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Polymer Technology

Mechanical properties of polymers

Polymers available to the designer

 Polymers, more than any other design material, offer such a wide
spectrum of properties that they must be given serious
consideration in most component designs.

 However, this does not mean that there is sure to be a polymer

with the correct combination of properties for every application.

 The designer must have an awareness of the properties of the

range of polymers available and keep an open mind.

 A good design always involves a judicious selection of a material

from the whole range available, including non-polymers.

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Selection of Polymers
Material selection requires an awareness of the
general behaviour of polymers as a group, as well
as a familiarity with the special characteristics of
individual polymers.

The first and most important steps in the design

process are to define clearly the purpose and
function of the proposed product and to identify the
service environment. Then one has to assess the
suitability of a range of candidate materials.

Selection of Polymers
The following are generally regarded as the most important
characteristics requiring consideration for most engineering
components.
mechanical properties - strength, stiffness, specific strength and stiffness,
fatigue and toughness, and the influence of high or low temperatures on
these properties
corrosion susceptibility and degradation
wear resistance and frictional properties;
special properties, for example, thermal, electrical, optical and magnetic
moulding and/or other methods of fabrication.
total costs attributable to the selected material and manufacturing route.

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Mechanical Properties
Strength and Stiffness
Thermoplastic materials are viscoelastic. Thus when a thermoplastic is
stressed it responds by exhibiting viscous flow (which dissipates energy) and
by elastic displacement (which stores energy). The properties of viscoelastic
materials are time, temperature and strain rate dependent. Nevertheless the
conventional stress-strain test is frequently used to describe the (short-term)
mechanical properties of plastics.

• In the absence of any specific

information for a particular plastic,
design strains should normally be
limited to 1%.
• Lower values (-0.5%) are
recommended for the more brittle
thermoplastics such as acrylic,
polystyrene and values of 0.2-0.3%
should be used for thermosets.

Mechanical Properties

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Mechanical Properties
Ductility
A load-bearing device or component must not distort so much under the
action of the service stresses that its function is impaired, nor must it fail by
rupture, though local yielding may be tolerable. Therefore, high modulus
and high strength, with ductility, is the desired combination of
attributes.
However, the inherent nature of plastics is such that high modulus tends to
be associated with low ductility and steps that are taken to improve the one
cause the other to deteriorate

Mechanical Properties
Creep and Recovery Behaviour
Plastics exhibit a time-dependent strain response to a constant applied
stress. This behaviour is called creep. In a similar fashion if the stress on a
plastic is removed it exhibits a time dependent recovery of strain back
towards its original dimensions.

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Mechanical Properties
Stress Relaxation
plastics is that if they are subjected to a particular strain and this strain is held
constant it is found that as time progresses, the stress necessary to maintain
this strain decreases. This is termed stress relaxation and is of vital
importance in the design of gaskets, seals, springs and snap-fit assemblies.

Creep Rupture
When a plastic is subjected to a constant tensile stress its strain increases
until a point is reached where the material fractures. This is called creep
rupture or, occasionally, static fatigue.
It is important for designers to be aware of this failure mode
Reason - it is a common error, amongst those accustomed to dealing with metals, to assume that
if the material is capable of withstanding the applied (static) load in the short term then there need
be no further worries about it.
This is not the case with plastics where it is necessary to use long-term design
data, particularly because some plastics which are tough at short times tend to
become embrittled at long times.

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Mechanical Properties
Fatigue
Plastics are susceptible to brittle crack growth fractures as a result of cyclic
stresses, in much the same way as metals are.
In addition, because of their high damping and low thermal conductivity, plastics
are also prone to thermal softening if the cyclic stress or cyclic rate is high.
The plastics with the best fatigue resistance are polypropylene, ethylene-
propylene copolymer and PVDF.
Toughness
Some plastics are inherently very tough whereas others are inherently brittle.
Those which are nominally tough may become embrittled due to processing
conditions, chemical attack, prolonged exposure to constant stress, etc.
Where toughness is required in a particular application it is very important
therefore to check carefully the service conditions in relation to the above type
of factors.
At room temperature the toughest unreinforced plastics include nylon-6,6,
LDPE, LLDPE, EVA and polyurethane structural foam. At sub-zero
temperatures it is necessary to consider plastics such as ABS, polycarbonate
and EVA.
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Use of stress-strain curves

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Example: Comparing Mechanical

Properties of Thermoplastics

Compare the mechanical properties of LDPE, HDPE, PVC,

PP, and PS, and explain their differences in terms of their
structures.
SOLUTION

Let us look at the maximum tensile strength and modulus

of elasticity for each polymer.

