10.

Polymers

Lecture 16:
Polymers: Time dependent and fracture properties
Lecture outline

1. Learning outcomes

2. Why do we need to know

3. Effects of temperature

4. Time dependent behaviour

5. Failure in polymers

2
1. Learning outcomes
At the end of this lecture you should be able to do the following:

• Recognise that polymers are time (and temperature) dependent materials and be
able to describe qualitatively the response of a polymer to an applied load.

• Describe the origins of the glass transition and be able to explain how it is
affected by molecular structure and demonstrate awareness of its importance.

• Define creep modulus and calculate this from long term test data.

• Describe the difference between cold drawing, crazing and cracking in polymers,
and demonstrate an awareness of when each is important.

• Interpret measured toughness and fatigue data for polymers.

You should be able to complete tutorial sheet 9.

3
2. Why…..Challenger Space Shuttle disaster 1986.

Failure of the jointing in the

solid rocket booster (SRB)

Elastomeric O-ring…behaviour very temp. dependent!

4
3.1 Temperature effects on tensile properties
• At moderate stress, polymer chains deform by bond rotation, which allows chains
to slide past one another → internal friction (internal viscosity).
• Thus, polymers are visco-elastic materials, exhibiting both elastic and viscous
behaviour.
• Thus, polymer properties are very time and temperature dependent.

Note 1: transition from brittle

to plastic behaviour

Note 2: similar effects of

(i) Increasing temperature

(ii) Decreasing rate

The effect of temperature on tensile behaviour of PMMA

5
3.2 Thermal transitions in polymers

Specific volume (1/r) versus temperature

C: Crystalline solid. The tightly
packed crystal structure breaks down
into an amorphous liquid at Tm.
→ This increases the free
volume in the structure.

A: Amorphous solid. The ‘glass’

shows a change of slope at Tg.

→ The T at which the polymer

transforms from ‘glassy’ to ‘leathery’
is called the glass-transition
temperature, Tg.

B: Semicrystalline solid.
Shows characteristics of both
A and C
6
The glass transition and ‘free volume’
• The Tg occurs when the secondary bonds between chains break and permit
molecular motion of the side groups (e.g. rotation).

• This rotation requires internal space in which to occur (i.e. free volume).

• A polymer with a high degree of crystallinity will have only limited free volume (as
the chains are packed quite closely together).

• An amorphous polymer will have more free volume due to the lack of order in its
structure.

• Thus we see that amorphous polymers show more severe glass transitions than
more crystalline ones.

7
The Glass transition
• The temperature at which the polymer transforms from ‘glassy’ to ‘leathery’ is
called the glass-transition temperature, Tg.

• The Tg is the temperature at which van der Waals bonds weaken sufficiently
between chains to permit large scale chain motion.

• Strictly, the Tg is a range of temperatures.

viscous liquid
Spec. vol (cm3/g)

soft &
rubbery
brittle solid

Tg Temperature
8
s-e behaviour of an amorphous thermoplastic.

viscous liquid
soft &

Spec. vol (cm3/g)

T4>T3>T2>T1 rubbery T4
brittle solid
T1
T3
T2
T1
T2
Stress

Tg Temp

T3=Tg

T4

Strain
9
3.3 Tg in thermoplastics

Semi- Approx Tg values:

HDPE: -90°C

PP: -27 °C

PVC: +80°C

PS:+100°C

Fig. 4 Glass transition

• General rules:
(i) Tm↑ as: degree of crystallinity ↑,chain stiffness ↑, MW ↑, bonding↑

(ii) Tg↑ as: chain stiffness ↑, MW ↑, bonding↑

10
3.4 Tg in thermosets and elastomers
• Thermosets are amorphous and thus show a Tg despite not melting.
• Same is true for elastomers.
• Severity of Tg ↓ as number of crosslinks ↑.

