IB Paper 3: Materials

Materials Processing:
Handout 3, Lectures 15-16
Polymer Processing, Creep

Dr Graham McShane
gjm31@cam.ac.uk

Michaelmas 2023

Contents:
8. Polymer processing……………………………………………….…...p.2
9. Creep: materials at high temperatures……………..………..p.9

1
8. Polymer processing
This section of the course will switch attention from metals to the processing of
polymers. Polymers have a wide variety of molecular structures and properties. They
are extensively used, for a number of reasons:

(a) Relatively low cost (per unit volume):

Mild steel: ~ £5000 / m3
Aluminium alloys: ~ £6000 / m3
Polyethylene: ~ £1000 / m3
(b) Low density: ρ ~ 1000 kg / m3

(c) Reasonable mechanical properties, on a unit mass basis.

(d) Low melting temperature: easy (therefore cheap) to process.
(e) Environmental and corrosion resistance
(but bringing problems with disposal, end of life). Images: DuPont Media Gallery

Molecular structure of polymers

The molecular structure plays an important role in their response to processing. This
was covered in Part IA, but is briefly revised here.

Consider first the simplest polymer structure: polyethylene (PE).

• The basic unit cell of polyethylene is a monomer of hydrogen and carbon atoms.
• These monomers link together to form polymer chains.

ethylene molecule (C2H4) polyethylene chain

monomer
A wide range of polymers are obtained by varying aspects of this basic structure:

(1) Replace some of the H atoms with other atoms or molecules: side-groups. The four
most common (thermoplastics) are:

1. Polyethylene (PE) - ?=H

2. Polypropylene (PP) - ? = CH3
3. Polyvinylchloride (PVC) - ? = Cl
4. Polystyrene (PS) - ? = C6H5
2
(2) Add branches to the polymer chains. For example, low density polyethylene
(LDPE) is a PE structure with chain branching.

polymer chains

branches

(3) Cross-linking between polymer chains:

• Thermosets and elastomers consist of polymer chains with a high and low degree of
covalent cross-linking, respectively.

polymer chains

cross linking

• Their molecular structure is fixed at the point of polymerisation:

mould once-only, cannot be softened, reshaped, recycled

• Thermoplastics have no cross-links: only weak van der Waals bonds between
polymer chains. These bonds break down through the glass transition temperature
Tg , with viscous flow above the melting point (typically 1.5 x Tg):
easy to mould, re-melt, recycle

This section will focus on two aspects of the processing of thermoplastics:

• Moulding: solidification, and control of crystallinity.
• Deformation processing: use of orientation strengthening.

8.1 Moulding thermoplastics

Injection moulding is a common technique for
shaping thermoplastics:
• Polymer granules are heated until they
become a viscous liquid.
• The polymer is then squeezed under
pressure into a two-part mould.
• When solidification is complete, the mould is
separated and the component removed.
Controlling crystallinity on solidification is an
important consideration in moulding processes.
3
A characteristic of thermoplastics is that they can be semi-crystalline, solidifying to a
mixture of crystalline and amorphous regions:

amorphous region
random molecular
arrangement

crystalline region
polymer molecules
are aligned

The properties of a thermoplastic are affected by the degree of crystallinity:

(1) Density
• The closer molecular packing of crystalline regions makes them denser than the
amorphous equivalent.
• If the densities in the fully crystalline and fully amorphous states are known, the
density of a semi-crystalline polymer can be estimated by a rule-of-mixtures based
on volume fractions.
• Note also that crystallisation leads to shrinkage, so has to be considered in
maintaining dimensional precision in moulded semi-crystalline polymer parts.

(2) Young’s modulus

modulus, E little polymer chain
• Young’s modulus increases with
entanglement high %
crystallinity.
• For a highly crystalline polymer, E crystallinity
remains high through the glass
transition temperature, until the
temperature is sufficient to break amorphous
down the van der Waals bonds in
the crystalline regions.
rubbery behaviour:
untangling of chains
temp., T

4
Polymer crystallisation is dependent on temperature and time in a similar way to
diffusion-dependent phase transformations in metals. Crystallisation follows C-curves,
and has a similar TTT diagram:

• Above the melting temperature temperature

(Tm) the amorphous state of the amorphous (stable)
polymer is stable: it is a viscous Tm
liquid with randomly orientated amorphous
molecules. (unstable)
crystalline
• Below Tm, the difference in free
energy between the amorphous
and crystalline states provides a Tg
driving force for crystallisation,
increasing with undercooling
(Tm – T). log (time)

• However, to crystallise, the polymer chains have to rearrange by diffusion. The rate of
diffusion reduces as the temperature reduces. This trade-off leads to the C-curves.

