ME205: Engineering Materials

Lecture # 8: Polymers

Dr MZ Ansari
Mechanical Engineering
 1. Polymers
• Almost all biological systems are built of polymers which not
only perform mechanical functions (like wood, bone, cartilage,
and leather) but also contain and regulate chemical reactions
(like leaf, veins, and cells).
• Most polymers are made from oil
Four classes of engineering polymers are of interest to us
here:
(a) Thermoplastics such as polyethylene, which soften on
heating.
(b) Thermosets or resins such as epoxy which harden when two
components (a resin and a hardener) are heated together.
(c) Elastomers or rubbers.
(d) Natural polymers such as cellulose, lignin, and protein, which
provide the mechanical basis of most plant and animal life.
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 2. Thermoplastics
• Polyethylene is the commonest of the thermoplastics. They
are often described as linear polymers, that is the chains are
not cross-linked (though they may branch occasionally).
• That is why they soften if the polymer is heated: the secondary
bonds which bind the molecules to each other melt so that it
flows like a viscous liquid, allowing it to be formed.
• The molecules in linear polymers have a range of molecular
weights, and they pack together in a variety of configurations.
• Some, like polystyrene, are amorphous; others, like
polyethylene, are partly crystalline.
• This range of molecular weights and packing geometries
means that thermoplastics do not have a sharp melting point.
Instead, their viscosity falls over a range of temperature, like
that of an inorganic glass.
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 Cont’d
• The fiber and film-forming polymers polyacrylonitrile (ACN)
and polyethylene teraphthalate (PET, Terylene, Dacron, Mylar)
are also thermoplastics.

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 3. Thermosets or resins
• Thermosets are made by mixing two components (a resin and
a hardener) which react and harden, either at room
temperature or on heating. The resulting polymer is usually
heavily cross-linked, so thermosets are sometimes described
as network polymers. The cross-links form during the
polymerization of the liquid resin and hardener, so the
structure is almost always amorphous.
• On reheating, the additional secondary bonds melt, and the
modulus of the polymer drops; but the cross-links prevent true
melting or viscous flow so the polymer cannot be hot-worked
(it turns into a rubber). Further heating just decomposes it.
• The generic thermosets are the epoxies and the polyesters
(both widely used as matrix materials for fiber-reinforced
polymers) and the formaldehyde-based plastics (widely used
for molding and hard surfacing).
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Cont’d

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 4. Elastomers
• Elastomers or rubbers are almost-linear polymers with
occasional cross-links in which, at room temperature, the
secondary bonds have already melted. The cross-links provide
the “memory” of the material so that it returns to its original
shape on unloading.

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 5. Natural polymers
• The rubber polyisoprene is a natural polymer. So, too, are
cellulose and lignin, the main components of wood and straw,
and so are proteins like wool or silk. We use cellulose in vast
quantities as paper and (by treating it with nitric acid), we
make celluloid and cellophane out of it.

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6. Properties of Polymers

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 7. Mechanical Properties of Polymers
• Polymers have a spectrum of mechanical behavior, from brittle
elastic at low temperature, through plastic to viscoelastic or
leathery, to rubbery and finally to viscous at high temperature.
• Metals and ceramics have a range of mechanical behavior,
but, because their melting points are high, the variation near
room temperature is unimportant.
• With polymers it is different: between -20C and +200 C a
polymer can pass through all of the mechanical states listed
above, and in doing so its modulus and strength can change
by a factor of 103 or more.
• So while we could treat metals and ceramics as having a
constant stiffness and strength for design near ambient
temperatures, we cannot do so for polymers.

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 Cont’d
• The mechanical state of a polymer depends on its molecular
weight and on the temperature; or more precisely, on how
close the temperature is to its glass temperature, TG.
• Some polymers, like PMMA, and many epoxies, are brittle at
room temperature because their glass temperatures are high
and room temperature is only 0.75 TG .
• Others, like polyethylene, are leathery; for these, room
temperature is about 1.0 TG. Still others, like polyisoprene, are
elastomers; for these, room temperature is well above
TG(roughly 1.5 TG).
• So it makes sense to plot polymer properties not against
temperature T , but against T/ TG, since that is what really
determines the mechanical state. The modulus and strength
diagrams described in this chapter are plotted in this way.
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 Cont’d
• It is important to distinguish between the stiffness and the
strength of a polymer. The stiffness describes the resistance to
elastic deformation, the strength describes the resistance to
collapse by plastic yielding or by fracture.

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 Cont’d
• Linear-amorphous polymers (like PMMA or PS) show five
regimes of deformation in each of which the modulus has
certain characteristics. They are:
(a) The glassy regime, with a large modulus, around 3 GPa.
(b) The glass-transition regime, in which the modulus drops
steeply from 3 GPa to around 3 MPa.
(c) The rubbery regime, with a low modulus, around 3 MPa.
(d) The viscous regime, when the polymer starts to flow.
(e) The regime of decomposition, in which chemical breakdown
starts.

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 Cont’d
• Much engineering design—particularly with polymers—is
based on stiffness: the designer aims to keep the elastic
deflections below some critical limit. Then the material
property which is most important is Young’s modulus.
• Metals and ceramics have Young’s moduli which, near room
temperature, can be thought of as constant. Those of
polymers cannot.
• When a polymer is loaded, it deflects by an amount which
increases with the loading time and with the temperature. The
deflection is elastic—on unloading, the strain disappears again
(though that, too, may take time). So it is usual to speak of the
time and temperature dependent modulus.

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Cont’d

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 Cont’d
• Engineering design with polymers starts with stiffness. But
strength is also important, sometimes overridingly so.
• A plastic chair need not be very stiff— it may be more
comfortable if it is a bit flexible—but it must not collapse from
plastic yield, or fail in a brittle manner, when sat upon.
• There are numerous examples of the use of polymers
(luggage, casings of appliances, interior components for
automobiles) where strength, not stiffness, is the major
consideration.
• The “strength” of a solid is the stress at which something starts
to happen which gives a permanent shape change: plastic
flow or the propagation of a brittle crack, for example.

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 Cont’d
• At least five strength-limiting processes are known in
polymers. Roughly in order of increasing temperature, they
are:
(a) Brittle fracture, like that in ordinary glass.
(b) Cold drawing, the drawing-out of the molecules in the solid
state, giving a large shape change.
(c) Shear banding, giving slip bands rather like those in a metal
crystal.
(d) Crazing, a kind of microcracking, associated with local cold
drawing.
(e) Viscous flow, when the secondary bonds in the polymer have
melted.

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Cont’d

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8. Processing of Polymers

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