal distribution.
Repeat unit Element which repeats along the chain to produce the polymer (may be the
same as the monomer residue, but in a copolymer, for example, may be larger).
Reptation a process by which a polymer chain can escape its entanglements with
neighbouring chains by diffusing along its length in a characteristic time that is a very
strong function of molecular weight. As a result, the viscosity of molten thermoplastic
polymers is much higher than other liquids. Reptation does not occur in rubbers, even
above Tg, and for other types of polymer, it is essentially negligible below Tg.
Rubber [q.v. elastomer] a type of thermosetting elastomer that has been chemically crosslinked (usually by a process of vulcanization) so that it adopts a particular permanent
shape. Large-scale plastic deformation (by reptation) is prevented by the presence of
the cross-links.
Rulands method a technique for calculating degree of crystallinity of polymers from X-ray
diffraction measurements by separating the scattering from crystalline and amorphous
components.
Scherrer equation a formula relating the contribution to peak width of X-ray reflection
from finite crystal size, derived from Braggs law. Note that since there may be other
contributions to peak width, the size estimate is always an upper bound.
Semi-crystalline [polymer] Containing both amorphous and crystalline regions typically
small chain-folded lamellae dispersed randomly in an amorphous matrix, see also
lamellar and fringed micelle model.
Spherulite Approximately spherical region of high crystallinity in a polymer solidified from
the melt, containing crystalline lamellae radiating from a central nucleus.
Step-growth polymerisation Progressive growth of a polymer chain by the reaction of a
terminal group with a monomer molecule or the reactive end of another chain; often
involves condensation (e.g. elimination of a water molecule). Rate-controlling step is
the reaction of the end group, rather than initiation of chain growth (cf. addition
polymerisation). Polyesters and polyamides, for example, form by step-growth.
CG7
CG7
Stereoregular Configuration in which side-groups are systematically located along the

chain (e.g. in a syndiotactic or isotactic isomer).
Syndiotactic see tacticity.
Tacticity Configurational isomerism. A monotactic polymer (i.e. with a single kind of
substitutional side group) may be: isotactic, with successive side groups all in the
same orientation; syndiotactic, with side groups alternating regularly between the two
possible orientations; atactic, with the side groups randomly oriented along the chain.
Thermogravimetric analysis (TGA) A thermal analysis technique in which the mass loss of
a sample is measured as a function of temperature. Can be used to determine the
degradation temperature of polymers, and the level of volatile organic or non-volatile
inorganic additives present in them.
Thermoplastic Polymer which can be softened and melted, reversibly, by the application of
heat; implies the absence of cross-links. Examples: polyolefins, polyesters (PET) and
polyamides (nylons).
Thermoset Cross-linked plastic which cannot be softened or melted by the application of
heat (but chars/decomposes instead). Usually formed by reaction between liquid
precursors, often but not necessarily above room temperature. Example: epoxy resins.
Above the glass transition temperature, a thermoset will become a rubber.
Torsion angle [in a polymer] the angle at which the two extensions of the backbone chain are
oriented when viewed along the axis of the bond joining the pair.
Trans Conformation [at a pair of backbone atoms] in which the two extensions of the
backbone chain are oriented at an angle of 180 when viewed along the axis of the
bond joining the pair (cf. gauche).
Translational entropy the entropy possessed by system by virtue of the motion of its
constituent particles. In general, it is difficult to compute by a combinatorial approach,
but for an ideal gas, it is given exactly by the Sackur-Tetrode formula.
True stress/strain [cf. engineering stress/strain] the instantaneous stress and strain in a
material undergoing uniaxial deformation, taking into account any changes in crosssectional area from its initial value.
Voronoi construction a geometrical construction in which a series of points (or nuclei) is
enclosed by polygons or polyhedra within which all distances to the enclosed point
are shorter than those to neighbouring points. Model for a soap film or grain structure.
Vulcanization the process of chemically cross-linking a rubber by the addition of sulphur,
along with various other accelerants and stabilization agents, at high temperature and
pressure, resulting in the reduction of surface tackiness and increase in elastic
modulus. Excessive vulcanization results in a hard, brittle material known as ebonite.
Ziegler-Natta polymerization A process in which a combination of titanium chloride and
triethylaluminium catalyst (also other classes of metallorganic compounds) are used
to produce highly stereoregular (usually isotactic) polyolefins with a very low degree
of chain branching (cf. free radical additional polymerization, which leads to high
branching and atacticity in vinyl polymers). Polymers typically formed by a ZieglerNatta process include polyethylene and isotactic polypropylene with high crystallinity.
CQ1
CQ1
Question Sheet CQ1 : Polymer molecules and identification
1.
A sample of material containing an unknown polymer taken from the item shown below
was found to be almost neutrally buoyant in water and not easily scratched by a fingernail.
The infrared spectrum showed a strong absorption band near 2900 cm1 and a doublet near
1400 cm1. Thermogravimetric analysis revealed a non-degradable residue of inorganic
material comprising 15% of the original sample weight and with a density of 2.71 Mg m3.
Stating your reasoning, give the most plausible identification of the samples constituents.
Discuss why this material may have been chosen for its intended purpose.
2.
Hydrogen peroxide, H2O2, acts as the initiator for the addition polymerisation of ethene by
the mechanism shown below.
Sketch ways in which chain growth can terminate.