• Below the glass transition temperature (Tg), the van der Waals bonds become stronger,
and chain mobility is inhibited, restricting further crystallisation.

Crystallisation occurs by the nucleation and growth of plate shaped ‘lamellar’

crystallites within the amorphous regions. Radially arranged lamellar crystallites form
structures called ‘spherulites’.

lamellar structure crystalline

amorphous

growth
‘nucleus’
direction

spherulites

(Images: Callister, online resources supporting

Materials Science 7th edition)
5
Controlling crystallisation
In applications where transmission of light is important (such as lenses for spectacles
and polymer screens and windows), avoidance of crystallinity is a critical part of the
processing route. Large crystallites will scatter light and make the polymer appear
cloudy, so it’s necessary to avoid crystallisation, or keep the crystallites small.

(1) Choice of polymer

The times taken for crystallisation to start and complete (i.e. the position of the C-
curves) depends on the molecular structure of the polymer:

complex molecule slow to rearrange difficult to

• large side groups • C-curves pushed crystallise
• side branches to longer times

Example: PMMA (‘Perspex’).

Complex molecule has poor complex side
mobility, so crystallisation is groups
minimised.

(2) Controlling cooling rates

Because crystallisation follows C-curves, as with metals there is a critical cooling rate
that is just fast enough to miss the C-curves, avoiding the onset of crystallisation.

High cooling rates can be achieved in injection moulding processes as follows:

• Small section thickness: This avoids slow cooling in the centre (which may
crystallise), but requires a high injection pressure to force the viscous polymer into a
mould with narrow sections.
• Chill the mould: This can be achieved by using a metal mould (high thermal
conductivity) which is cooled internally by a flow of water.

8.2 Deformation processing of thermoplastics

Plastic deformation of a polymer can be used both for shaping purposes, and to alter
properties. Amorphous or semi-crystalline thermoplastics near to Tg have an elastic-
plastic tensile response as shown below:
stress molecular chains
untangle, lining up with failure
loading direction
yield
molecular chains
fully aligned

strain
Stretching the polymer to align the molecular chains, which significantly increases the
strength and stiffness, is known as orientation strengthening. Two processes which
exploit this behaviour are fibre drawing and blow moulding.

Fibre drawing
The fibre drawing process uses a screw extruder to produce a polymer filament which
is then drawn out, aligning the molecular chains, by applying tension:

tension applied: small diameter die

fibres drawn out

coiling drum

small diameter extrusion:

cools quickly → initially amorphous

By orientation strengthening, polymer fibres have a high strength and stiffness:

polyethylene, 40% crystallinity - E = 0.2 GPa
polyethylene, 80% crystallinity - E = 0.7 GPa
polyethylene, drawn fibre - E = 170 GPa

Unlike bulk polymers, the

strength and stiffness of
polymer fibres can
σf / ρ (MPa m3 kg-1)
specific strength,

outperform all metals and

some composites on a per
unit weight basis
(i.e. 𝜎𝑓 /𝜌 and 𝐸/𝜌).

specific stiffness, E / ρ (GPa m3 kg-1)

e.g. Kevlar fabric body armour

To exploit these properties in
products, the drawn polymer
fibres are used in yarns and
woven textile products: fabrics,
clothing, ropes, geotextiles, sails,
parachutes, etc. woven aramid fibres 7
(Images: DuPont media gallery)
Stretch blow moulding
Another polymer shaping process utilising orientation strengthening is stretch blow
moulding, illustrated below.
(1) An injection moulded
polymer preform called a
‘parison’ is pre-heated and
transferred to a mould.
(2) A stretch rod elongates the
preform.
(3) Compressed air inflates the
preform to fill the mould.
(4) The mould is separated and
the component ejected.

