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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
thermosetting
amorphous
(random arrangement)
Arrangement of chains
crystalline
(chains aligned)
Polymer crystallinity
• Cooling rate
• Chain complexity and regularity
• Side group size
• Tacticity
• Cross-linking
• Branching
HDPE and LDPE
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
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
stress strain
time time
Load Response
Viscous component is time-dependent!
strain stress
time time
Load Response
Viscous component is time-dependent!
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
50 MPa
5 strain
r
Callister (6th ed.) p. 497