Week 15 All Combined

Engineering Materials
MECH1280
Semester 2
1 POLYMERS | 1.3 Polymer Mechanical Properties – Part A
[PRE-REC]
MECH1280 | Week 15 Copyright © 2020 University of Leeds UK. All rights reserved. Dr A. Herbert
Session being recorded
The recording of this session will
be made available in the following
places:
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Leeds Portal Login for Students)
Information about recordings at the University of Leeds
http://help.leeds.ac.uk/lectures
1.3.1 Characteristic stress-strain behaviour
• Simple stress-strain test is used for
determining properties
• Mechanical properties are specified in

same way as metals; i.e.
• Modulus of elasticity
• Yield strength
• Tensile strength
• Mechanical characteristics are sensitive to

external factors (strain rate, the temperature
and chemical nature of the environment, …)
1.3.2 Effect of Temperature on mechanical
properties
1.3.2 Effect of Temperature on mechanical
properties
Influence of temperature and strain rate of thermoplastics
• Decreasing T...
- increases modulus
- increases tensile strength
- decreases % elongation
• Increasing strain rate...

- same effects as decreasing T
1.3.3 Strength-limiting process in polymers
Roughly in order of increasing temperature, these are:

a) Brittle fracture
b) Cold drawing, the drawing-out of the molecules in the solid state,

giving a large shape change
c) Shear banding (giving slip bands like in metal crystals)
d) Crazing, micro-cracks associated with local cold drawing
e) Viscous flow, when secondary bonds in the polymer melt
1.3.3 Brittle failure
Below about 0.75 Tg polymers are brittle
• Polymers have small surface cracks (depth c), from machining,
abrasion or environmental attack
1.3.3 Deformation of a Brittle Polymer
Aligned, crosslinked Network
polymer polymer
As a general rule…
Thermosetting polymers (heavily networked) – fracture mode is brittle
1.3.3 Cold drawing Macroscopic Polymer
deformation
Consider a semi-crystalline polymer
Upper yield point,
small neck forms and
within this chains are
orientated
Causes localised strengthening
(some resistance to extension)
Lower yield point
Ongoing elongation proceeds by

extension of neck region along
gauge length
deformation
Two adjacent chain folded lamellae and

Interlamellar amorphous material before
deformation
deformation
Elongation of amorphous tie chains

deformation
deformation
Consider a semi-crystalline polymer Separation of crystalline
block segments
Increase in lamellar crystallite thickness (which
is reversible) due to bending and stretching of
chains in crystallite regions

deformation
deformation
block segments

deformation
deformation
block segments

Orientation of block
segments and tie
chains with tensile
axis in final
deformation stage
deformation
1.3.4 Fracture of Polymers
For thermoplastic polymers, ductile and brittle fracture modes are
possible, and many materials experience a ductile to brittle transition
• Factors that favour brittle fracture are:
– Reductions in temperatures
– Increase in strain rate
– Sharp notch
– Increase in specimen thickness
– Modification to polymer that increases Tg
1.3.4 Fracture of Polymers - crazing
Thermoplastic polymers can undergo crazing
• Very localised plastic deformation, • If load is sufficient, bridges elongate and break.
leads to microvoids with fibrillary • The craze is followed by a crack
bridges between them
1.3.5 Deformation of Elastomeric Polymer
Elastomers have the ability to
substantially deform and then
elastically return to shape.
Crosslinks provide the force
(“memory”) to restore chains to
their undeformed configurations.
Elastomers must be:

• Amorphous
• Relatively free chain bond
rotations
• Crosslinked
• Above the Tg
1.3.6 Viscoelastic Behaviour
Viscoelasticity is a type of deformation
exhibiting the mechanical characteristics
of viscous flow and elastic deformation
• An amorphous polymer may behave like:
– A glass at low temperatures (<Tg)
– A rubbery solid at intermediate temp (>Tg and <Tm)
– A viscous liquid at higher temperatures (>Tm)
• At intermediate temperature range, polymer has the

combined viscous flow and elastic deformation – it is
viscoelastic
• Also dependent on time (rate of stress application)
1.3.6 Viscoelastic extreme example
• You tube - silly putty
1.3.7 Viscoelastic Creep
Irreversible process in which the long

molecular chains slide along each other
HMPE
Creep deformation
Taken from Galvin et al., Engineering in Medicine. 2007.

1.3.8 Viscoelastic modulus
• Viscoelastic behaviour of polymers is dependent on time and
temperature
Experiments can be used to measure this behaviour
• Stress relaxation experiments

• Specimen is strained rapidly in tension to a predetermined (relatively low) strain level
• Stress required to maintain this strain is measured as a function of time (at constant T)
• Stress decreases with time (because of the molecular relaxation processes in the polymer)
Relaxation modulus (a time dependent elastic modulus):
1.3.8 Relaxation modulus
• Relaxation modulus
– σ(t) = measured time dependent stress
– ε0 Strain level (which is maintained constant in experiment)
• Function of temperature
– To fully characterise a polymer, isothermal experiments
undertake over a range of temperatures (schematic plot)
1.3.8 Relaxation modulus
• Relaxation modulus
– σ(t) = measured time dependent stress
– ε0 Strain level (which is maintained constant in experiment)
• Function of temperature
– To fully characterise a polymer, isothermal experiments
undertake over a range of temperatures (schematic plot)
1.3.8 Viscoelastic modulus
Plot for polystyrene
– Low T – material is rigid and brittle (chains essentially

“frozen” in position)
– T increases – leathery (see viscoelastic type behaviour)
– Highest T – viscous liquid (chain motion significant)
MECH1280
Semester 2
1 POLYMERS | 1.3 Polymer Mechanical Properties – Part B
[LIVE]
Case study – Relaxation Modulus
Models for viscoelasticity
• Simplified parallel or series circuits based on springs and

dashpots
• Springs used to model elastic behaviour

σ = E.ε
• Dashpots used to model viscous components
𝑑ε
σ= η.
𝑑𝑡
• Models used to predict material responses under

creep/stress relaxation conditions
Maxwell model
Viscous dashpot and elastic spring in series – fixed strain applied
Kelvin-Voigt model
Viscous dashpot and elastic spring in parallel –fixed stress applied
1.3.8 Viscoelastic modulus REMINDER
• Viscoelastic behaviour of polymers is dependent on time and
temperature
Experiments can be used to measure this behaviour
• Stress relaxation experiments

• Specimen is strained rapidly in tension to a predetermined (relatively low) strain level
• Stress required to maintain this strain is measured as a function of time (at constant T)
• Stress decreases with time (because of the molecular relaxation processes in the polymer)
Relaxation modulus (a time dependent elastic modulus):
Maxwell-Weichert model
Relaxation modulus
1 𝑡 𝑡0 𝑡 𝑡0
− −
𝐸𝑟 𝑡 = 𝐸0 + [𝐸1 𝜏1 𝑒 𝜏 1 𝑒 𝜏 1 − 1 + 𝐸2 𝜏2 𝑒 𝜏 2 𝑒 𝜏 2 − 1 ]
𝑡0
E1 , τ1
E2 , τ2
E0
Case study – Application of Polymers
Methane (and other liquidifed natural gases – LNG) Cooled to -163◦C to transport as a liquid
Opgewerkte tekening van LNG tanker, zelf getekend, Peter Welleman

http://en.wikipedia.org/wiki/File:LNGtanker.jpg
• Tanks are Aluminium Alloy (to avoid brittle fracture at low
temperature)
• Tank also in a leak proof mild steel jacket with insulating layer
between the two (so steel is kept above the ductile to brittle
transition temperature)
• What happens if there is a leak and if insulation is porous?
• Inner wall is coated with layer of closed cell foam made of rigid
polyurethane
Polyurethane
Tank structure
• If tank leaks, contained by PUR structure,

protecting ships steel hull
• But there are incidents when PUR has

cracked
Thermal stresses in PUR foam
• PUR TG ≈ 100◦C
• Under normal operating conditions, temperature of foam increases

linearly with distance from foam
• Foam wants to contract as it gets cold, but prevented from doing this by
steel it is stuck to
• Temperature differential ΔT generates biaxial tensile stress σ in plane of

layer:
α = coefficient of thermal expansion

E = Young’s modulus
υ = Poisson's ratio of foam
• So presume that foam failed by brittle cracking when maximum thermal
stress was reached the fracture stress of the foam
• Check this against PUR foam data sheet
Cell size ≈ 0.5mm

Thermal expansion coefficient α≈10-4◦C-1
Poissons ratio υ = 0.3
Youngs modulus E ≈ 34MNm-2 at -100◦C
Fracture stress σf ≈ 1.4 MNm-2 at -100◦C
Fracture toughness Kc ≈ 0.05 MNm-3/2 at -100◦C
Reasonable estimates are:
T1≈0◦C
T2≈-100◦C
ΔT(t) ≈100◦C
• For a temperature differentiation of this magnitude σ ≈0.5 MNm-2
• But this is substantially less than the fracture stress of 1.4 MNm-2 at -100◦C
• So based on this – no fracture should have occurred
• Also consider fracture mechanics
• Estimate size of critical defect in the foam layer using the fast fracture equation:
Fracture toughness Kc =0.05 MNm-3/2

σ(t) = 0.5 MNm-2
c ≈ 3mm (defect is small, but compare to PUR cell size!)
• Formation of cracks in foam layer is due to small defects, this becomes critical as
temperature of the foam fell during filling with liquid methane
• Likely for crack to initiate from inner face of foam where thermal stress was
maximum
MECH1280
Semester 2
1 POLYMERS | 1.4 Polymer Characteristics – Part A
[LIVE]
Session being recorded
The recording of this session will
be made available in the following
places:
• MINERVA/VLE (University of
Leeds Portal Login for Students)
Information about recordings at the University of Leeds
http://help.leeds.ac.uk/lectures
1.4.1 Crystallization, Melting and Glass
Transition
Crystalline
Amorphous
As cooled,
ordered solid structure As cooled, go through
Produced (crystallisation) glass transition,
Melting become a rigid solid but

maintain disordered
is reverse (and occurs on molecular structure
heating)
1.4.1 Crystallization
• Degree of crystallinity influences the mechanical and thermal

properties, therefore important to understand the mechanism and
kinetics
• Occurs by nucleation and growth processes

Read 15.10 “Crystallisation” in Callister (page 591 in 8th edition) –
no need to memorise formula
Or “Polymer crystals” in Ashby and Jones (page 257 in 3rd edition)
1.4.1 Melting
Solid material, ordered Viscous liquid, highly

structure of aligned chains random structure
Features in polymers (not observed in ceramics or metals)
• Occurs over a range of temperatures

• Melting behaviour depends on polymer history; temperature at which crystallised
because thickness of lamellae will depend on crystallisation temperature (thicker
lamellae = higher Tm)
• Impurities in the polymer and imperfections in the crystals will decrease Tm
• Tm will be elevated by increasing the rate heating
1.4.2 Glass transition Tg
Glass transition occurs in amorphous and
semi-crystalline polymers due to a reduction
in the motion of large segments of the
molecular chain with decreasing temperature
(because of the formation of secondary bonds)
• On cooling, glass transition is the gradual

transformation from liquid to a rubbery material
and then rigid solid
• Glass transition temperature (Tg) is the temp at

which the material changes from rubbery to rigid
1.4.2 Glass transition temperature
Why ironing works… and synthetic fabrics
need lower temperatures
• A fabric is heated through this transition so that
the polymer chains become mobile.
• The weight of the iron then imposes a preferred

orientation.
Source http://en.wikipedia.org/wiki/Glass_transition accessed on Jan 2019
• Tg can be significantly decreased by addition of

plasticizers into the polymer matrix. Smaller molecules
of plasticiser embed themselves between the polymer
chains, increasing the spacing and free volume, and
allowing them to move past one another even at lower
temperatures (NB plasticisers make things softer)
1.4.2 Importance of Tm and Tg
• Important parameters relative to in-service applications of
polymers
• They define the upper (Tm) and lower (Tg) temperature limits of
applications, especially for semi-crystalline polymers
• Also influence fabrication and processing parameters
1.4.2 Factors that influence Tg and Tm
• Magnitudes of Tm and Tg increase with

increasing chain stiffness (stiffness is
enhanced by the presence of chain double
bonds and side groups that are either
bulky or polar)
• At low molecular weights Tm and Tg
increase with molecular weight and over
a range
• Small amount of branching tends to
decrease Tm and Tg (introduce defects
into the crystalline structure)
Understand reasons for this, go through Callister 15.14 “Factors
that influence melting and glass transition temperatures”
(Pg 594 in 8th edition)
deformation Reminder!
block segments