The elongation and inflation stages provide different molecular alignment in the
longitudinal and hoop-wise directions (recall that the stress is twice as great in the
hoop direction):

properties of PET (typical material for a drinks bottle)

blow moulded

injection moulded

Example: fizzy drinks bottle

Internal pressure: p ≈ 0.4 MPa

Radius: R ≈ 50 mm

Wall thickness: t ≈ 0.3 mm

Longitudinal stress: pR / 2t ≈ 33 MPa

Hoop stress: pR / t ≈ 66 MPa

• Stresses are high: some crystallinity and molecular alignment is desirable. Stretch
blow moulding is suitable.
• The moulding temperature is kept just above Tg to restrict crystallinity to about 20%.
Otherwise, it reduces the optical transparency of the bottle. 8
Film blowing
coiling drum
Film blowing is another type of blow
moulding: extruded polymer is
inflated by internal pressure, cooled
and wound onto a drum. guide rolls

The inflation produces polymer films

with some alignment in the
molecular structure. This alignment inflated thin-walled tube
improves the mechanical properties extruded
of the film, minimising the weight
(and cost) of material, e.g. for
packaging applications, shopping
bags.

air

8.3 Summary of the learning outcomes: polymer processing

After completing section 8 you will be able to do the following:

1. Explain how the molecular structure of a polymer affects its response to

processing.
2. Describe the crystallisation of thermoplastics, the effect of crystallinity on
properties, and how it can be controlled.
3. Describe how control of molecular alignment during processing can be used to
manipulate the mechanical properties of polymers.

9
8.4 Quiz W8.1: polymer processing
A thermoplastic polymer and moulding process are to be chosen to produce a final
product with a high degree of crystallinity.

Which of the following material and process attributes would increase crystallinity
(more than one may be correct)?

1. Slow cooling.
2. Fast cooling.
3. Polymer molecules with no chain branching.
4. Polymer molecules with extensive chain branching.

Additional worked example: polymer processing

For further explanation, a video will be available with the following worked example:
• Tripos Question 2013 Q5, which helps with Examples Paper 5 Q4.

Now attempt: Examples Paper 5, Q.4

9. Creep: materials at high temperatures

We switch attention back to metals now, to consider their behaviour at high
temperatures. Metals can undergo deformations at high temperatures during shaping
processes, such as hot rolling. Components can also experience high temperatures in
service: we will consider the example of turbine blades.

The models for metal plasticity encountered relate yielding to the applied stress, but
are time independent. At high temperatures “creep” deformation occurs:

• Plastic deformation depends on the applied stress, but also temperature and time:

𝜀 = 𝑓(𝜎, 𝑇, 𝑡)
We will consider models relating the creep strain rate 𝜀ሶ = 𝑑𝜀/𝑑𝑡 to (𝜎, 𝑇).

• Creep also enables plastic straining to occur at applied stresses that would be too
low to cause yielding at room temperature.

10
Consequences of creep
The response to creep shares many parallels with viscoelasticity, encountered in IA
(which is the time-dependent equivalent of linear elasticity).

(1) Continued straining (i.e. non-zero strain rate) at a constant applied stress.

𝜎 𝜎 = constant 
creep

elastic = 𝜎 / 𝐸
t t
• For room temperature plasticity, an increase in stress is necessary to cause a further
increase in strain.
• Excessive creep straining can lead to component contacts (e.g. turbine blades
touching the engine housing), or necking and tensile failure ( “creep rupture”).

(2) Stress relaxation at a constant applied strain:

 total = constant 𝜎
creep 𝜎=𝐸 elastic

elastic

t t
total = elastic + creep

• An example of stress relaxation is bolts slackening over time at high temperatures.

At what temperatures does creep occur?

For crystalline materials (metals and ceramics), this depends on the ratio of the
temperature to the melting temperature, 𝑇/𝑇𝑚 (both in Kelvin). Creep becomes
significant at 𝑇/𝑇𝑚 ≈ 0.5 .
𝑇𝑚 𝑇 ≈ 0.5 𝑇𝑚
pipes, cladding
lead 600 K 30°C
low alloy steels 1780 K 617°C power plant
ice 273 K -137°C glaciers
alumina (Al2O3) 2325 K 890°C
11
9.1 Modelling creep deformation
The time-dependent strain of a material undergoing creep at constant applied nominal
stress (i.e. constant applied load) and constant temperature shows three stages of
behaviour:

 X Rupture

Stage III

Stage II

Stage I
Elastic
t
• Stage I: Primary creep – occurs over a short time period
• Stage II: Steady-state creep - dominates creep life
• Stage III: Tertiary creep – leads up to rupture

Design against creep generally focusses on Stage II.