Note: Tg (rubber):
-100 °C to -55 °C

Tg of rubber is increased by
Vulcanisation (S is added) by
increasing number of crosslinks.

Note: increase in E in range

0-50ºC with increasing crosslinks

The influence of cross-linking on modulus of polyisoprene

11
Summary of Tg effects in polymers
• Semi-crystalline polymers
– A semi-crystalline polymer will have both crystalline and amorphous regions
and will thus show characteristics of both these regions.
– Their relative influence on properties will depend on the degree of crystallinity
present.

• Themosetting (cross-linked) polymers

– The cross-links make these polymers amorphous (prevent order) .
– Whilst they do not melt, they do show a glass-transition.

• Elastomers (Rubbers)
– These are (usually) also cross-linked polymers so do not melt.
– Again a glass-transition is exhibited.
– As the number of cross-links increases (vulcanisation) the severity of the
transition decreases, as cross-links hinder molecular mobility of the network.

12
4. Time-dependent behaviour

(a) Instantaneous load applied, held and removed (b) Strain response for an elastic material

so
eo 
E

(c) Strain response for a viscoelastic material (d) Strain response for a viscous material

e t   e o  At n
13
4.1 Creep in polymers
• Unlike metals, polymers creep significantly at room temperature.
• This is due to polymer chains uncoiling and sliding past one another.
• Since the properties of polymers are very time dependent, the use of creep tests is
common, i.e. a constant stress is imposed and the strain is measured as a function of
time.

Time dependent component of strain, e(t):

(s and T const) log e s and T const)

e  A.t n log e  log A  n log t

time, t log t

14
Creep modulus and the effect of s and temperature
• There is an equivalence between the effects of stress and temperature.

Constant T: s3>s2>s1) Constant s : T2>T1)

e e
s3
T2

s2

T1
s1

log t log t

so
• Creep modulus Ec t  
e t 
A low creep modulus → polymer creeps easily
15
Example: determination of creep modulus
The figure below shows creep data at constant temperature for a polymer measured in
tension. Determine the 1000s creep modulus for a stress of 5MPa.
Creep modulus, Ec(t) = s/e(t)
e 8MPa Ec=5 MPa/0.012 = 0.42 GPa
0.02
5MPa

0.01

1MPa

0
101 102 103 104 105 106 107 108
Log time (s)
16
5. Failure in polymers…tensile failure
• Below about 0.75 Tg (Tg in Kelvin), polymers are brittle and so in a tensile test, a
surface defect (scratch, machining line etc) can initiate brittle failure.

Brittle fracture in a tensile test for a polymer in the glassy state

From Ashby & Jones, Engineering Materials 2, p248

17
Cold drawing of polymers
• At higher temperatures, from ≈ 50°C below Tg and upwards, thermoplastics
become plastic.
• Their stress strain response can then be split into 3 regions:
– linear elastic, yield and drawing:

Cold drawing of a linear polymer (From Ashby & Jones, Engineering Materials 2, p249)
18
Crazing of polymers
• Many polymers, e.g. PE, PP and nylon draw at room temperature. Others, with
higher Tg, e.g. PS, do not.

• If PS is loaded in tension at room temperature it crazes. A craze is a cracked

region with areas of drawn material (ligaments) connecting the faces.

• Crazes lead to stress whitening in the polymer prior to final fracture.

Crazing of a linear polymer (From Ashby & Jones, Engineering Materials 2, p250)

19
5.2. Impact of polymers (toughness)
• We use similar tests to those used for metals however, polymers are very
sensitive to impact rate and temperature.
• Can use Charpy tests (notched bar tests).

Impact Energy
kJ/m2 PS co-polymer with rubber
60 (HiPS)-a ‘polymer alloy’

40

PS
20 Impact

-100 -60 -20 20 60

Temperature (°C)
20
Fatigue of polymers

• Like metals, some polymers show a fatigue limit and others do not.

See Callister p. 534

• Can characterise via the usual SN approach
21