Polymers, Ceramics &

Composites
IM 514 E

Dr Yehia M. Youssef

Copyright © YM Youssef, 11-Mar-22 Polymers, Ceramics & Composites 1

 Addition Polymers
• These polymers are formed by sequential addition of one
bifunctional or polyfunctional monomer to growing
polymer chains (say, Pn) without the elimination of any
part of the monomer molecule. With the subscript n
representing the chain length, the polymerization can be
schematically represented as follows:

• M represents a monomer molecule; this chain growth

step is usually very fast.
• The classic example of addition polymerization is the
preparation of vinyl polymers.

Copyright © YM Youssef, 11-Mar-22 Polymers, Ceramics & Composites 2

 Addition Polymers
• Vinyl monomers are unsaturated organic compounds
having the following structure:

• where R is any of a wide variety of organic groups: a

phenyl, a methyl, a halide group, and so forth. For
example, the polymerization of vinyl chloride to give
poly(vinyl chloride) can be written in the simplified form:

• Ring-opening reactions, such as the polymerization of

ethylene oxide to give poly(ethylene oxide), offer another
example of the formation of addition polymers:

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 Condensation Polymers
• These polymers are formed from bifunctional or
polyfunctional monomers with the elimination of a small
molecular species. This reaction can occur between any two
growing polymer molecules and can be represented by:

• where Pm and Pn are polymer chains and W is the

condensation product.
• Polyesterification is a good example of condensation
polymerization. In the synthesis of poly(ethylene
terephthalate), ethylene glycol reacts with terephthalic acid
according to the following scheme:

Copyright © YM Youssef, 11-Mar-22 Polymers, Ceramics & Composites 4

 Condensation Polymers
• As indicated by the double arrow, polyesterification is a
reversible reaction. Polyamides (sometimes called nylons)
are an important class of condensation polymers that are
formed by reaction between amine and acid groups, as in:

• Both of these polymers are classified as polyamides because

the repeat units contain the ̶ [CO ̶ NH] ̶ amide group.

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 Glass-Transition Temperature

Specific volume of polymers as a function of temperature. Amorphous polymers,

such as acrylic and polycarbonate, have a glass-transition temperature, Tg, but do not
have a specific melting point, Tm. Partly crystalline polymers, such as polyethylene
and nylons, contract sharply at their melting points during cooling.
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 Degree of Crystallinity

c (  s −  a )
% crystallinity =
 s ( c −  a )

Amorphous and crystalline regions in a polymer. Note that the

crystalline region (crystallite) has an orderly arrangement of
molecules. The higher the degree of crystallinity, the harder, stiffer,
and less ductile is the polymer.
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 Additives to Polymers
Improve mechanical properties, processability,
durability, etc. These include:
• Fillers
– Added to improve tensile strength & abrasion
resistance, toughness & decrease cost
– ex: carbon black, silica gel, wood flour, glass,
limestone, talc, etc.

• Plasticizers
– Added to reduce the glass transition
temperature Tg
– Commonly added to PVC - otherwise it is brittle

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 Additives to Polymers
• Stabilizers
– Antioxidants
– UV protectants
• Lubricants
– Added to allow easier processing
– “slides” through dies easier – ex: Na stearate
• Colorants
– Dyes or pigments
• Flame Retardants
– Cl/F & B

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 Polymer Melt Rheology
• The stress-strain relationships for solids do not apply to
liquids. This can be easily seen by imagining a sample of
water being pulled in tension – the water is incapable of
being pulled in this way.
• Hence a tensile stress on water will not produce a
displacement (strain). Therefore, different mechanical
behavior relationships must be developed from those used
for elastic solids.
• The most common mechanical formulation involves the
relationship between stress (shear stress) and the velocity
gradient (i.e. the change in velocity with distance) as
illustrated in the figure.

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 Polymer Melt Rheology

Moving Plate of area A

Force

Fluid

Velocity gradient Stationary Plate

or shear rate

Stress and velocity gradient relationships

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 Polymer Melt Rheology
• A fluid is contained between two plates, one stationary
and the other movable. The movable plate has an area
A, and is subjected to a force F. This force causes the
layer of liquid to next to the moving plate to be
displaced at a certain velocity.
• The movement of that layer of fluid influences the next
lower layer and make it move but its velocity is less
than the first layer and so on.
• This reduction in velocity from layer to layer is caused
by the tendency of the second layer of fluid to resist
movement. This resistance to movement is much like
inertia and is called the viscosity of the fluid. High
viscosity fluids have higher resistance to flow.