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SOLUTION (Continued)

We can conclude that:

1. Branching, which reduces the density and close packing of
chains, reduces the mechanical properties of polyethylene.
2. Adding atoms or atom groups other than hydrogen to the
chain increases strength and stiffness. The methyl group in
polypropylene provides some improvement, the benzene ring of
styrene provides higher properties, and the chlorine atom in
polyvinyl chloride provides a large increase in properties.
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THERMOPLASTICS VS THERMOSETS
• Thermoplastics:
T
Callister,
rubber
--little cross linking viscous
Fig. 16.9
--ductile mobile liquid Tm
liquid tough
--soften w/heating
plastic
--polyethylene (#2) Tg
polypropylene (#5)
polycarbonate partially
crystalline
polystyrene (#6) crystalline
solid
solid

Molecular weight
• Thermosets: Adapted from Fig. 15.18, Callister 6e. (Fig. 15.18 is from F.W.
Billmeyer, Jr., Textbook of Polymer Science, 3rd ed., John Wiley
--large cross linking and Sons, Inc., 1984.)
(10 to 50% of mers)
--hard and brittle
--do NOT soften w/heating
--vulcanized rubber, epoxies,
polyester resin, phenolic resin 7 27

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Mechanical Properties

As temperature is increased the material becomes more flexible

and so for a given stress the material deforms more.
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Mechanical Properties

If a thermoplastic is subjected to a rapid change in strain it appears stiffer

than if the same maximum strain were applied but at a slower rate.

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Mechanical Properties
It is important to realise also that within the range of grades that exist for
a particular plastic, there can be significant differences in mechanical
properties.

very often a grade of material

selected for some specific
desirable feature (e.g. high
impact strength) results in a
decrease in some other
property of the material (e.g.
tensile strength).

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Effect of humidity on mechanical

properties of plastics

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Shish-kebab morphology

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Physical significance of important parameters

Stiffness — Defines the ability to carry stress without changing

dimension. The magnitude of the modulus of elasticity is a measure of
this ability or property.
Elasticity — Stipulates the ability to undergo reversible deformation or
carry stress without suffering a permanent deformation. It is indicated
by the elastic limit or, from a practical point of view, the proportional
limit or yield point.
Resilience — Defines the ability to absorb energy without suffering
permanent deformation. The area under the elastic portion of the
stress-strain curve gives the resilient energy.
Strength — Indicates the ability to sustain dead load. It is represented
by the tensile strength or the stress at which the specimen ruptures σB.
Toughness — Indicates the ability to absorb energy and undergo
extensive plastic deformation without rupturing. It is measured by the
area under the stress-strain curve.
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Factors that affect mechanical properties

• Molecular weight, Mw: Mass of a mole of chains.

smaller M w larger Mw
• Tensile strength (TS):
--often increases with Mw.
--Why? Longer chains are entangled (anchored) better.

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• % Crystallinity: % of material that is crystalline.

--TS and E often increase
with % crystallinity.
--Annealing causes
crystalline regions crystalline
to grow. % crystallinity region
increases.
amorphous
region
3

Adapted from Fig. 14.11, Callister 6e.

(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of
Materials, Vol. III, Mechanical Behavior, John
Wiley and Sons, Inc., 1965.)

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• Drawing...
--stretches the polymer prior to use
--aligns chains to the stretching direction
• Results of drawing:
--increases the elastic modulus (E) in the
stretching dir.
--increases the tensile strength (TS) in the
stretching dir.
--decreases ductility (%EL)

•Annealing after drawing...

--decreases alignment Adapted from Fig. 15.12,
Callister 6e. (Fig. 15.12 is from
--reverses effects of drawing. J.M. Schultz, Polymer
• Compare to cold working in metals! Materials Science, Prentice-
Hall, Inc., 1974, pp. 500-501.)

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TENSILE RESPONSE: ELASTOMER CASE

σ(MPa)
60 xbrittle failure

plastic failure
40 x

20 x
elastomer
final: chains
0
0 2 4 6 ε 8
are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, heavily cross-linked. is reversible!

