EMS430U

Materials Engineering
Week 8-1 Polymers
Liz Tanner
Polymers
• Long chain molecules with repeats (mers) of a group of atoms
• Produced by polymerising - joining the individual monomers together

Ethylene Polyethylene

H H H H H H H H

C C + C C C C C C

H H H H H H H H
Polymers
Poly = Many mer = Unit
• Polymer: A substance composed of macromolecules
• Macromolecule: A molecule of high relative molecular mass, the
structure of which essentially comprises the multiple repetition of
units derived, actually or conceptually, from molecules of
low relative molecular mass

Polymerisation
 History of polymers – Natural polymers
Wood Rubber 1840s Rubber balls

Woody Woodpecker

Cotton Silk

Silk road

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 What is a Polymer?

Poly mer
many repeat unit

repeat repeat repeat

unit unit unit

H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Poly(vinyl chloride) (PVC) Polypropylene (PP)

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Adapted from Fig. 5.2, Callister & Rethwisch 9e.
Polymer Composition
• Most polymers are hydrocarbons • Unsaturated Hydrocarbons
– i.e., made up of H and C • Double & triple bonds somewhat
• Saturated hydrocarbons unstable – can form new bonds
• Each carbon singly bonded to four • Double bond found in ethylene or
other atoms ethene - C2H4
• Example:
• Ethane, C2H6 H H
C C
H
H H H H
C C
• Triple bond found in acetylene or
H H ethyne - C2H2
H
H C C H
Polymerisation 1. Initiation

2. Start reaction
• Three main steps in the chain
reaction:
• Initiation 3. Chain reaction (propagation)
• Production of free radical which
reacts with monomer
• Propagation
4. Termination I
• Joining of monomers together
• Termination
• Put the end atom/group of atoms
on the chain
Polymers
• Chains are entangled so
loading material moves
chains NOT stretch the C-
C backbone
• Strong forces
• Bonding between chains
is by van der Waals forces
• Weak forces

Ashby & Jones, 2006

Molecular Weight
• Factors which control chain length are:
• Number of free radicals
• Number of end groups
• Time available for chain growth
• Catalysts

Park & Lakes 2007

Molecular Weight
• Typically have a range of
molecular weights
• Two methods of defining
• Number average (Mn) averaged
over the number of molecules
• Weight average (Mw) averaged
over the weight of EACH chain ∑ NM
i i
• Where Ni is number of moles of i Mn =
and Mi is molecular weight of i ∑N i

Mw =
∑ NM
i i
2

∑N M i i

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Molecular Weight Calculation
• Example: average mass of a class
Student Weight What is the average weight of the
mass (kg) students in this class:
1 47
2 53
a) Based on the number fraction
of students in each mass range?
3 64
b) Based on the weight fraction of
4 65 students in each mass range?
5 82
6 83 NOTE: For 10 students can do
7 87 mean (85.6kg) but for large
8 100
numbers not practical
9 102
Median = 82.5kg
10 173
 Molecular Weight Calculation
• What is the importance of the Mass distribution

one “heavy” student?

4

• In behaviour of polymers this is 3

one “very long piece of string”

Number of Students
2

0
41-60 61-80 81-100 101-120 121-140 141-160 161-180
Mass ranges /kg

4 short strings 4 short strings plus 1 long

How do polymer chains behave?
• Each chain moves • Indiana Jones and the Raiders of
• Activity of movement is related the Lost Ark
to: • https://www.youtube.com/watc
• Chain length h?v=ClwIj3x24Q4
• Links between the chains
• Temperature
• Relative to Tg and Tm
• Can think about a pit of
snakes/worms/ or plate of
spaghetti/noodles
 Molecular Weight Calculation
Weight Number Median Number Weight
• Calculate the number and range of Weight fraction fraction
Students
weight fraction of students in Ni Mi xi NiMi NiMi2
each weight range: Mass /kg Mass /kg /kg /kg2
41-60 2 50.5 0.2 10.1 510
• The first step is to sort the 61-80 2 70.5 0.2 14.1 994
students into weight ranges. 81-100 3 90.5 0.3 27.15 2,457
Using 20 kg ranges gives this 101-120 2 110.5 0.2 22.1 2,442
table: 121-140 0 130.5 0 0 0