• Typical creep strain-rates (s-1): 10-10 → 10-5

• Time taken for 10% creep strain: 32 years 3 hours

The steady-state creep rate in Stage II is well modelled by a power law dependence on
the applied stress, at fixed temperature:

ሶ ∝ 𝜎𝑛
𝜀𝑠𝑠
This can be verified experimentally, by plotting log 𝜀ሶ against log 𝜎. This should give a
straight line with gradient 𝑛 .

Furthermore, if creep experiments are performed at a range of temperatures, the

constant of proportionality in this relationship is seen to obey the Arrhenius law:

𝑄
𝜀𝑠𝑠
ሶ = 𝐴 exp − 𝜎𝑛 (1)
𝑅𝑇
Here, 𝑄 = activation energy (J / mol), 𝑛 = creep exponent (no units), 𝐴 = the creep
constant (a material parameter). To determine the activation energy, plot:
1
ln 𝜀𝑠𝑠
ሶ vs at constant stress
𝑇
12
Note that an alternative form of equation (1) is sometimes used, replacing the creep
constant 𝐴 with material parameters 𝜀0ሶ and 𝜎0 :
𝑛
𝜀𝑠𝑠
ሶ 𝑄 𝜎
= exp −
𝜀0ሶ 𝑅𝑇 𝜎0

9.2 Creep mechanisms

The fact that the creep strain rate is found to follow the Arrhenius law indicates that
atomic diffusion plays a role in creep. Recall that the diffusion coefficient follows the
same relationship: 𝐷 = 𝐷0 exp(−𝑄/𝑅𝑇) .

There are two important creep mechanisms, that both depend on atomic diffusion:

(1) Power-law (or dislocation) creep

In conventional yielding, dislocation motion is
resisted by obstacles (precipitates, other
dislocations etc.), leading to work hardening.
An increase in the stress is required for further
straining to occur.

Power-law creep is the mechanism of

dislocations escaping from obstacles at high
temperatures by local diffusion of atoms:
• Diffusion allows dislocation climb to occur.
• A segment of the dislocation line moves
onto an alternative slip plane, and glide of
the dislocation continues.

(Images: Ashby,
Shercliff, Cebon)

The steady state creep rate during power law creep is given by equation (1), with the
creep exponent:

𝑛 =3−8
Because the exponent applies to the stress term in equation (1), this mechanism is
therefore sensitive to the applied stress.

13
(2) Diffusion creep (or “diffusional flow”)
In diffusion creep, grains elongate in the
direction of applied tensile stress by the
diffusive rearrangement of atoms throughout
the material (rather than just locally at
dislocations, as in power law creep).

Atoms can diffuse along two routes:

• along grain boundaries (easier, occurs at
lower temperatures),
• bulk diffusion through the crystal itself
(more difficult, occurs at higher
temperatures).

The steady state creep rate during diffusion creep is given by equation (1), with the
creep exponent:
𝑛=1
It is therefore sometimes known as ‘linear viscous creep’. This mechanism doesn’t
depend on dislocation motion, and is therefore less sensitive to the applied stress.

However, diffusion creep is sensitive to the grain size:

• large grains ⟹ larger diffusion distances required, lower grain boundary area
⟹ slower creep
• small grains ⟹ larger grain boundary area, giving rapid diffusion pathways
⟹ faster creep
Note that the ‘dislocation creep’ mechanism is not sensitive to grain size: it is
dependent on atomic rearrangement locally at dislocations.

Failure during creep: creep rupture

Creep failure begins with the nucleation of
voids on the grain boundaries.
• Eventually, growth of voids leads to a
reduction in the load-bearing cross-
section, increasing the stress.
• The creep rate accelerates in the damaged
section (particularly for power-law creep,
with large exponent 𝑛), giving the
transition to tertiary creep, and creep
rupture.

