Relaxation modulus and Creep

compliance
Fundamental viscoelastic material functions.
Give relationship between stress and strain in a constant stress
experiment (creep compliance) and a step strain experiment
(relaxation modulus).

D (t ) =

Creep
time

Step strain

time

21 (t )
E (t ) =
0

time

GCH 6101- Viscoelasticity and mechanical properties

21 (t )
0

time
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The Maxwell element

In many cases we can represent linear viscoelastic behavior
by a Maxwell element.
Single Maxwell element in parallel
with a spring:

E(t ) = E exp( t ) + E e

or = /E
Maxwell element: it has a
modulus associated with the
spring and a viscosity
associated with the dashpot.
GCH 6101- Viscoelasticity and mechanical properties

E( )
E ' () =
+ Ee
2
1 + ( )
E( )
E ' ' () =
2
1 + ( )
2

Model of a viscoelastic solid if Ee > 0, or

a viscoelastic liquid if Ee = 0.
is the relaxation time.
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The Voight Element

Maxwell elements cannot describe creep response. In
this case we use the Voight element.
Voight element:

Single Voight element:

D(t ) = D[1 exp( t )]

E=1/D

or = /E

GCH 6101- Viscoelasticity and mechanical properties

Mechanical model of a
viscoelastic solid.
is the retardation time.

PM Wood-Adams

Mechanical behavior of polymers

Problems: fatigue, fracture and failure in polymers
In the past, treated empirically
Nowadays, ideas of thermodynamics, viscoelasticity and
molecular bonding are used to explain failure

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Structural and environmental factors that

affect mechanical properties

MW
Cross-linking
Crystallinity
Copolymerization
Plasticizers
Polarity
Steric factors
T
Rate of deformation
Pressure

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Thermodynamics energy balance

for deformation and fracture
First law of thermodynamics
Consider a closed system with an increment of energy U1
given by mechanical work
U1 is divided into 3 types of energy in a closed system:
U1 = U2 + U3 + U4

U2 irreversible dissipation
U3 stored or potential energy
U4 change in kinetic energy
U1

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Thermodynamics energy balance

for deformation and fracture
U2 irreversible dissipation
Ex. viscous flow converted to heat
Adiabatic systems: T rise
Isothermal systems: thermal energy
transferred to surroundings
U3 stored or potential energy
Ex. stored elastic ( spring concept)
U4 change in kinetic energy
Ex. changes in energy associated with
variations in linear or angular velocity

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Net input for the isothermal case

Under a displacement u:

U1 U 2 U3 U 4
=
+
+
u
u u u
Spring:

Dashpot:

Force (f = Ma)

U 3
= E
u
U 2
d
=
u
dt

GCH 6101- Viscoelasticity and mechanical properties

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Net input for the isothermal case

Results in the equation of forced vibration of a viscously
damped system:
2

d
d
= + E + M 2
dt
dt

Describes the motion of a Maxwell element, including mass

and acceleration concepts (last term)

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Mechanical deformation of a body

(including that of a polymer)
Governed by simple thermodynamic laws applied to
mechanical systems
Case of a body fracturing, where the crack increases by A
energy change:

U1 U 2 U3 U 4
=
+
+
A A A A

R = fracture resistance
Second term energy dissipated in propagating a fracture
over an increment of crack A work required to create a
new surface
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Mechanical deformation of a body

R = fracture resistance higher R, tougher material

U 2
R=
A

G = strain energy release rate

U1 U3

G=
A A
If G > R unstable system, crack velocity increases
(fracture occurs)
G = work of fracture, fracture energy per unit area of crack
created
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Toughness
Toughness area under the stress-strain curve to break.
Energy per unit volume, work expended in deforming the
material

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Increasing toughness of a polymeric

material
Small amounts of rubber in
small phase separated domains
stress concentrators (result
of the large mismatch between
modulus of the rubber and the
rigid matrix)
promotes the formation of
crazes throughout the body of
the sample
crazes are regions of highly
oriented chains and non
continuous microvoids
GCH 6101- Viscoelasticity and mechanical properties

ABS plastic
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Increasing toughness of a polymeric

material
Two brittle materials:
glass fibers in a thermosetting polyester resin (high Tg)
disperse one in the other, but keep the interface weak

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Deformation and fracture in polymers

Evaluation of the deformation and fracture behaviour

Three tests:
1. Stress-strain (slow)
2. Impact (fast)
3. Fatigue (cyclic)
Stress-strain and impact tests energy is absorbed by
viscoelastic deformation of polymer chains and by the
creation of new surface areas
Creep and relaxation damages caused, but generally no
fracture

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Stress-strain behaviour of polymers

Three different behaviours:

1. Brittle plastic
2. Tough plastic
3. Elastomer

Elastomer

Initial slope gives

Young's modulus E

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Viscoelastic characteristics of -
behaviour
( t ) = E( t )d
d
( t ) = E ( t x ) dx
dx
0
t

dx time increments

d
speed of tensile
dx
test
GCH 6101- Viscoelasticity and mechanical properties

Modulus for an amorphous material

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Viscoelastic effects on - behaviour

yield stress

Effect of deformation rate

GCH 6101- Viscoelasticity and mechanical properties

Effect of temperature

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Tensile strength
Metals/
Alloys

Tensile strength
stress to break the
material
Simple to measure,
inexpensive test,
widely reported
Increases with
MW, orientation
and crystallinity

Tensile strength, TS (MPa)

5000

GCH 6101- Viscoelasticity and mechanical properties

3000
2000
1000

300
200
100
40
30
20

Graphite/
Ceramics/ Polymers
Semicond

Composites/
fibers
C fibers
Aramid fib
E-glass fib

Steel (4140)qt
Diamond
W (pure)
Ti (5Al-2.5Sn)a
Steel (4140)a
Si nitride
Cu (71500)cw
Cu (71500)hr Al oxide
Steel (1020)
Al (6061)ag
Ti (pure)a
Ta (pure)
Al (6061)a
Si crystal
<100>

Glass-soda
Concrete
Graphite

AFRE(|| fiber)
GFRE(|| fiber)
CFRE(|| fiber)

Nylon 6,6
PC PET
PVC
PP
HDPE

wood(|| fiber)
GFRE( fiber)
CFRE( fiber)
AFRE( fiber)

LDPE

10

wood(

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fiber)

19

Drawn fibers

GCH 6101- Viscoelasticity and mechanical properties

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Cold-drawing of crystalline polymers

Necking shear yielding

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Yield strength
Yield strength very useful for design
Corresponds to formation of neck
Onset of permanent damage
the neck region is strengthened (and stiffened) due to
aligned chains and crystallitesdeformation continues outside
of the neck region (this is a form of shear yielding)

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Brittle vs. ductile material

Brittle material: little or

no plastic deformation
before fracture: normally
crazing
GCH 6101- Viscoelasticity and mechanical properties

Ductile material: significant

plastic deformation occurs:
shear yielding involving
molecular slip
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Yield criteria
For plastic deformation of glassy polymers in general
stress fields von Mises criteria

(1 2 )2 + ( 2 3 )2 + ( 3 1 )2 = 6C 2
(tri-axial stresses)

C = f ( P, T , &) for polymers

2
3

If left-hand side > 6C 2 yielding

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Application of von Mises criterion to PMMA in

biaxial stress (3=0, room temperature)
Tensile in both
stress components

Compressive in
both stress
components
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Impact testing
Impact resistance is the energy
required to fracture a material
when struck with a sharp blow
Impact strength is affected by
things which influence the speed
of crack propagation in the
material eg. the presence of a
rubbery phase or the presence
of shear yielded zones or crazes

Charpy impact test

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Effect of Tg on Impact resistance

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Deformation and fracture in polymers

Energy may be absorbed by:

Shear yielding
Crazing
Cracking

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Deformation modes
Plastic deformation during a tensile test can be caused by
shear yielding or by crazing
Plastic flow contributes to the toughness of a material and
is therefore desirable
Some polymers show both modes of deformation (crazing
and shear yielding), others only one mode

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Craze vs. crack

Craze:
Not an open fissure fibrils
composed of highly oriented polymer
chains join 2 sides
Microscopic voids
Increase of volume (not recoverable).
Not related to the volume increase
related to Poissons ratio which is
recoverable
Whitening of material
Crack:
Catastrophic failure
Initiated by a flaw
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Crazing
Craze precursor to a crack
Runs perpendicular to the loading
direction in uniaxial testing
Can support a load, unlike a crack,
because its 2 surfaces are connected
by a multitude of fine fibers ( = 5 - 30
nm)
Occurs mostly at the surface but can
nucleate in the interior of the polymer
as well
crazing is also called normal stress
yielding

Arrows are showing the

direction of loading

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Shear yielding

There are shear forces present

in a material even when it is
subjected to a simple tensile
elongation.