Mn =
∑ NM
i i 141-160 0 150.5 0 0 0
Ni 161-180 1 170.5 0.1 17.05 2,907
xi = ∑N i
∑ Ni S 10 1 90.5 9,310
NiWi Mw =
∑ NM
i i
2

wi =
∑ NiWi ∑N M i i
Med=82.5 Mean=85.6 Mn=90.5 Mw=102.9

€
Properties of Polyethylene
• Depend on molecular chain length, number of cross-links,
entanglements, crystallinity
• Low density (LDPE)
• High density (HDPE)
• Ultrahigh molecular weight (UHMWPE) (MW 2-8 million)
• Cross linked (XLPE)
Polyethylene

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PE types
• LDPE, HDPE and UHMWPE all linear
chains of increasing length so
increasing properties (except
elongation)
• Wear relatively easy as chains can be
pulled off surface
• XLPE is irradiated (at high radiation
level) so develops cross links
between chains so more wear Cross-polarized light used
-- a Maltese cross appears in each spherulite
resistant
Effect of Isotropy on PE
• Isotropic PE is low modulus (c.1GPa) highly ductile (ef>300%) material
• Can be drawn into fibres, leading to orientation of PE chains, stiffer
and stronger than isotropic
• Modulus can be upto 1TPa (from 1GPa)
• Used as reinforcing fibres
• Reinforce denture bases
• Orthodontic braces
Effect of crosslinks in polymers
• Increasing number of
crosslinks increases
the modulus
• Diamond can be
considered to be
100% cross-linked
polymer

Ashby & Jones, 2006

Properties of PEs
LDPE HDPE UHMWPE Enhanced XLPE
UHMWPE

Molecular Weight 3-4 ´103 5 ´105 2-8 ´106 2-8 ´106 ´103
/g mol-1

Density /Mg m-3 0.90-0.92 0.92-0.96 0.93-0.94 0.930.94 0.90-0.97

Strength /MPa 7.6 23-40 >27 >35 20-26

Elongation /% 150 400-500 200-250 200-250 200-500

Modulus /MPa 96-260 410-1200 2000 2200 680-720

Crystallinity /% 50-70 70-80 >80 >85

Polypropylene

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Polypropylene
• Polypropylene fibres in
polypropylene composite
• All melts to PP to give easy
recycling
Paraffins
Composition Structure Boiling point (˚C) Boiling Point (K)
Methane CH4 -164 109
Ethane C 2H 6 -88.6 184.4
Propane C 3H 8 -42.1 230.9
Butane C4H10 -0.5 272.5
Pentane C5H12 36.1 309.1
Hexane C6H14 69.0 342.0
Fluorocarbons
• Hydrogen atoms replaced with fluorine
• Very good blood compatibility
• Polytetrafluoroethylene (PTFE) or Teflon®
• High crystallinity (<94%), high density 2.2Mg m-3

F F F F F F F F

C C + C C C C C C

F F F F F F F F
ePTFE
• Expanded PTFE used as porous
material for tissue ingrowth
• Arterial grafts and ligament
replacements
• Gortex®

Park & Lakes (2007)

Properties of some Polymers
LDPE HDPE UHMWPE Enhanced XLPE PP PVC
UHMWPE
Molecular 3-4 ´103 5 ´105 2-8 ´106 2-8 ´106 ´103 10-40 ´103
Weight /g mol-1

Density /Mg m- 0.90-0.92 0.92-0.96 0.93-0.94 0.93-0.94 0.90-0.97 0.88-0.93 1.38

3

Strength /MPa 7.6 23-40 >27 >35 20-26 25-33 50-80

Elongation /% 150 400-500 200-250 200-250 200-500 150-300 20-40

Modulus /MPa 96-260 410-1200 2000 2200 680-720 1000-1400 50-80

Crystallinity /% 50-70 70-80 >80 >85 30-60 10-15

 H H H H H H H H

C C + C C C C C C
PE
H H H H H H H H
H H H H H H H H

C C + C C C C C C
PP

H CH
H 3 H CH
H3 H CH
H3 H CH
H 3
F F F F F F F F

C C + C C C C C C
PTFE
F F F F F F F F