CHAPTERS 15:

POLYMER APPLICATIONS, &

PROCESSING
ISSUES TO ADDRESS...
How do these features dictate room T tensile
response?
Hardening, anisotropy, and annealing in polymers.
How does elevated temperature mechanical
response compare to ceramics and metals?

Stress Strain Behavior

The Mechanical characteristics of polymers are
highly sensitive to
Rate of deformation (strain rate)
Temperature
Chemical nature of environment (presence of water,
oxygen, organic solvents etc)

Stress-strain character for

a brittle polymer fractures while deforming elastically.
a plastic material is that initial deformation is elastic,
which is followed by yielding and a region of plastic
deformation.
elastomers is totally elastic, rubber like elasticity (large
recoverable strains produced at low stress levels)

Stress Strain Behavior

For plastic polymers

the yield point is taken as the point which occurs just

beyond the termination of linear elastic region.
The tensile strength corresponds to the stress at which
fracture occurs. Tensile strength may be greater than or
less than yield strength.

Stress strain behavior of polymethyl methacrylate

at several temperatures between 4C and 60C
(fig.15.3) shows that, increase in temperature
produces
Decrease in elastic modulus
Reduction in tensile strength
Enhancement of ductility

Decreasing the strain rate (rate of deformation)

has the same influence on the stress-strain
characteristics as increasing the temperature

T AND STRAIN RATE: THERMOPLASTICS

Decreasing T...
--increases E
--increases TS
--decreases %EL

Increasing
strain rate...
--same effects
as decreasing T.
Adapted from Fig. 15.3, Callister 6e. (Fig. 15.3 is from T.S. Carswell
and J.K. Nason, 'Effect of Environmental Conditions on the
Mechanical Properties of Organic Plastics", Symposium on Plastics,
American Society for Testing and Materials, Philadelphia, PA, 1944.)

Macroscopic deformation

Tensile stress strain curve for a semi crystalline

material
shows upper and lower yield points followed by a near
horizontal region.
At upper yield point a small neck forms within the
gauge section of specimen.
Within this neck, the chains become oriented, i.e., chain
axes become aligned parallel to the elongation
direction, which leads to localized strengthening.
Consequently there is a resistance to continued
deformation at this point, and specimen elongation
proceeds by the propagation of this neck region along
gauge length; the chain orientation phenomenon,
accompanies this neck extension.

This tensile behavior is in contrast to that found in

ductile metals wherein once neck is formed, all
subsequent deformation is confined to neck region

Macroscopic deformation

An amorphous polymer may behave like

a glass at low temperatures, a rubbery solid at

intermediate temperatures, and a viscous liquid as the
temperature is further raised.

For relatively small deformations, the mechanical

behavior
at low temperatures may be elastic, at higher
temperatures viscous or liquid-like behavior prevails.
For intermediate temperatures is found a rubbery solid
(viscoelastic)

Elastic deformation is
instantaneous ie. strain occurs the instant the stress is
applied or released (fig.15.5b)

For a totally viscous behavior deformation is

delayed in response to applied stress. (fig.15.5d)

Viscoelastic behavior results in

an instantaneous elastic strain, followed by viscous
time dependent strain. (fig.15.5c)

Viscoelastic relaxation modulus

Viscoelastic behavior of polymeric materials is

dependent on both time and temperature.

In stress relaxation measurements

specimen is initially strained rapidly in tension to a
predetermined and relatively low strain level.
The stress necessary to maintain this strain is measured
as a function of time, while temperature is held
constant.
Stress is found to decrease with time due to molecular
relaxation processes that take place within the polymer.

Relaxation modulus is defined as

(t )
Er (t )
(0)

the time dependent elastic modulus for viscoelastic

polymers as ratio of measured time dependent stress to
the strain level, which is maintained constant

Relaxation modulus decreases with time

Lower values of relaxation modulus occurs with
increasing temperature.

TIME DEPENDENT DEFORMATION

Stress relaxation test:
--strain to o and hold.
--observe decrease in
stress with time.

Data: Large drop in Er

for T > Tg.

(amorphous
polystyrene)
Adapted from Fig.
15.7, Callister 6e.
(Fig. 15.7 is from
A.V. Tobolsky,

Properties and
Structures of
Polymers, John

Wiley and Sons,

Inc., 1960.)

Relaxation modulus:
(t )
Er (t )
o

Sample Tg(C) values:

PE (low Mw)
PE (high Mw)
PVC
PS
PC

-110
- 90
+ 87
+100
+150

Selected values
from Table 15.2,
Callister 6e.

Viscoelastic
Viscoelastic creep

creep

Many polymeric materials are susceptible to time dependent

deformation when stress level is maintained constant.

Viscoelastic creep deformation may be significant

even at room temperature and under modest stresses that lie below
the yield strength of material.

