國立清華大學材料科學工程學系

111 下學期課程

Materials Science and Engineering

II

Polymeric Materials PART II:

Deformation/Processings/Common types

An-Chou Yeh/Andrew
葉安洲

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Deformation:
Depending on the deformation is at temperatures above or below Tg, the deformation
of thermoplastics can be primarily elastic, plastic or a combination of both. For
example PMMA, Tg for PMMA Tg @72 degreeC, so a ductile to brittle transition
occurs @ Tg:

(a) Elastic: stretching out of the covalent bonds within the molecular chains.
(b) Elastic & plastic: uncoiling of the linear polymers.
(c) Plastic: sliding of molecular chains by the breaking and remaking of secondary
bonds.

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Strengthening of thermoplastics:
 Increasing average molecular mass increases strength upto a certain critical
mass. However, after a critical molecular mass is reached, this method does not
further increase its strength.
 Increasing degree of crystallinity increases strength, modulus of elasticity and
density. For example HDPE vs LDPE:

Another example is nylon6,6:

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 Strengthening by introducing pendant atomic groups: Chain slippage can be
hindered by introduction of pendant atomic groups to main carbon chain.
HDPE:1vs PP:1.5vs PS: 3.5GPa (Tensile Modulus), PP has CH3 and PS has
phenylene ring. However, elongation is drastically reduced. So this method can
increase stiffness, strength, but decrease ductility.

 Strengthening by bonding highly polar atoms on the main chain: Strength

can be increased by bonding highly polar atoms on the main carbon chain. PE:35
 PVC:76 MPa (TS)
 Strengthening by O or N in the main chain: O and N in the main chain can
increase the rigidity of the molecule.

 Strengthening by introducing Phenylene rings in combination with N, O, S

in main chain: phenylene rings can cause hindrance to rotation within the
molecule, and such combination can cause electronic attraction between chains
of molecules.

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 Strengthening by addition of Glass Fibers: the optimal content of the fibers is
a trade-off between desired strength, cost, ease of processing. Nylon: 84 MPa vs.
Nylon+40 vol% Gf: 210 MPa (TS)., however, elongation can be reduced from 60
to 2.5%.

Strengthening of thermosets:
 Strength can be increased by introduction of oxygen and nitrogen atoms into
main carbon chain. (rigid main chain)
 Introduction of phenylene ring into main polymer chain with other elements
increases strength. (rigid main chain)
 Thermosetting plastics can be strengthened by reinforcements (carbon fibres)
and creation of covalent bonds network by chemical reaction during setting
(unsaturated polyester, epoxy resin).
 UTS: Polyester 70 MPa vs. Epoxy 84 MPa vs. Unidirection carbon fibre
Reinforced Epoxy 1750 MPa.

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Effect of temperature on strength of plastic materials:
 Thermoplastics soften as temperature increases, because the secondary bonding
between molecules become weaker. Strength dramatically decreases after Tg.
 Thermosets also become weaker but not viscous (strong covalent bonding).
 Thermosets are more stable at high temperature than thermoplastics.

Creep:
Creep increases with increased tensile stress and temperature. Creep is low below Tg.
Above Tg, the behavior is viscoelastic (materials that exhibit both viscous and elastic
characteristics when undergoing deformation, exhibit time-dependent strain). Glass
fiber reinforcements decreases creep.

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Stress relaxation in polymers: Decrease in stress at constant strain, due to chain
sliding by breaking and formation of secondary bonds/untangling and recoiling of
chains (causing viscous flow internally). It is temperature dependent associated with
an activation energy.

t
   0e 
Q
1
 Ce RT

σ = Stress after time t.
σ0= Initial stress
τ = relaxation time.
T= temperature, R= molar gas constant.
C=rate constant dependent on temperature
Q=activation energy

Fracture of Polymers
Brittle fracture (glassy thermoplastic, such as PMMA): Extra energy is required for
fracture due to distorted localized regions (crazes) before crack occurring.

Change in microstructure of craze as it thickens (aligning chains).

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Ductile fracture: above Tg, it can exhbit plastic yielding before fracture. During
plastic yielding, chains are uncoiled and slipping past each other, and gradually align
closer. Eventually, stress is too high, covalent bonds break and fracture occurs.

Processing techniques:
For thermoplastics:
Injection Molding

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 Extrusion

Blow molding

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 Thermoforming

For thermosets:
Compression molding

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Transfer molding

Injection molding

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Common types of polymeric materials:

PE

PVC

PP
Thermoplastics Common types
PS

PAN

SAN

ABS

PMMA

PTFE

PCTFE

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 PA (nylons)

PC

PPO
Thermoplastics Engineering
types POM (Acetals)

PET/PBT

PSU/PPS

PEI

Phenolics resin

Epoxy resin
Thermosets

Unsaturated
polyesters

Amonio resin

Natural rubber
Elastomers
Synthetic
rubber

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