Essentials of Polymer Engineering

(Introduction to Polymers)
ChE 197
Mechanical Properties of Polymers
 What we have discussed so far
• Introduction – basic concepts and definitions; classification of polymers
• Polymerization mechanisms – chain-reaction; ionic and coordination polymerization;
step-growth and ring-opening polymerization
• Chemical bonding and polymer structure – primary, secondary, and tertiary structures
• Thermal transition in polymers – Tg and Tm
• Polymer modification – copolymerization; postpolymerization reactions; functional
polymers
• Condensation (Step-Reaction) polymerization – mechanism; kinetics; stoichiometry;
molecular weight control and distribution
• Chain-Reaction (Addition) Polymerization
• Copolymerization
• Solution properties of polymers – solubility parameter, conformations of polymer
chains in solutions, thermodynamics of polymer solutions, solution viscosity
• Mechanical properties of polymers – mechanical tests, stress-strain behavior,
deformation, compression vs tensile tests, effects of structural and environmental
factors
 General Outline
• Mechanical tests – stress-strain experiments; creep
experiments; stress relaxation experiments; dynamic
mechanical experiments; impact experiments
• Stress-strain behavior – elastic stress-strain relations;
deformation of solid polymers; compression vs. tensile
tests
• Effect of structural and environmental factors on
mechanical properties – MW, cross-linking, crystallinity,
copolymerization, plasticizers, polarity, streric factors,
temperature, strain rate, pressure
 Overview on
mechanical properties of polymers
• Mechanical stability and durability coupled w/
their light weight – preferable alternative to
ceramics and metals
• Mechanical behavior – function of
microstructure or morphology
• Strong dependence to temperature and time
(viscoelastic behavior)
• Linear elastic behavior
yield phenomena

plastic deformation/cold drawing
 Mechanical tests
Failure of a polymer to perform its function can be due to:

Excessive elastic deformation – in structural, load-bearing applications; inadequate

rigidity or stiffness; controlling property is the elastic modulus

Yielding or excessive plastic deformation – in carrying design loads and occasional

accidental overloads; inadequate strength properties; controlling property is the yield
strength and corresponding strain
Fracture– cracks are regions of material discontinuity; precipitates failure through
fracture; fracture can be brittle or through fatigue

Brittle fracture – occurs where the absence of local yielding results in a build-up of
localized stresses
Fatigue failure - parts are subjected to alternating or repeated loads; no visible signs of
yielding since they occur at strengths well below the tensile strength of the
material

A variety of test methods exist for predicting mechanical performance limits under a
variety of loading conditions.
Stress-Strain Experiments

Specimen is deformed (pulled) at a

constant rate, and the stress required for
this deformation is measured
simultaneously

This test can be enhanced if they can be

carried out over a wide range of
temperatures and strain rates
Creep Experiments

Specimen is subjected to a constant load, and

the strain is measured as a function of time

The elongation may be measured

at time intervals using a travelling
microscope. Measurements may be
conducted in an environmental chamber.

Can be done in tension, shear, torsion,

flexure, or compression

Usually measures compliance

Stress Relaxation Experiments

Specimen is rapidly (ideally, instantaneously)

extended a given amount, and the stress
required to maintain this constant strain is
measured as a function of time

Stress that is required to maintain

the strain constant decays with time

Usually measures the relaxation

modulus Er(t,T) = time-varying stress
over constant strain
Dynamic Mechanical Experiments

Response of a material to periodic stress is measured

Torsion pendulum - a polymer sample is clamped at one end, and the

other end is attached to a disk that is free to oscillate

Provide useful information about the

viscoelastic nature of a polymer
 Dynamic Mechanical Experiments

Assume we impose a sinusoidal strain to two types of

materials (extreme): 1) elastic and 2) viscous ε0 – amplitude
ω – frequency (rad/s; = 2πf)

Stress response if material is purely elastic,

by Hooke’s law:
Stress and strain are in phase! G – shear modulus

Stress response if material is purely viscous,

by Newton’s law of viscosity:
Stress and strain are 900 out of phase!

In case of polymers (viscoelastic materials), response falls between the two extremes.
Sinusoidal stress and strain are out of phase by an angle δ
Dynamic Mechanical Experiments

Phase relation is shown between dynamic strain and stress for

viscous, elastic, and viscoelastic materials.
Dynamic Mechanical Experiments
Lag angle between stress and strain is defined by
the dissipation factor or tan δ
Denotes material damping characteristics
Complex modulus G = G’ + iG”
Ratio of energy viscously dissipated as heat G” over
the maximum energy stored in the material G’
during one cycle of oscillation

We can measure damping from experiments:

A1 and A2 are the amplitudes of two consecutive peaks

This may be expressed in terms of log

decrement (Δ) for free vibration instruments
like the torsional pendulum
 Impact Experiments
Prediction of failure due to rapid stress loading (impact load)

Measurement of the area under the stress strain

curve in the high-speed (rapid) tensile test

Falling ball or dart test - measurement of the

energy required to break a specimen by a ball of
known weight released from a predetermined
height

Izod test - measurement of the energy required

to break a H × H in. notched cantilever specimen
that is clamped rigidly at one end and then
struck at the other end by a pendulum weight
Charpy test - hammerlike weight
strikes a notched specimen that is
Brittle polymers (e.g. PS) – low impact resistance
rigidly held at both ends
Engineering thermoplastics (e.g. PA, PC) – high
impact resistance/impact strength
Stress-Strain Behaviors of Polymers

Typical polymer specimen for the tensile test

L0 – initial gauge length
Dog bone shape – encourages failure at the thinner middle portion

It is clamped at both ends and pulled at one of the clamped ends (usually downward) at
constant elongation

Engineering (nominal) stress Engineering (nominal) strain

 Stress-Strain Behaviors of Polymers
Engineering stress–strain curves generally depend on the shape of the specimen
Plot of true stress vs true strain - more accurate measure of intrinsic material performance
Ratio of the measured force (F) to the instantaneous
cross-sectional area (A) at a given elongation

Sum of all the instantaneous length changes,

dL, divided by the instantaneous length L

True strain and engineering strain

True stress and engineering stress

Note: AL = A0L0 since plastic deformation is a constant
volume process up to the onset of necking
L
σt = σ ⋅ = σ ⋅ (1 + ε )
L0 For small deformations
true stress ≈ engineering stress
 Elastic Stress-Strain Relations
When a material is subjected to small stresses, it responds elastically

Since stress may act on a plane in different ways, this constant is defined in different
ways depending on the applied force and the resultant strain

τ = Gγ
τ – shear stress
G – shear modulus

Elastic shear strain = tangent of angle of

deformation
 Elastic Stress-Strain Relations
∆V
D= Dilatation strain
V

σ = KD K – bulk modulus

Majority of cases – mixture of shear and dilatation E – Young’s modulus (or

(tensile and compressive tests) modulus of elasticity)

For most polymers, there

Poisson’s ratio
v = 0.5 (incompressible
materials; constant
volume deformation)
is a change in volume
For isotropic materials w/
elastic deformations:

Axial elongation accompanied by transverse contractions

 Example 1
In a tension test, a brittle polymer experienced an elastic
engineering strain of 2% at a stress level of 35 MN/m2. Calculate:
a) True stress; b) True strain; and c) fractional change in cross-
sectional area
 Example 2
Polypropylene has an elastic modulus of 2 × 105 psi and Poisson’s ratio of
0.32. For a strain of 0.05, calculate the shear stress and the percentage
change in volume.
 Deformation of Solid Polymers
To relieve stress, all materials under the influence of external load undergo some
deformation.

Elastic deformation - up to a certain limiting load, a solid will recover its original
dimensions on the removal of the applied loads; ability of deformed bodies to recover
their original dimensions

Plastic deformation - beyond the limit of elastic behavior (elastic limit); a material will
experience a permanent set or deformation even when the load is removed
Deformation of Solid Polymers
Gradient of the initial linear
portion of the curve, within
which Hooke’s law is obeyed,
gives the elastic, or Young’s,
modulus

Maximum on the curve

denotes the yield strength -
marks the limit of usable
elastic behavior or the
onset of plastic deformation

Stress at which fracture

occurs (material breaks
apart) = ultimate tensile
strength or, simply, tensile
strength σB
 Deformation of Solid Polymers – Physical
Significance of Measured Parameters
• Stiffness — ability to carry stress without changing dimension;
magnitude of the modulus of elasticity is a measure of this ability or
property
• Elasticity — ability to undergo reversible deformation or carry stress
without suffering a permanent deformation; elastic limit or yield
point
• Resilience — ability to absorb energy without suffering permanent
deformation; area under the elastic portion of the stress-strain
curve gives the resilient energy
• Strength — ability to sustain dead load; tensile strength or stress at
which the specimen ruptures σB.
• Toughness — ability to absorb energy and undergo extensive plastic
deformation without rupturing; area under the stress-strain curve
Deformation of Solid Polymers
Brittle polymers - fail with little or no
plastic deformation; no ability for
local yielding; local stresses build up
around inherent flaws, reaching a
critical level at which abrupt failure
occurs