In creep tests on polymers

stress is applied instantaneously and is maintained at constant level
while strain is measured as a function of time. Tests are performed
under isothermal conditions. E (t ) 0
c

(t )

Time dependent creep modulus may be defined as

the ratio of constant applied stress to the time dependent strain.
Creep modulus diminishes with increasing temperature.
Creep modulus increases as the degree of crystallinity increases.

Deformation of Semicrystalline Polymers

(Spherulitic structure)
Mechanism of elastic deformation in response to
the tensile stress is the
elongation of chain molecules from their stable
configurations, in the direction of applied stress, by
bending and stretching of strong chain covalent bonds.
In addition slight displacement of adjacent molecules
resisted by weak secondary or van der Waals bonds.

Elastic modulus may be taken as some

combination of moduli of crystalline and
amorphous phases.

Deformation of Semicrystalline Polymers

(Spherulitic structure)
Mechanism of plastic deformation is due to
The tie chains within the amorphous regions become
extended.
In the second stage deformation occurs by tilting of the
lamellae so that the chain folds become aligned with the
tensile axis.
Next, crystalline block segments separate from the
lamellae.
In the final stage, the blocks and tie chains become
oriented in the direction of tensile axis.

TENSILE RESPONSE: BRITTLE & PLASTIC

Stress-strain curves adapted from Fig. 15.1, Callister 6e. Inset figures along plastic response curve
(purple) adapted from Fig. 15.12, Callister 6e. (Fig. 15.12 is from J.M. Schultz, Polymer Materials Science,
Prentice-Hall, Inc., 1974, pp. 500-501.)
4

Factors that influence the Mechanical

Properties of Semicrystalline Polymers
Increasing the temperature or decreasing the strain
rate leads to
decrease in the tensile modulus, reduction in tensile
strength and an enhancement of ductility.

Tensile modulus rises as both the secondary

bonding strength and chain alignment increase.
Extensive chain entanglements or a significant amount
of intermolecular bonding inhibit relative chain
motions.
Significant intermolecular forces result from the
formation of large number of van der Waals inter chain
bonds.

Molecular weight
Tensile strength increases with increasing molecular
weight.
This is due to increased chain entanglement with rising
number average molecular weight.

Factors that influence the Mechanical

Properties of Semicrystalline Polymers
Degree of crystallinity:
Tensile modulus increases significantly with degree of
crystallinity.
Degree of crystallinity affects the extent of
intermolecular secondary bonding.
Extensive secondary bonding ordinarily exists between
adjacent chain segments for crystalline regions in which
molecular chains are closely packed in an ordered and
parallel arrangement.

Predeformation by drawing:
Strength and tensile modulus are improved by
deforming the polymer in tension (drawing).
During drawing the molecular chains slip past one
another and become highly oriented.
For materials drawn in uniaxial tension, tensile
modulus and strength are significantly greater in the
direction of deformation than in other directions.

PREDEFORMATION BY DRAWING
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.
Adapted from Fig. 15.12,
Callister 6e. (Fig. 15.12 is from
--decreases ductility (%EL)
J.M. Schultz, Polymer
Materials Science, Prentice Annealing after drawing...
Hall, Inc., 1974, pp. 500-501.)
--decreases alignment
--reverses effects of drawing.

Compare to cold working in metals!

Factors that influence the Mechanical

Properties of Semicrystalline Polymers
Heat treating (Annealing) For undrawn materials
increasing annealing temperature leads to
Increase in tensile modulus
Increase in yield strength
Reduction in ductility

Annealing effects in semicrystalline polymers are

opposite to that observed in metallic materials

Deformation of Elastomers
In an unstressed state
An elastomer will be amorphous and composed of
molecular chains that are highly twisted, kinked and
coiled.

Elastic deformation upon application of tensile

load
Is partial uncoiling, untwisting, and straightening and
the resultant elongation of the chains in the stress
direction.

Driving force for elastic deformation is entropy

which is a measure of disorder within a system.
Entropy increases with increasing disorder.
As an elastomer is stretched and the chains become
more aligned, the system becomes ordered.
If the chains return to the original kinked and coiled
contours, entropy increases.

TENSILE RESPONSE: ELASTOMER CASE

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.)

Compare to responses of other polymers:

--brittle response (aligned, cross linked & networked case)
--plastic response (semi-crystalline case)
6

Deformation of Elastomers
Criteria that must be met for the polymer to be
elastomeric are:
It must not easily crystallize (elastomeric chains are
amorphous)
Chain bond rotations must be relatively free for the
coiled chains to respond to an applied force
For relatively large elastic deformations, onset of
plastic deformation should be delayed.
Motion of chains past one another should be restricted by cross
linking. Cross links act as anchor points between chains and
prevent chain slippage from occurring.

The elastomer must be above its glass transition

temperature.
Below its glass transition temperature, an elastomer becomes
brittle.

Vulcanization: Crosslinking process in Elastomers

Vulcanization is achieved by a
nonreversible chemical reaction ordinarily carried out at
an elevated temperature.