Stress-strain curves adapted from Fig. 15.1, Callister 6e. Inset figures along elastomer curve
(green) adapted from Fig. 15.14, Callister 6e. (Fig. 15.14 is from Z.D. Jastrzebski, The Nature
and Properties of Engineering Materials, 3rd ed., John Wiley and Sons, 1987.)

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Effect of crosslinking

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• Compare to responses of other polymers:

--brittle response (aligned, cross linked & networked case)
--plastic response (semi-crystalline case)

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TIME DEPENDENT DEFORMATION

• Stress relaxation test:
• Data: Large drop in Er
(amorphous
--strain to εο and hold. for T > Tg. polystyrene)
--observe decrease in 105 rigid solid
Er(10s) (small relax) Adapted from Fig.
stress with time. in MPa 10
3 15.7, Callister 6e.
transition (Fig. 15.7 is from
A.V. Tobolsky,
tensile test 101 region Properties and

εo
Structures of
strain 10-1 Polymers, John
viscous liquid Wiley and Sons,

σ(t ) 10-3 (large relax) Inc., 1960.)

60 100 140 180T(°C)

time Tg
• Relaxation modulus: • Sample Tg(C) values:
σ(t ) PE (low Mw) -110
Er (t ) = PE (high Mw) - 90
εo PVC + 87
Selected values
from Table 15.2,
PS +100 Callister 6e.

PC +150
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Example: Design of Initial Stress in a Polymer

A band of polyisoprene is to hold together a bundle of steel
rods for up to one year. If the stress on the band is less
than 1500 psi, the band will not hold the rods tightly.
Design the initial stress that must be applied to a
polyisoprene band when it is slipped over the steel. A
series of tests showed that an initial stress of 1000 psi
decreased to 980 psi after six weeks.
SOLUTION

We can use the following equation and our initial tests to

determine the relaxation time for the polymer:
σ = σ o exp( − t )
λ
6
980 = 1000 exp( − 6 ), λ = = 297 weeks
λ 0.0202
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SOLUTION (Continued)

Now that we know the relaxation time, we can determine

the stress that must be initially placed onto the band in
order that it still be stressed to 1500 psi after 1 year (52
weeks).

1500 = σo exp(−52 / 297) = σo exp(−0.175) = 0.839σo

σo = 1500 = 1788 psi
0.839
The polyisoprene band must be made significantly
undersized so it can slip over the materials it is holding
together with a tension of 1788 psi. After one year, the
stress will still be 1500 psi.

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Hardness

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Wear Resistance and Frictional

Properties
There is a steady rate of increase in the use of plastics in bearing
applications and in situations where there is sliding contact e.g.
gears, piston rings, seals, cams, etc.
The advantages of plastics
low rates of wear in the absence of conventional lubricants
low coefficients of friction
the ability to absorb shock and vibration
the ability to operate with low noise and power consumption
Also when plastics have reinforcing fibres they offer high strength
and load carrying ability.
Typical reinforcements include glass and carbon fibres and fillers
include PTFE and molybdenum disulphide in plastics such as
nylon, PES, PPS, PVDF and PEEK.

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Wear Resistance and Frictional

Properties

The wear rate of plastics is governed by several mechanisms.

The primary one is adhesive wear which is characterised by fine
particles of polymer being removed from the surface. This is a
small-scale effect and is a common occurrence in bearings
which are performing satisfactorily.
However, the other mechanism is more serious and occurs when
the plastic becomes overheated to the extent where large
troughs of melted plastic are removed.

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Wear Resistance and Frictional

Properties

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Plastics are used extensively in the medical industry. One of the most interesting
medical applications for plastics is the “artificial hip”. Each prosthesis is made up of
two parts: the acetabular component (socket portion) that replaces the acetabulum,
and the femoral component (stem portion) that replaces the femoral head. The
femoral component is made of titanium, while the acetabular component is made of a
metal shell with a plastic inner socket liner. The plastic liner is molded from Ultra High
Molecular Weight Polyethylene and acts like a bearing. The UHMWPE is extremely
tough, abrasion resistant and has a very low coefficient of friction. This is a very good
example of how plastics and metals work together to enhance our quality of life.