Ductile polymers - ability to undergo

plastic deformation; this property
assists in the redistribution of
localized stresses
 Deformation of Solid Polymers
At small strains, polymers (both
amorphous and crystalline)

linear elastic behavior; from bond
angle deformation and bond
stretching
Further increase in strain
strain-
induced softening ; reduction of the
instantaneous modulus; uncoiling and
straightening of chains

Onset of necking
increase in the

local stress at the necked region due
to the reduction in the load-bearing
cross-sectional area (cold drawing)
Schematic representation of macroscopic changes in
Polymer chains in the amorphous
tensile specimen shape during cold drawing
regions undergo conformational
changes; become oriented in the
direction of the applied tensile stress
 Example 3
The mechanical properties of nylon 6,6 vary with its moisture content. A nylon
specimen with a moisture content (MC) of 2.5% has an elastic modulus of 1.2 GN/m2,
while that for a sample of moisture content of 0.2% is 2.8 GN/m2. Calculate the elastic
energy or work per unit volume in each sample subjected to a tensile strain of 10%.

In the elastic region:

 Example 4
Two nylon samples of moisture contents 2.5% and 0.2% have εB of 300% and
60%, respectively. Calculate the toughness of each sample if the stress-strain
curve of nylon for plastic deformation is given by:
 Compression versus Tensile Tests
Normal stresses can be either tensile or compressive

Compressive stress–strain data for two Compressive stress–strain data for two
amorphous polymers: polyvinyl chloride crystalline polymers:
(PVC) and cellulose acetate (CA) polytetrafluoroethylene (PTFE) and
polychlorotrifluoroethylene (PCTFE)

Stress–strain curves for the amorphous polymers are characteristic of the yield
behavior of polymers; no clearly defined yield points for the crystalline polymers
Compression versus Tensile Tests
In tension
polystyrene exhibited
brittle failure
In compression
behaved as a
ductile polymer

Strength and yield stress are generally

higher in compression than in tension

Tensile properties of brittle materials

depend to a considerable extent on the
cracks and other flaws inherent in the
material; brittle fracture occurs by
propagation of these cracks

Stress–strain behavior of a normally Compressive stresses close open

brittle polymer, polystyrene, under cracks; enhances strength
tension and compression.
Criterion for plastic deformation to occur
during application of tensile stress
Shear stress on A’

Max shear stress

at φ = π/4

Plastic deformation occurs when

τmax is at least equal to the yield
strength of the material

for plastic deformation to occur, the imposed

tensile stress must be at least twice the
magnitude of the shear stresses generated; the
Generation of shear stress tensile strength must be at least twice the
due to uniaxial loading shear strength (theoretical only)
 Effects of Structural and Environmental Factors
on Mechanical Properties – Molecular Weight
Schematic representation of the effect of molecular
weight on shear modulus temperature curve. Tg is
the glass transition temperature while Tfl is the flow
temperature. Tfl′, Tfl″, Tfl”’ - represent low-, medium-,
and high-molecular-weight materials, respectively
T < Tg – glassy region
T = Tg – transition from glassy to rubbery
T > Tg – rubbery region
T = Tfl – transition from rubbery to melt flow

If Tg > room temp, polymer is rigid at room
temp

If Tg < room temp, polymer is rubbery or
viscous at room temp
MW has practically no effect on the
modulus in the glassy region; also in
location of Tg and modulus drop
High MW
high number of
entanglements
high T at which viscous
flow becomes predominant over rubbery
behavior; longer rubber plateau
 Effects of Structural and Environmental Factors
on Mechanical Properties – Cross-Linking
Glassy region
increase in modulus due to
cross-linking is relatively small

Increase in modulus in the rubbery region and

the disappearance of the flow regions

Cross-linking raises the glass transition

temperature at high values of cross-link density

Cross-linking increases polymer ability to resist

deformation under load
increases its
modulus
Effect of cross-linking on shear modulus of
natural rubber; mean number of chain atoms
between successive cross-links is indicated (Mc);
low Mc, high cross-link density
 Example 5
The densities of hard and soft rubbers are 1.19 and 0.90 g/cm3, respectively.
Estimate the average molecular weight between cross-links for both materials
if their respective moduli at room temperature are 106 and 108 dynes/cm2.
average molecular weight between cross-links
ρ = density, R = gas constant, T = absolute temperature, and G = shear modulus

Hard rubber

Soft rubber
 Effects of Structural and Environmental Factors
on Mechanical Properties – Crystallinity

Crystallinity has only a small effect on modulus

below the Tg but has a pronounced effect
above the Tg

Intensity of modulus drop at the Tg decreases

with increasing degree of crystallinity

Sharper drop at the melting point

Melting temperature generally increases

Effect of crystallinity on the modulus with increasing degree of crystallinity
temperature curve. The numbers of the
curves are rough approximations of the
percentage of crystallinity
 Effects of Structural and Environmental Factors
on Mechanical Properties – Copolymerization