5 g of hydrogen peroxide is added as an initiator to a mixture of 1 kg of ethene (CH2=CH2)
and 2 kg of propene (CH2=CH-CH3). Calculate the number average degree of
polymerisation and the average molecular weight when all the peroxide has reacted.
The actual molecular weight distribution of the polymer was characterized experimentally
and is shown in the figure below. Calculate the number average and weight averaged
molecular weights, and hence estimate the extent of reaction and polydispersity index.
REC/2012
CQ1
CQ1
0.3
0.25
0.2
0.15
0.1
0.05
0
0-5
5-10
10-15
15-20
20-25
25-30
30-35
35-40
Molecular Weight [range, x103 g/mol]
3.
Show how a condensation reaction between hexamethylene diamine:

H2N(CH2)6NH2
and adipic acid:
HOOC(CH2)4COOH
leads to the formation of nylon 6,6.
If exactly equal molar quantities of each reagent are completely reacted together, how
many polymer chains will result? What will be the effect of adding a small amount of
acetic acid (ethanoic acid CH3COOH) to the reaction mix?
Calculate the number average molecular mass of the polymer produced by completely
reacting 1 mole of hexamethylene diamine with 0.99 moles of adipic acid and 0.02 moles
of acetic acid.
4.
The random walk or Gaussian chain model for an amorphous polymer chain gives the
probability of a chain end being some distance r to r + dr from the origin as:
3
b
P=
(r )4
rd r
exp

2
( b r 4
)
2 2
rd2 r
where b =
3
2na 2
and n is the number of monomer segments of length a.

Use this to derive separate expressions for the mean-squared end-to-end distance and most
probable end-to-end distance of the chain, and compare their values. Explain how the
limiting behaviour of a real polymer chain would differ from the random walk model at
large and small end-to-end distances.
1
2
exp ( x ) dx =
2
0
REC/2012
CQ1
5.
CQ1
The root mean square end-to-end distance of polymer chains in an amorphous polyethylene
depends on n, where n is the number of C-C links in the chain. However polystyrene
deviates from this relation. Why, and in what direction, would you expect this deviation to
occur?
What is the lowest enthalpy chain conformation for polyethylene? Why may polyethylene
chains in an amorphous sample adopt other, higher enthalpy, conformations, and what influence
does this have on polymer microstructure? How could you estimate the relative proportions of
the different conformations, and why is this dependent upon temperature?
Describe the difference between isotactic, syndiotactic and atactic polymer chains.
2008 Paper 2 q 10 (part)
Numerical Answers
1.
2.
Degree of polymerisation = 567, M N = 18950 g mol1 from graph, extent of reaction 0.97,
polydispersity index = 1.16
3.
Approximately 22,600 g mol1
4.
5.
-
REC/2012
CQ2
CQ2
Question Sheet CQ2 : Polymer States

1.
2.
Explain what is meant by the glass transition temperature of a polymer. Sketch the
temperature dependence of specific volume, thermal expansion coefficient and specific
heat capacity in the vicinity of a glass transition and account in molecular terms for the
form of these variations. Outline the effects on the glass transition temperature of:
(a)
changing the cooling or heating rate;
(b)
introducing bulky side groups on to the polymer chain;
(c)
increasing the chain length of the polymer
Sketch the variation of stiffness with temperature for an amorphous polymer. Indicate the
glass transition on your diagram. How and why is the behaviour modified at long loading
times? Why is some cross-linking beneficial in an elastomer, and how can it be achieved in
polyisoprene (natural rubber)?
3.
A bungee jumper dives from a platform 100 m above sea level and weighs 90 kg. The
bungee cord is made from a cross-linked elastomer which is 40 m long when unstretched,
with an initial cross-sectional area of 5000 mm2. On the first bounce, the jumper is
submerged up to their chest in water, and eventually comes to rest at some height above sea
level. Estimate the cross-link density of the bungee cord rubber and hence (using an
approximate iterative method or otherwise) their height above sea level.
A component in a device that operates at 20 C is made from natural vulcanised rubber and
is designed to give a certain extension ratio for a known nominal stress. It is proposed to
run the device at 37 C rather than at 20 C. What changes will need to be made to the
rubber to ensure that the same stress gives the same extension ratio? Explain what will
happen if the device is run at 50 C and at 90 C. What changes, if any, can be made to the
polymer to preserve the behaviour of the device?
2004 paper 2 q 10 (part)
5.
A sample of polyethylene quenched rapidly from the melt has a density at 20 C of 0.865
Mg m-3. Polyethylene crystallises with an orthorhombic unit cell containing four carbon
atoms and eight hydrogen atoms, with lattice parameters a = 0.736 nm, b = 0.492 nm and c
= 0.254 nm. Stating any assumptions you make in your calculation, estimate the percentage
crystallinity of a polyethylene sample which has been cooled slowly from the melt and
which has a density at 20 C of 0.940 Mg m-3.
6.
Describe by means of a sketch the principles of differential scanning calorimetry (DSC).

A schematic DSC trace from a semi-crystalline polymer is shown below, using a heating
rate of 10 K s1. Identify the glass transition and melting temperatures, and calculate the
specific heat capacity of the glassy phase (i.e. below Tg) if the sample mass was 4 mg.
Estimate quantitatively the degree of crystallinity in the sample if the heat of fusion of the
crystalline phase is 10 J g1, and explain qualitatively how would you expect this to change
if the sample was cooled quickly from the melt state?
REC/2012
CQ2
CQ2
Numerical Answers
1.
2.
3.
nseg = 5.4 1025 m3, height = 45.8 m.
4.
decrease cross-links by factor 0.945; increase cross-links by factor 1.31; not possible
5.
51.4% by volume.
6.
cp = 1.5 J K 1 g 1 , about 65% crystalline by mass.
REC/2012
CQ3
CQ3
Question Sheet CQ3 : Polymers in Practice

1.
Syndiotactic polypropylene (PP) is known to crystallize in a C-centred orthorhombic lattice,

similar to polyethylene, with two chains per unit cell. If the first four lines in the powder Xray data shown below, obtained using Cu K radiation ( = 0.154 nm), are indexed as 200,
110, 201 and 111, then determine the lattice parameters of the unit cell.
Thinking carefully about the number of repeat units in the c-direction, calculate the density
of fully crystalline syndiotactic PP. If the density of fully amorphous PP is 0.88 g cm3,
calculate the degree of crystallinity by mass of a PP sample with density 0.91 g cm3.
2.
(a) Examination of a thin section of polymer film using light microscopy reveals a semicrystalline microstructure containing large spherulites that display a Maltese cross pattern and
circumferential banding when viewed between crossed polarisers. Explain the appearance of
these spherulites, and outline the relationship between the chemical structure of the polymer
chains and the observed microstructure.
(b) Explain why the polymer polyhydroxybutyrate (PHB) forms spherulites readily on cooling
from the melt (Tm=195 C), whereas atactic polystyrene (PS) remains amorphous. Draw
schematic diagrams of the type of microstructure that would be expected from:
(i) A sample of PHB quenched to 120C and held at that temperature until fully
crystallised;
(ii) A sample of PHB quenched to 50C and held at that temperature until 60%
crystalline.
Which of these heat treatments would be best suited to the manufacture of a carbonated drinks
container? Discuss the advantages and disadvantages of selecting PHB versus PS as the polymer
from which to make the container.
2005 paper 2 q 12
REC2012
CQ3
CQ3
3.
Explain why the ratio of glass transition temperature to melting temperature has a similar
value for many polymers. How might these temperatures be varied more or less
independently of one another?
4.
Many polymers exhibit cold drawing. Explain the molecular basis of this phenomenon.
Cold drawing is often associated with a yield drop in the true stress versus true strain
curve. Outline the two most common explanations for the yield drop, and describe how
their relative importance could be assessed.
5.
A sample of atactic polystyrene was extruded from the melt into a rectangular bar of initial
length L0= 7.7 cm, thickness t = 1 mm, and cooled to just above glass transition temperature
where it was subjected to a tensile load parallel to its length which extended it to L = 10.0 cm.
The sample was then quenched to room temperature and viewed between crossed polarizers,
as shown schematically below, under monochromatic illumination by a sodium lamp ( = 590
nm). The regions are numbered counting from one end of the sample to the other.
Region
Original length [cm]
Strained length [cm]
Transmittance [I/I ]
1
2
3
4
5
6
7
8
9
1.5
0.3
0.5
0.8
1.5
0.8
0.5
0.3
1.5
1.65
0.35
0.63
1.15
2.44
1.15
0.63
0.35
1.65
0.10
0.30
0.75
1.00
0.60
1.00
0.75
0.30
0.10
Neglecting any absorbance in the material, the intensity of sodium light transmitted relative to
the unattenuated signal, I/I , is given by:
0
and whereis the birefringence. Determine the strain optical coefficient (i.e. the birefringence
per unit strain). How would you determine the sign?
REC2012
CQ3
6.
CQ3
s-PS is used for high performance medical applications, where sterilisation by exposure to
high pressure steam (autoclaving) or irradiation is required, whereas atactic polystyrene is
used to make disposable drinking cups. Discuss the reasons, both physical and economic,
why this might be the case.
Numerical Answers
1.
About 32% crystalline by volume.
2.
3.
4.
5.
strain optical co-efficient is about 7.4 x 10-4
6.
-
REC2012