14
The overall time to failure 𝑡𝑓 at a given stress often follows the empirical Monkman-
Grant relationship:

𝑡𝑓 𝜀𝑠𝑠
ሶ =𝐶
Here, the material constant 𝐶 represents a critical strain at failure.

Example: A stainless steel component was designed to operate at a stress of

𝜎1 = 180 MPa, at a temperature in the power law creep regime, for which 𝑛 = 7.5.
• If the stress is reduced to 𝜎2 = 150 MPa, by how much would the creep failure time
increase?

Taking ratios at constant temperature:

𝑛 7.5
𝜀2ሶ 𝜎2 150
= = = 0.255
𝜀1ሶ 𝜎1 180
Assuming failure occurs when: 𝑡𝑓 𝜀𝑠𝑠
ሶ =𝐶

𝑡𝑓2 𝜀1ሶ 1
= = = 3.9
𝑡𝑓1 𝜀2ሶ 0.255
A 17% reduction in the applied stress therefore results in nearly a 400% increase in
component creep life.

Creep mechanism maps

The dominant creep mechanism depends on both the temperature and the applied
stress. This is encapsulated in a creep mechanism map for steady state creep:
• axes of log (stress) and temperature, contours of constant strain rate
• boundaries separate regions where a particular mechanism dominates.

hot working
regime (see
Handout 3)

Interpolating:

log10 𝜎 = 0.25
⇒ 𝜎 = 1.8 Mpa

log10 𝜀ሶ = − 9.5
⇒ 𝜀ሶ = 10−9.5 s-1

15
The creep mechanism map can be
used to calculate the value of the
creep exponent 𝑛 :

• At a fixed temperature, read off

the change in stress between a
pair of strain rate contours:

Δ[ log10 𝜎 ] , Δ [log10 𝜀𝑠𝑠

ሶ ]

• Choose an interval of strain rates

within a single creep regime.

• Taking log10 of equation (1), and noting that 𝑇 is constant:

1 𝑄
log10 𝜀𝑠𝑠
ሶ = 𝑛 log10 𝜎 + log10 𝐴 −
ln 10 𝑅𝑇
∴ Δ [log10 𝜀𝑠𝑠
ሶ ] = 𝑛 Δ log10 𝜎 → 𝑛

Note that the spacing of the strain rate contours (and therefore the creep exponent)
changes across the map. Care has to be taken over the range of strain rates spanned
when determining a value for 𝑛.

9.3 Case study: processing for creep resistance

This case study will look at the creep resistant design of jet engine turbine blades:

85% of air flow

15%
2.8 m

Source for case study: Michael Cervenka, Rolls-Royce plc

16
The most critical component for creep
resistant design is the first stage turbine
blade, which follows the combustion
chamber:
• it experiences the highest temperatures,
• high longitudinal stresses (typically 250 turbine
MPa) result from the high rotational
speed: 10,000 rpm in the Rolls Royce high pressure stage: compressor
Trent 800. 10,000 rpm

Increasing the combustion temperature (the ‘turbine entry temperature’) leads to

increased efficiency:
• Turbine entry temperatures >1500 °C are now used.

Rate of elongation of a turbine blade 𝑅2

For the turbine blade, the stress varies 𝑅1
with position along the blade:
• centripetal self-loading due to the
angular velocity
• root has a higher stress than the tip.

Writing F = ma for a small element of

𝜔 𝑑𝜎
turbine blade gives: 𝜎 𝑟 𝜎+ 𝛿𝑟
𝑑𝑟
𝑑𝜎
= −𝜌𝜔2 𝑟 → 𝜎 𝑟
𝑑𝑟

The rate of elongation of a small element of length 𝛿𝑟 is: 𝜀𝑠𝑠

ሶ 𝑟 𝛿𝑟

The overall rate of elongation must therefore be found by integrating the local strain-
rate (which depends on the local stress) over the length:
𝑅2
𝑑𝐿
= න 𝜀𝑠𝑠
ሶ 𝑟 𝑑𝑟
𝑑𝑡
𝑅1

The full calculation is covered in Examples Paper 5. The life of the turbine blade is
improved by reducing the creep strain rate 𝜀𝑠𝑠
ሶ . Different processing strategies to
achieve this are discussed next.