Titanium
stem

UHMWPE
acetabular

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Wear Resistance and Frictional

Properties

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Wear Resistance and Frictional

Properties
In linear bearing applications the suitability of a plastic is usually
determined from its PV rating. This is the product of P (the bearing load
divided by the projected bearing area) and V (the linear shaft velocity).
Fig. 1.9 shows the limiting PV lines for a range of plastics - combinations of
P and V above the lines are not permitted.
The PV ratings may be increased if the bearing is lubricated or the mode of
operation is intermittent.
The PV rating will be decreased if the operating temperature is increased.
Correction factors for these variations may be obtained from
material/bearing manufacturers.
The plastics with the best resistance to wear are ultra high molecular
weight polyethylene (used in hip joint replacements) and PTFE lubricated
versions of nylon, acetal and PBT. It is not recommended to use the same
plastic for both mating surfaces in applications such as gear wheels.

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Fracture of polymers
Fracture is defined as stress-based material disintegration
through the formation of new surfaces within a body. Fracture
starts out as a localized event that eventually encompasses the
whole object.
Fracture is synonymous with rupture and breakage but not with
failure. The latter term is more general and also encompasses
non-mechanical breakdown through heat (thermal failure) or
environmental degradation (chemical attack, irradiation).

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Fracture of polymers

Brittle fracture of a polyethylene

pipe subjected to a burst test at
500 kPa

Ductile failure of an internally

pressurized polyethylene pipe.

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Fracture of polymers
For fracture to occur, it is generally necessary that a specimen be
subjected to mechanical loads and that the resulting, initially
homogeneous (viscoelastic) material deformation—which
eventually would lead to creep and ductile failure—becomes
heterogeneous and initiates material separation.
The most likely sites for material separation are structural
irregularities, growing material defects, or pre-existing cracks.
In a polymeric material, such sites are for instance given by
inclusions of particles or voids, craze-like features, or cracks.
Crazes and subsequently cracks extend as the material between
voids and adjacent to a crack tip deforms and/or disintegrates.

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Fracture of polymers
Depending on the nature and the extent of such deformation,
breakdown occurs in quite different modes of failure: as brittle
fracture by rapid crack propagation, crazing, or slow crack
growth, or by ductile failure
The mode of failure (of a cracked specimen) is not an inherent
property of a given material in a given environment.
It also depends on the loading rate and especially on the local
state of stress, which is strongly influenced by the configuration
of the crack itself.

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Fracture of polymers

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Fracture of polymers

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Fracture of polymers

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Fracture of polymers

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Fracture of polymers

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Fracture of polymers

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Fatigue

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Improving mechanical properties

Over the last several decades, plastics have gone from being
inexpensive substitutes for metals, concrete, and timber to
becoming materials of choice.
This has come about due to a combination of factors. As the
scientific community has come to better understand the behaviour
of polymeric materials, their structure and properties have been
improved to such an extent that they now compete with other
materials for traditional applications on both quality and price.
In addition, some of the unique properties of polymers have
resulted in the creation of new markets in such diverse areas as
transportation, housing, food packaging, healthcare, and
information and communication. Indeed, workers in both academic
and industrial research laboratories are constantly striving to
improve polymer properties and to create new polymers with
enhanced properties in order to bring improved products to market
and also find new applications for existing polymers.
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Improving mechanical properties

Several strategies have been followed to achieve these objectives.
For homopolymers, improving mechanical properties has largely
been a process of relating the internal structure of the polymer to
its properties. For amorphous polymers, we seek to align all of the
polymer chains in the same direction; this anisotropy results in a
higher glass transition temperature and an increase in both
stiffness and strength in the direction of molecular chain
orientation.
Semicrystalline polymers can be annealed to induce crystallization.
This, again, makes the polymer stiffer. Different structures can be
formed by drawing the polymer and by varying the temperature and
conditions of crystallization. These structures differ from each
other in the size, shape, and amount of crystals and in the
orientation of polymer chains in the amorphous and crystalline
regions, resulting in different mechanical properties.
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Improving mechanical properties

Textile engineers have long studied the effect of these different
variables using polymers such as nylons, polyethylene
terephthalate, and polypropylene; a considerable body of
knowledge now exists.
This has allowed for the production of not only high-quality textile
yarns but also of high strength, high-modulus fibers from
conventional polymers such as high-density polyethylene of high
molecular weight (> 106).
By careful control of molecular orientation and packing density, it
is now possible to manufacture high-density polyethylene fibers
having a modulus of 100 GPa and a strength of 1.4 GPa. Of
course, these results have been achieved only through the
development of special polymer processing techniques such as
solid-state extrusion and gel spinning.