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Natural Sciences Tripos Part IB

Name .................................... College .........................

Materials Science Part IB Course C : Polymers

Materials Science Part IB Course C : Polymers

Natural Sciences Tripos Part IB: Materials Science and Metallurgy

PART II: POLYMER MOLECULES

Materials Science Part IB Course C : Polymers

7.1 Polymer Crystals

PART IV: POLYMERS IN PRACTICE

Materials Science Part IB Course C : Polymers

Key general texts

Texts on more specific aspects of polymers

Practicals and Question Sheets

Polymer Characterisation and Identification

Beginning 24/1/12 (after L3)

Rubber Elasticity and the Entropic Spring

Beginning 31/1/12 (after L6)

Polymer Alignment and Crystallinity

Beginning 7/2/12 (after L9)

Materials Science Part IB Course C : Polymers

Teaching and Learning Packages (TLPs) available at http://www.doitpoms.ac.uk/tlplib

Optical Microscopy and Specimen

Introduction to Mechanical Testing

Examination of an Artefact (Polymer

Crystallisation of Polymers (CP3)

Polymer Basics (Introduction)

The Glass Transition in Polymers

The Stiffness of Rubber (CP2)

Materials Science Part IB Course C : Polymers

In some cases, polymer structures are described as self-organising or hierarchical, with

Some examples of polymers

Materials Science Part IB Course C : Polymers

Materials Science Part IB Course C : Polymers

Greek - poly = many - mer = part, share.

Characteristic structural features of polymers

Materials Science Part IB Course C : Polymers

Form a network by which every other chain is connected to every other

Materials Science Part IB Course C : Polymers

Always read the label

(PETE = PET, V = PVC)

Carry out some simple identification tests

Materials Science Part IB Course C : Polymers

Water test why do polymers have different densities?

Materials Science Part IB Course C : Polymers

Apply some more sophisticated laboratory techniques

X-ray diffraction (XRD)

Thermal analysis (DSC, TGA)

Materials Science Part IB Course C : Polymers

Infrared (IR) spectroscopy

Frequency range [cm1]

Materials Science Part IB Course C : Polymers

HOW ARE POLYMERS MADE?

Addition Polymerisation (= chain polymerisation)

Materials Science Part IB Course C : Polymers

Process involves 3 stages: initiation, propagation and termination of chain growth.

Propagation: Initiator radical I reacts with a monomer molecule:

The rate-controlling step is the initiation of the reaction.

Materials Science Part IB Course C : Polymers

Step Growth Polymerisation

This is an example of a condensation reaction removal of a small molecule, in this case

The number of functional groups is referred to as the functionality: e.g. bifunctional,

Materials Science Part IB Course C : Polymers

p = extent of reaction = (no. of functional groups reacted) / (no. present initially),

Mean chain length