Appears as bands at an angle to the tensile axis (maximum

when = 45)
No change of density
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Brittle-ductile transition
Craze forms at right angle to the applied stress
Shear yielding molecular slip at ~ 45 to the applied
stress (assuming uniaxial - relationship)
Crazing 1-2% (brittle)
Shear yielding 10-20% (ductile)
Function of T
Compression or hydrostatic pressure suppresses crazing
and failure occurs by shear yielding

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Compression vs. tensile tests

Strength and yield stress are higher in compression
In contrast to tensile stresses, compression tends to close
cracks instead of opening them

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Crack growth
Griffith equation:

2E s
c =

1/ 2

A material is strained energy is stored internally by

chain extension, bond bending and bond stretching
This energy is dissipated if VE flow or bond breakage
occurs
s surface tension (intrinsic surface energy) (same
symbol as shear strain)
a half the crack length
Equation derived for center-notch panels
Crack will grow if > c.
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Analysis in terms of the stress intensity

1/ 2
factor K
EG
p = energy involved in plastic
deformation
ys = yield stress

ry = radius of plastic zone at

crack tip

K = stress intensity factor,

represents the number of times
the stress is magnified at the
crack tip, depends on the
particular deformation
conditions
GCH 6101- Viscoelasticity and mechanical properties

U
a
G = 2( s + p )
G=

1 K2
ry =
2 ys2

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36

Stress intensity factor K

For plane stress:

K2 = EG

(Plane stress = State of stress in which one of the three

principal stresses is zero and the remaining two are
nonzero)
For plane strain:

EG
K =
2
(1 )
2

(Plane strain = only the strain components in one plane

are non-zero)
For a center-notch panel: K = (a)

Critical conditions of crack spreading: Kc = c(a)

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Critical values for polymers under plane

strain (tensile testing conditions)

K1c is known as the fracture toughness of a material.

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Cyclic deformations

Simulate mechanical vibrations

Low stress but ~ 105 cycles
Fatigue material failure
Stress vs. number of cycles to failure (S-N curves)
Three regions:
1. Crack initiation
2. Crack propagation
3. Final failure

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Fatigue properties of polymers

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Cyclic deformations
On a molecular level, two mechanisms:
Material may get hot owing to adiabatic heating (@
crack tip)
Growth of the crack itself
N depends on stress level (S)
High MW and narrow MWD are more fatigue resistant

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Fatigue

Failure occurs by:

1. Craze formation
2. Craze growth
3. Crack nucleation
4. Crack propagation

Two kinds of fatigue failure for glassy polymers:

Brittle failure
Thermal softening
T rise in the sample can result from damping
characteristics (tan ), and can lead to fatigue failure

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Molecular aspects of fracture and

healing in polymers
Interdiffusion at polymer-polymer interface healing
process: disappearance of the interface
Reptation theory:
Portion of the chain that has escaped its original
conformation (tube) can contribute to interdiffusion
across the interface

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Molecular basis of fracture in glassy

plastics

Tougher materials VE energy dissipation, major energy

consuming factor in most polymer fractures

Chain scission is therefore delayed

Effect of external stress on relaxed amorphous state:

Elongate coil segments residing in the fracture plane
Followed by chain scission or pullout

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Molecular mechanism of fracture

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Chain scission
Steps in chain scission:
1. 109 C-C bond angle is opened
to 180
2. 0.154 nm C-C distance
increases to a larger value
0.254 nm is apparently
required to break the bond
Evidence points to the stretching
and orientation action of craze fibril
formation (crazing) as the actual
site of chain scission

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Chain pullout
Chain pullout:
Pullout energy related to the velocity of a chain moving
through its tube
Molecular frictional coefficient per unit length of mer:
E : energy for chain pullout

2E
0 = 2
nL

: velocity of the chain being pulled out

n = N0 N a
N0 : total number of chains per unit volume
Na : number of chain scissions per unit volume
L : length of segment being pulled out

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Chain pullout
Example: for PS, energy for chain pullout
E ~ 280 J/m3 for MW = 150 kg/mol
T of chains being pulled out:
Even if a sample is fractured at room T, through
frictional dissipation the T of a PS chain being pulled
out can be as high as 150-200C (this is above Tg)
Growing evidence that the actual fracture of polymers
takes place in the melt state (growing crack tip in fatigue is
quite hot)

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