Orientation of block
segments and tie
chains with tensile
axis in final
deformation stage
deformation
Case study:
Shape Memory Polymers
Case study:
Tg < T < Tm
Coates et al., 2013

Case study:
• Polymer is die drawn at a temperature T, where Tg < T < Tm
• Die drawing re-orientates the polymer’s internal structural orientation –

improved mechanical properties
• When the polymer experiences a temperature above Tg again, it reverts back

to it’s original structural orientation (or near to it). The rate of reversion is
dependant on how far above Tg the temperature is
• Tg is different for different polymers – but can be controlled with additives,

fillers etc.
Case study:
What kind of applications could this be used in?
Herbert screw
Self-tightening sutures
MECH1280
Semester 2
1 POLYMERS | 1.4 Polymer Characteristics – Part B
[PRE-REC]
1.4.3 Polymer Fabrication and Processing
Understand:
• Polymerisation; addition and condensation
• Polymer additives (fillers, plasticizers, stabilisers; colorants and flame

retardants)
• Fabrication of fibres and films
See 15.20 “Polymerisation” to 15.24 “Fabrication of films and fibres” Callister

(pages 607-615 in 8th ed)
1.4.3 Forming techniques
Forming techniques used, depend on;
– If the polymer is thermoplastic or thermosetting
– If thermoplastic, the temperature at which is softens
– The atmospheric stability of the material being formed
– The geometry and size of the finished product
• Usually occurs at elevated temperatures and often with application of pressure
1.4.3 Forming techniques - Thermoplastics
• Formed above Tg if amorphous
• Formed above Tm if semi-crystalline
• An applied pressure must be maintained as the part cools (to retain

shape)
• Thermoplastics can be recycled, scrap is remelted and reformed into

new shapes
1.4.3 Forming techniques - Thermosets
Usually in two stages:
1. Preparation of a linear polymer (sometimes called a pre-polymer) as a liquid

with a low molecular weight
2. Converted into the final hard and stiff shape during second stage usually in a
mould of the final shape (termed curing)
– May occur with heating and/or addition of catalysts (and often under pressure)
– This is when cross-linked or network structure forms
– Thermoset polymers can be removed from the mould because they are geometrically stable
• Difficult to recycle, do not melt and are usable at higher temperatures
1.4.3 Moulding
Most common method of forming, several methods, including:
– Compression
– Transfer
– Blow
– Injection
– Extrusion
• For all – a finely pellitised or granulised plastic is forced at an elevated

temperature and pressure, to flow into, fill and assume the shape of a
mould cavity
1.4.3 Compression and transfer Moulding
• Forming process where polymer is placed directly into heated metal mould, softened by the heat,
and forced to conform to the shape of the mould as the mould closes.
• Preheating of the preform reduces moulding time and

pressure, extends the die lifetime and produces a
more uniform finished piece
• Can be used for both thermoplastic and thermosetting

polymers; however, its use with thermoplastics is
more time consuming and expensive than the more
commonly used extrusion or injection moulding
techniques
• In transfer moulding – a variation of compression

moulding – the solid ingredients are first melted in a
https://www.youtube.com/watch?v=KXxGqNzAry8
heated transfer chamber
1.4.3 Injection Moulding
Most widely used technique for fabricating thermoplastic materials
• Very quick process (each cycle about 10-30 s)
• Can also be applied to thermosetting polymers, curing occurs while material is under pressure in a heated
mould - results in longer cycle times than thermoplastics
https://www.youtube.com/watch?v=b1U9W4iNDiQ
1.4.3 Extrusion
Forming viscous thermoplastic lengths under pressure through an open-ended die
• Solidification of the extruded length is expedited by blowers, water spray or bath

• Can produce continuous lengths that have constant cross-sectional geometries
• Used for rods, tubes, hoses, channels, sheets, filaments
https://www.youtube.com/watch?v=zcBv_JvFDBI
1.4.3 Blow Moulding
Fabrication of plastic containers (similar to that used for blowing glass bottles)
(Extrusion, injection and stretch blow moulding)
The temperature and viscosity of the parison must be regulated carefully

https://www.youtube.com/watch?v=AD_Y4yZc54U
Case study – Car bumpers
• Until 1974 most car bumpers were made of steel
electroplated with chromium
• Legislation was introduced requiring bumpers to

withstand collisions without permanent damage to
car
– Europe 4km per hr

– USA 8.5km per hr
• Prompted design to absorb energy
Different approaches
• Collapsible Al tube, that was replaced after collisions (1976