Random and alternating copolymers

are homogeneous; block and graft
copolymers with sufficiently long
sequences exhibit phase separation

Random and alternating copolymers
single

transition that is intermediate between those
of the two homopolymers of A and B; shifts
the the modulus–temperature curve

Effect of plasticization or copolymerization on the

modulus–temperature curve. The curves
correspond to different copolymer compositions.
(B) Unplasticized homopolymer; (A) either a
second homopolymer or plasticized B.
 Effects of Structural and Environmental Factors
on Mechanical Properties – Copolymerization

Block and graft copolymers, which exist

as a two-phase system, have two
distinct glass transitions, one for each
of the homopolymers

modulus–temperature curve shows two

steep drops (Tg of poly butadiene =
-800C; Tg of postyrene = 100oC)

Behaves like a polybutadiene (rubber)

matrix reinforced with polystyrene
(hard) phase
Shear modulus as a function of temperature for
styrene–butadiene–styrene block copolymers. Wt.%
styrene is indicated on each curve
 Effects of Structural and Environmental Factors
on Mechanical Properties - Plasticizers

Effect of plasticization or copolymerization on the modulus–temperature curve. The curves

correspond to different copolymer compositions. (B) Unplasticized homopolymer; (A) either a second
homopolymer or plasticized B.
 Effects of Structural and Environmental
Factors on Mechanical Properties - Polarity

Tg of polar poly(vinyl chloride) is about 90°C

higher than that of the nonpolar polypropylene.

Effect of the substitution of the chlorine atom

for the methyl group depends on the
molecular environment of the chlorine atom.

Shear modulus (a) and damping (b) as a function of

temperature: solid line is PVC; dashed line is PP
 Effects of Structural and Environmental
Factors on Mechanical Properties - Polarity

Tg of poly(2-chloroethyl methacrylate)
is only 20°C higher than that of poly(n-
propyl methacrylate)
Shear modulus (a) and damping (b) at 1 Hz as
a function of temperature:
(———) poly(2-chloroethyl methacrylate);
(––––) poly(n-propyl methacrylate
 Effects of Structural and Environmental Factors
on Mechanical Properties – Steric Factors
Long, flexible side chains reduce Tg, while
stiff side chains increase Tg

Long, flexible side chains increase the free

volume and ease the steric hindrance
from neighboring chains and as such facilitate
the movement of the main chain

Increase in modulus in the glassy region

with increase in length of the alkyl group
for poly(n-alkyl methacrylate).

Shear modulus (a) and damping (b) at 1 Hz as a function

of temperature for poly(n-alkyl methacrylate):
(––––) Polymethyl methacrylate;
(– – –) polyethyl methacrylate;
(— — —) poly(n-propyl methacrylate);
(· · · ·) poly(n-butyl methacrylate)
 Effects of Structural and Environmental Factors
on Mechanical Properties – Steric Factors

Softening temperature of polyolefins with

Brittleness temperatures for polyacrylates as a branched side chains
function of the total length of the side chain
Effects of Structural and Environmental Factors
on Mechanical Properties – Steric Factors

Effects of the Introduction of Rings into the Main Chain of Some Polyamides
Effects of Structural and Environmental Factors
on Mechanical Properties – Steric Factors

Polymer Stiffening Due to the Introduction of Rings into the Main Chain
Effects of Structural and Environmental Factors
on Mechanical Properties – Temperature

Modulus of a polymer decreases

with increasing temperature

Below the Tg, the modulus is high;

no yield point,brittle polymer

As the temperature is increased,

the modulus and yield strength
decrease and the polymer
becomes more ductile

Stress–strain behavior of cellulose acetate at

different temperatures
 Effects of Structural and Environmental Factors
on Mechanical Properties – Strain Rate

Polymers are very sensitive to the

rate of testing

As the strain rate increases, polymers

in general show a decrease in ductility
while the modulus and the yield or
tensile strength increase

Effect of decreasing temperature

is equivalent to that of increasing
the strain rate

Schematic illustration of the effect of strain

rate on polymers
Effects of Structural and Environmental Factors
on Mechanical Properties – Pressure

Modulus and yield stress

increase with increasing pressure

Tensile strength tends to increase

for ductile polymers, but
decrease for some brittle
polymers

Elongation at break increases for

some ductile polymers, but
decreases for most brittle polymers

The stress–strain behavior of polypropylene at Increase in pressure
decrease in free

different pressures volume
increase in packing density