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 Polymer Melt Rheology
• Therefore, the stress (F/A) causes a velocity gradient in
the fluid. The velocity gradient can be also thought of
as a change in the shear with respect to time, a shear
rate (  ).
• This resistance to flow, viscosity, is defined by the
following equation:
F dv •
= = = 
A dx
where  = F/A is the shear stress, dv/dx is the velocity
gradient,  , is the shear rate, and  is the viscosity.
• The study of the flow of viscous fluids is called
‘Rheology’, and devices that assist in determining the
viscosity are called rheometers.
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 Newtonian and Non-Newtonian Fluids
• When the stress-velocity gradient or shear rate curve is
linear, the fluid system is said to be Newtonian and the
viscosity is constant. Water is an example of a
Newtonian fluid. Gases, true solutions and non-
colloidal liquids are Newtonian.
• When the shear stress and the velocity gradient or
shear rate are not linear, the fluid is non-Newtonian.
Two types of non-Newtonian fluids are possible, as
shown in the figure.

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 Newtonian and Non-Newtonian Fluids
• Materials in which the increase in viscosity with shear
rate is less than linear are called shear-thinning or
pseudoplastic, whereas materials that thicken at more
than linear shear rates are called shear-thickening or
dilatant.
• Most polymer liquids are shear-thinning. An example
of a shear-thinning material is the ink in a ball-point
pen. The ink flows readily when sheared (such as
during writing) but not otherwise.
• Dilatant behavior is observed in some ionomers or
ionically stabilized dispersions. Quicksand and some
sand-filled emulsions show this behavior.

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 Newtonian and Non-Newtonian Fluids

Non-Newtonian (shear
thickening or dilatant)
Shear stress (= Fs/As)

Non-Newtonian (shear
thinning or pseudoplastic)

Newtonian

Velocity gradient or shear rate (  )

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 Polymer Melt Rheology
• Polymer melts are invariably pseudoplastic. It has been
already mentioned that pseudoplastic fluids exhibit a
property of shear-thinning, i.e. there is not a simple
linear relationship between the shear stress and shear
rate.
• The estimation of the true non-Newtonian viscosity,
true, is time consuming since the slope of the tangent
of the pseudoplastic curve is continually changing; it is
necessary each time to produce the full flow curve, so
that its tangent can be measured at specific values of
strain rate. , on the other hand in Newton’s equation is
a true constant.

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 Polymer Melt Rheology
• It is more common and of more practical use if a value
analogous to the Newtonian viscosity is used.
Parameters called ‘apparent strain rate’ and ‘apparent
viscosity’ have been defined.
• Instead of measuring the tangent of the stress-strain
rate curve, the secant to the curve is considered and
the slope, , obtained is defined as the ‘Apparent
viscosity’.
• The true and apparent viscosities decrease with
increasing shear rate. This is a very important
characteristic of polymer melts since it means that the
viscosity of the melt decreases as the screw speed in
an extruder or an injection moulding machine
increases.
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 Polymer Melt Rheology
• The difference between the viscosity at very low shear
rates, i.e. at very low screw speeds such as those
experienced as the machine starts up, and that at the
higher screw speeds commonly used in processing can
be as much as 2 orders of magnitude or more.
• This is important since without it polymer processing as
we know it would probably be uneconomic. Since the
strain rate is a function of the screw speed of the
extruder, as the screw speed increases the viscosity of
the polymer melt decreases and so does the power
requirement.

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 Polymer Melt Rheology
• If this was not the case, motors for extruders and other
processing equipment would need to be much larger
than they are, and certainly much more costly, possibly
making the manufacture of certain products too
expensive to be commercially viable.

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 Polymer Melt Rheology

Viscosity of some thermoplastics as a function of (a) temperature

and (b) shear rate. Source: After D.H. Morton-Jones.

Copyright © YM Youssef, 11-Mar-22 Polymers, Ceramics & Composites 21

 Polymer Melt Rheology
• The magnitude of the shear thinning behaviour can be
seen in the following table.

Polystyrene Linear Low Density Polypropylene

Polyethylene
, s-1 , Pa.s
1 8,000 9,000 10,400
100 700 1,400 800
1000 110 310 140
10000 20 40 20

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 Polymer Melt Rheology
• There are a number of empirical mathematical models,
some more complex than others, which attempt to
describe the relationship between stress and strain rate
for pseudoplastic fluids.
• These include the Carreau model, the Ellis model and
the Polynomial model, but that which is most widely
used and which has found many important engineering
applications is the Power Law equation.

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