17
Strategy 1: creep resistant alloy
Current engines make extensive use of
nickel-based alloys (more than 40% by
weight in a modern engine):
• High melting temperature:
reduces 𝑇/𝑇𝑚
• Note that 𝑇𝑚 = 1453°C for pure Ni, but
blade cooling maintains 𝑇/𝑇𝑚 ≈ 0.7
• High alloy content gives solid solution
and precipitation hardening:
reduces dislocation creep

Deformation mechanism maps:

(a) Pure Ni:

• The grey box indicates typical
blade operating conditions:
ሶ ~10−1 s −1
𝜀𝑠𝑠
• Blade would double in length
in 10 seconds!
• Power law creep regime:
creep is due to dislocation
motion. Alloying is needed to
stop this (see above).

(b) Ni superalloy MAR-M200:

• Ni plus 10% Co, 12% W, 9%
Cr, 5% Al, 2% Ti.
• Now, at the blade operating
conditions:
ሶ ~10−7 s −1
𝜀𝑠𝑠
• By increasing the resistance
to dislocation motion,
alloying reduces the power
law creep regime.
• Operating point moves into
the diffusional flow regime,
and strain rates reduce by 6
orders of magnitude.
Deformation-Mechanism Maps: The Plasticity and Creep of 18
Metals and Ceramics, Frost and Ashby, Pergamon Press, 1982
 Strategy 2: grain size control during casting
Alloying has moved the blade operating point into the diffusional flow creep regime.
Recall that grain size and grain boundary area influences the rate of diffusion creep:
• atoms diffuse most easily along grain boundaries.

Further improvement in life results if blades are cast with only columnar grains (see
earlier lectures) running along the axis, known as ‘directional solidification’:
• the diffusion distances required to elongate the grain become large.

Move mould slowly

down through a
growth direction
furnace to achieve
steady solidification
from the bottom Grain boundaries
all vertical

motion nucleation only occurs at the

bottom of the casting

The creep life can be improved further if grain

boundaries are eliminated altogether:
• The whole blade is cast as one single crystal.
• This requires innovative processing: a spiral
“pigtail” at the bottom of the mould permits the
growth of just one nucleus with a specific crystal
orientation.

Evolution of turbine blade casting technology:

1994
1979
1977

Equiaxed Directionally Single

crystal structure solidified crystal Accelerated lab creep tests of
MAR-M200
[Source: CH White, chapter 4 in The development of gas turbine
materials, GW Meetham (ed.), Applied Science Publishers, 1981]
19
Strategy 3: blade cooling
A negative consequence of alloying is to reduce the melting temperature, and hence
increase 𝑇/𝑇𝑚 , for a fixed turbine entry temperature (>1500°C )
• Pure Ni: 𝑇𝑚 = 1453°C
• Ni superalloy: 𝑇𝑚 = 1280°C

Blade cooling strategies are needed to maintain 𝑇/𝑇𝑚 ≈ 0.7 :

(a) Cooling the blade from the inside. (b) A zirconia (ZrO2) ceramic thermal barrier
A flow of cooling air reduces the coating provides an insulating layer between
surface temperature by >200°C . the hot gasses and the Ni superalloy.
• A coating 150 µm thick reduces the
surface temperature by a further 170 °C.

9.4 Summary of the learning outcomes: creep

After completing section 9 you will be able to do the following:
1. Describe the mechanisms of power law creep and diffusion creep, and identify
them on a creep mechanism map.
2. Use a model for steady state creep to predict the creep life of components.
3. Explain how alloying, processing and component design can influence creep life.

9.5 Quiz W8.2: creep

A weight hangs from the end of a cantilevered metal strut within a furnace. Which of
the following strategies will increase the creep life of the strut (more than one may be
correct)?

1. Reduce the grain size, in order to increase the yield strength.

2. Increase precipitation and solid solution hardening.
3. Reduce the cross-sectional area, to reduce the total grain boundary area.
4. Use a low melting temperature alloy, in order to reduce casting defects.

Additional worked example: creep

For further explanation, a video will be available with the following worked example:
• Tripos Question 2015 Q5, which helps with Examples Paper 5 Q5-8.

Now attempt: Examples Paper 5, Q.5-8 20