AMC Matador Coupe)
• Energy absorbing device mounted inside rubber bellows in

front of wheel arch (Porsche 911, 1980)
• Differing legislation in Europe and USA led to different designs
Europe 1982 -1988 BMW USA 1982 -1988 BMW
• In Europe – lower speed limit of legislation meant more plastics used earlier
Materials performance – what is required?
– Impact resistance down to -30ºC
– Adequate rigidity to stay within dimensional tolerances of structure
– Resistance to UV radiation and fuel spillage
– Dimensional stability to prevent distortion over expected operating temperature
– Ability to be finished to match surrounding painted metal parts
Processed in low molecular weight

mass form and reacted to give high
molecular weight
Must be processed
as high molecular weight material
Choosing a material
• Choice of material, brings restrictions on process, further restricted by

shape required:
Reaction injection moulding (RIM)
is similar to injection moulding
• Possible processes: except thermosetting polymers are
used, which requires a curing
– Injection moulding reaction to occur within the mould.
– Reaction injection moulding

Contact moulding requires a
single mould against which
– Compression moulding combination of resin and reinforcing
fibres are formed without the need
– Contact moulding for pressure or heat.
Production costs
– All processes need permanent moulds

– All need direct labour
Mould for a large bumper (1988 prices)
For small volumes, most cost efficient process is a manual process with high labour and tooling costs
• Contact moulding – is used in prototyping
• RIM and compression moulding – comparable in medium volumes (i.e. limited editions / prestige cars)
• Injection moulding for high volumes
1.4 Polymer characteristics - Summary
Polymers - Summary

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Engineering Materials

• Mechanical properties are specified in

• Mechanical characteristics are sensitive to

• Increasing strain rate...

Roughly in order of increasing temperature, these are:

b) Cold drawing, the drawing-out of the molecules in the solid state,

c) Shear banding (giving slip bands like in metal crystals)

d) Crazing, micro-cracks associated with local cold drawing

e) Viscous flow, when secondary bonds in the polymer melt

Lower yield point

Ongoing elongation proceeds by

Two adjacent chain folded lamellae and

Elongation of amorphous tie chains

Two adjacent chain folded lamellae and

Elongation of amorphous tie chains

Two adjacent chain folded lamellae and

Elongation of amorphous tie chains

Two adjacent chain folded lamellae and

Elongation of amorphous tie chains

• Factors that favour brittle fracture are:

Elastomers must be:

• At intermediate temperature range, polymer has the

• You tube - silly putty

Irreversible process in which the long

Taken from Galvin et al., Engineering in Medicine. 2007.

Experiments can be used to measure this behaviour

• Stress relaxation experiments

Relaxation modulus (a time dependent elastic modulus):

Plot for polystyrene

– Low T – material is rigid and brittle (chains essentially

– T increases – leathery (see viscoelastic type behaviour)

– Highest T – viscous liquid (chain motion significant)

• Simplified parallel or series circuits based on springs and

• Springs used to model elastic behaviour

• Models used to predict material responses under

Viscous dashpot and elastic spring in series – fixed strain applied

Viscous dashpot and elastic spring in parallel –fixed stress applied

Experiments can be used to measure this behaviour

• Stress relaxation experiments

Relaxation modulus (a time dependent elastic modulus):

Opgewerkte tekening van LNG tanker, zelf getekend, Peter Welleman

• What happens if there is a leak and if insulation is porous?

• If tank leaks, contained by PUR structure,

• But there are incidents when PUR has

• Under normal operating conditions, temperature of foam increases

• Temperature differential ΔT generates biaxial tensile stress σ in plane of

α = coefficient of thermal expansion

• Check this against PUR foam data sheet

Cell size ≈ 0.5mm

• For a temperature differentiation of this magnitude σ ≈0.5 MNm-2

• So based on this – no fracture should have occurred

Fracture toughness Kc =0.05 MNm-3/2

Melting become a rigid solid but

• Degree of crystallinity influences the mechanical and thermal

• Occurs by nucleation and growth processes

Solid material, ordered Viscous liquid, highly

Features in polymers (not observed in ceramics or metals)

• Occurs over a range of temperatures