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Improving mechanical properties

If we incorporate aromatic structures into the polymer backbone,
not only can we make the molecule rigid and rodlike, we can also
raise its Tg, make it thermally stable at high temperatures, and
impart high strength and stiffness.
Thus, linear aromatic thermoplastics such as semicrystalline
polyetherether ketone have a Tg of 143 °C and a maximum
continuous-use temperature of 250 °C.
Ultrastiff, rodlike molecules can also be made to form liquid
crystals from both the melt and solution; molecules such as poly-
p-phenyleneterephthalamide and thermotropic copolyesters can
be spun into fibers in a highly oriented, extended-chain form to
yield strength and stiffness values up to 3 GPa and 140 GPa,
respectively.

Young`s modulus of aluminum is about 70 GPa

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Improving mechanical properties

In addition to manipulating the physical and chemical structures of
homopolymers, we can chemically react two monomers whose
homopolymers have two different desirable properties. We do so
with a view toward obtaining both properties in the copolymer.
Thus, a random copolymer of styrene with butadiene provides
strength with flexibility, whereas reacting styrene with acrylonitrile
gives toughness and solvent resistance to polystyrene. On the other
hand, block copolymers such as polystyrene–polybutadiene–
polystyrene form two-phase systems with the butadiene block
constituting a continuous threedimensional elastomeric network and
the polystyrene phase serving as junction points. This material
behaves like vulcanized rubber at room temperature but flows like a
thermoplastic above the Tg of polystyrene. Finally, grafting pendant
groups such as sodium methacrylate to the polystyrene backbone
can help raise the glass transition temperature of the polymer.
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Improving mechanical properties

Most current-day research, though, is not concentrated in developing
new polymers. Instead, it is focused on blending existing polymers to
formulate new and improved materials. The classical example of this
approach is the blending of polystyrene with polyphenylene ether
(PPE) to give a single-phase miscible blend.
Not only does adding polystyrene to PPE allow the latter polymer to
be melt processed at a lower temperature and over a wider
temperature range, but mechanical properties, such as the modulus,
show a significant synergistic behavior.
Most commercial polymer blends, however, are thermodynamically
incompatible, two-phase mixtures. They are still useful because they
typically have improved impact strength and toughness, properties
especially important in automotive applications. A characteristic
example of this is high-impact polystyrene (HIPS), which is made by
mixing or grafting polybutadiene onto polystyrene.
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Improving mechanical properties

Another example of great commercial interest is
acrylonitrilebutadiene- styrene (ABS), in which styrene–acrylonitrile
is grafted onto poly(butadiene) and then these graft polymers are
mixed with styrene–acrylonitrile copolymers.
The dispersed rubber particles initiate crazes without crack
formation, leading to a tough, self-reinforcing composite material.
The quintessential method of improving the strength and stiffness
of polymers is to form reinforced composites by adding filler
particles, whiskers, short fibers, or long fibers to polymer matrices
such as epoxies, unsaturated polyesters, and vinyl esters.
Composite materials containing 50–70% by weight of fibers of
glass, carbon, or polyaramid in thermoplastic or thermosetting
polymer matrices can be lighter than aluminum and stronger than
steel. Although most of the development in this area has been
motivated by aircraft, aerospace, and automotive applications,
future growth is likely to be in civil engineering construction.
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Time-temperature superposition

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The expression given holds between Tg and Tg+100°C. However, if a

different reference temperature is chosen an equation with the same
form the above equation can be used, but the constants on
the right hand side must be re-evaluated.

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Example: Design/Materials Selection for

Polymer Components

Design the type of polymer material you might select for the
following applications: a surgeon’s glove, a beverage container
and a pulley.
SOLUTION
 The glove must be capable of stretching a great deal in
order to slip onto the surgeon’s hand. This requirement
describes an elastomer.
 A thermoplastic such as polyethylene terephthalate (PET)
will have the necessary formability and ductility needed for this
application.
 A relatively strong, rigid, hard material is required to prevent
wear, so a thermosetting polymer might be most appropriate.

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