Polymers
Made up of chain molecules long-range connections
throughout material
In practice, mostly carbon atoms along length of the chain +
various side-groups (e.g. -H, -Cl,-OH, -CH3) attached to it at
regular intervals
Polymer materials
High Density Polyethylene for
storm water drainage system.
Replaces fired clay ceramics
(brittle, difficult to make long
sections, difficult to join) and cast
iron (heavy, low corrosion
resistance)
Also used in domestic plumbing,
displacing copper (expensive)
Polymer materials
Kevlar for body armour.
Replaces iron (heavy, stiff)
Polymer materials
Polyvinyl chloride for cable insulation:
flexible, easily formed, thermally and
electrically insulating.
Nylon for fabrics, replacing
silk (expensive)
Natural polymer materials
General characteristics
Cheap
Tough
Lightweight: polyethylene density = 0.96 g cm-3
Easy to shape
Flexible
Resistant to chemical attack
Thermally, electrically insulating
BUT
low stiffness / strength: E (polyethylene) = 1 GPa
limited temperature range: Tm (polyethylene) = 105°C
high coefficient of thermal expansivity: α (polyethylene) = 150 x 10-6 K-1
Degrade when exposed to UV light, oxygen
Describing polymers
Basic unit = mer
e.g. polyethylene polypropylene
(C C )n CH3
(C C)n
Cl
polyvinyl chloride
(C C )n
C6H5
polystyrene (C C )n = (C C )n
Mixtures copolymers
Describing polymers (cont.)
• Chain length (typically 103 - 105 mers)
• Extent of branching
• Extent of cross-linking thermoplastic
thermosetting
• Tacticity: spatial arrangement of side-groups
isotactic, syndiotactic, atactic
Describing polymers (cont.)
amorphous
(random arrangement)
Arrangement of chains
crystalline
(chains aligned)
Polymer crystallinity
Callister (6th ed.) p. 470
In practice, polymers are semi-crystalline
Callister (6th ed.) p. 471
Factors influencing crystallinity
• Cooling rate
• Chain complexity and regularity
• Side group size
• Tacticity
• Cross-linking
• Branching
HDPE and LDPE
• High density polyethylene: linear chains, branching
minimised efficient alignment of chains, 90%
crystallinity.
E = 1 GPa
• Low density polyethylene: branched chains
inefficient alignment of chains, 50-60% crystallinity.
E = 0.2 GPa
Uses e.g. cling film
Polymer categories
• Fibres (e.g. Kevlar®, silk): chains aligned parallel to
fibre axis
• Elastomers (e.g. rubber): loosely cross-linked
network
• Plastics
Mechanical properties
4 possible responses to loading:
1. stretching C-C bonds
2. stretching secondary bonds (weak forces between different
chains)
4. chains slide past each other }
3. chains unravel, straighten out only happen above glass
transition temperature (Tg)
liquid
specific supercooled
volume liquid
crystallisation
glassy solid
crystalline solid
Tg Tm temperature
crystalline solid
density
glassy solid
crystallisation
supercooled
liquid
liquid
Tg Tm temperature
Factors influencing Tg
• Cooling rate
• Chain flexibility
– Side group size
– Cross-linking
– Branching
– Chain length
Typical glass transition temperatures:
Polyethylene: -90°C
Polypropylene: -18°C
Polystyrene: +100°C
Polymer behaviour above and below Tg
Below Tg:
Polymer chains “frozen” into place, only bond stretching
possible.
Polymer is “glassy”: stiff, strong and brittle
Above Tg:
Polymer chains free to move around and change shape
Elastomers: chain motion restricted by cross-linking
Semi-crystalline polymers: amorphous sections pinned by
crystalline regions
Amorphous polymers: slight restriction on chain motion
provided by entanglements, but resistance to deformation
drops rapidly with temperature, until material flows
Amorphous polymers generally used below Tg
Callister (6th ed.) p. 488
Deformation of semi-crystalline polymers
Above Tg, behaviour is viscoelastic (‘leathery’):
Elastic component from bond stretching (mainly in
crystalline region) Hookean behaviour
Viscous component from chain segments sliding past
each other in amorphous region
Viscous component is time-dependent!
Two effects: (i) Creep
stress strain
time time
Load Response
Viscous component is time-dependent!
Two effects: (ii) Stress relaxation
strain stress
time time
Load Response
Viscous component is time-dependent!
Compliance / Elastic modulus are time-
dependent
ε = D(t)σ
σ
σ = constant):
Under creep conditions (σ
D(t) = ε(t)/ σ0
definition of creep compliance
How do viscoelastic materials deform?
Viscoelastic materials can be considered as composite
materials:
Viscous component (amorphous areas) + elastic component
(crystalline areas)
model using a Maxwell element:
spring dashpot
Deformation of elastomers
Typical modulus: 10 MPa
Extent of reversible deformation: ~400%
stress
50 MPa
5 strain
r
Callister (6th ed.) p. 497