In most vulcanizing reactions, sulfur compounds

are added to the heated elastomer
chains of sulfur atoms bond with adjacent polymer
backbone chains and crosslink them.

Unvulcanized rubber is soft and tacky and has

poor resistance to abrasion.
Modulus of elasticity, tensile strength are
enhanced by vulcanization.
The magnitude of modulus of elasticity is proportional
to the density of cross links.

To produce rubber of large extensions without

rupture of primary chain bonds
there must be relatively few cross links and these must
be widely seperated.

Crystallization
Crystallization
is a process upon cooling, an ordered solid phase is
produced from a liquid melt having highly random
molecular structure.

Chain folded layers

Upon cooling through the melting temperature nuclei
form wherein small regions of the tangled and random
molecules become ordered and aligned in the manner of
chain folded layers

Increase in chain folded layers or spherulite radius

Subsequent to nucleation and during crystallization
growth stage, nuclei grow by continued ordering and
alignment of additional chain segments i.e., chain
folded layers increase in lateral dimensions, or for
spherulitic structures there is an increase in spherulite
radius.

Melting
Transformation of a polymer crystal having an
ordered structure of aligned molecular chains, to a
viscous liquid in which the structure is highly
random.
Melting of polymers take place over a range of
temperatures.
Because every polymer is composed of molecules
having a variety of molecular weights and Tm depends
on molecular weight.

Melting of specimen depends on the temperature

at which it crystallized.
Thicker the chain folded lamellae, higher the
melting temperature
Increase in the rate of heating, results in elevation
of melting temperature

Melting and Glass Transition

Glass transition
Temperature at which polymer experiences the
transition from rubbery to rigid states is termed as glass
transition temperature Tg.

Melting and Glass transition temperatures

In a crystalline material there is a discontinuous change

in specific volume at melting temperature
Totally amorphous material experiences a slight
decrease in slope at glass transition temperature
In a semicrystalline polymer both melting and glass
transition are observed

Factors that influence the Melting (Tm) Temperatures

Chain stiffness, controlled by the ease of rotation

about the chemical bonds along chain has a
pronounced effect.
Presence of double chain bonds and aromatic groups
lower chain flexibility and cause increase in melting
temperature

Size and type of side groups influence the chain

rotational freedom and flexibility
Bulky or large side groups tend to restrict molecular
rotation and raise melting temperature
Polypropylene has a higher melting temperature than
polyethylene, the CH3 methyl side group for polypropylene is
larger than H atom found in polyethylene.

the presence of polar side groups (Cl, OH, CN) leads to

significant intermolecular bonding forces and relatively
high Tm.
Tm for polyvinyl chloride is higher than polypropylene.

Factors that influence the Melting (Tm)

Temperatures
Increasing average molecular weight (or chain
length) raises Tm.
Introduction of side branches introduces defects
into the crystalline material and lowers the melting
temperature.
High density polyethylene, a linear polymer has a
higher melting temperature than low density
polyethylene which has branching.

Factors that influence the and Glass Transition

(Tg) Temperatures
Chain flexibility is diminished and Tg is increased
by:
Presence of bulky side groups
Polar side atoms or groups of atoms
Double chain bonds and aromatic chain groups, which
tends to stiffen the molecular backbone.

Increasing the molecular weight raises Tg.

High density of branches raise Tg due to
reduced chain mobility

Crosslinked amorphous polymers elevate Tg

Crosslinks restrict molecular motion.

With high density of crosslinks molecular motion is
disallowed to the degree that glass transition is not
experienced by crosslinked amorphous polymers.

Tg lies between 0.5 to 0.8 Tm.

THERMOPLASTICS VS THERMOSETS
Thermoplastics:
--little cross linking
--ductile
--soften w/heating
--polyethylene (#2)
polypropylene (#5)
polycarbonate
polystyrene (#6)

T
mobile
liquid

viscous
liquid

crystalline
solid

Callister,
rubber
Fig. 16.9
tough
plastic

Tm
Tg

partially
crystalline
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
and Sons, Inc., 1984.)

--large cross linking

(10 to 50% of mers)
--hard and brittle
--do NOT soften w/heating
--vulcanized rubber, epoxies,
polyester resin, phenolic resin

SUMMARY
General drawbacks to polymers:

-- E, y, Kc, Tapplication are generally small.

-- Deformation is often T and time dependent.
-- Result: polymers benefit from composite reinforcement.
Thermoplastics (PE, PS, PP, PC):
-- Smaller E, y, Tapplication
-- Larger Kc
Table 15.3 Callister 6e:
-- Easier to form and recycle
Good overview
Elastomers (rubber):
of applications
-- Large reversible strains!
and trade names
Thermosets (epoxies, polyesters): of polymers.
-- Larger E, y, Tapplication
-- Smaller Kc

10

ANNOUNCEMENTS
Reading:

Core Problems:
Self-help Problems: