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