VISCOELASTIC PROPERTIES OF

AMORPHOUS POLYMERS
Log E
(Pa) Glassy
region
10

9 Measured over
8 Some arbitrary
7 Time period - say
10 secs
Cross-linked
6 elastomers
Rubbery
5 plateau

4 Low
molecular Melt
weight
3
Temperature
 TIME TEMPERATURE EQUIVALENCE
Log E
(Pa) Glassy

10
region
10 sec modulus
9

8
Glassy
7 region
Cross-linked
6 elastomers
10 Transition
Rubbery
5 plateau

Log E (t) (dynes cm- )

2
Rubbery
Low 8 plateau
4
molecular Melt
weight
3
Temperature 6

Low High
Stretch sample an arbitrary 4
molecular
weight
molecular
weight
Amount, then measure the - 10 -8 -6 -2 0 +2
-4
Stress required to maintain Log time (sec)

This strain .Then E(t) =

σ(t)/ε 0
 RELAXATION IN POLYMERS
First consider a hypothetical isolated
chain in space,then imagine stretching
this chain instantaneously so that there
is a new end - to - end distance.The
distribution of bond angles (trans,
gauche,etc) changes to accomodate
the conformations that are allowed
by the new constraints on the ends.
Because it takes time for bond rotations
to occur,particularlywhen we also add in the viscous forces due to
neighbours,we say the chainRELAXES to the new state and the
τt
relaxation is described by a characteristic time
 AMORPHOUS POLYMERS - THE FOUR
REGIONS OF VISCOELASTIC BEHAVIOUR
Log E GLASSY STATE - conformational
(Pa) Glassy
region changes severely inhibited.
10

9 Tg REGION - cooperative motions

8 of segments now occur,but the
7
motions are sluggish ( a maximumin
Cross-linked
tan δ curves are observed in DMA
6 elastomers experiments)
Rubbery
5 plateau

Low RUBBERY PLATEAU -τt becomes

4
molecular
weight
Melt shorter,but still longer than the
3
Temperature time scale for disentanglement

TERMINAL FLOW - the time scale for disentanglement becomes

Shorter and the melt becomes more fluid like in its behaviour
SEMI - CRYSTALLINE POLYMERS

•Motion in the amorphous domains

constrained by crystallites

•Motions above Tg are often more

complex,often involving coupled
processes in the crystalline
and amorphous domains

•Less easy to generalize - polymers

often have to be considered individually
- see DMA data opposite

Reproduced with permission from H. A. Flocke,

Kolloid–Z. Z. Polym., 180, 188 (1962).
 MECHANICAL AND THEORETICAL
MODELS OF VISCOELASTIC
BEHAVIOUR
DEFINITIONS

τ(t)
Relaxation modulus G(t) = _γ
0 1_
γ(t) G(t) =
J(t)
Creep compliance J(t) = _
τ0

GOAL - relate G(t) and J(t) to relaxation behaviour.

We will only considerLINEAR MODELS
ie if we double G(t) [orσ(t)],then γ(t) [or ε(t)] also
increses by a factor of 2 (small loads and strains).
 SIMPLE MODELS OF THE VISCOELASTIC
BEHAVIOUR OF AMORPHOUS POLYMERS
Keep in mind that simple
creep and recovery data for
viscoelastic materials looks
something like this

Strain

Retarded
elastic
response

Elastic
response Permanent
deformation
t1 t2 Time (t)
applied removed
 SIMPLE MODELS OF THE VISCOELASTIC
BEHAVIOUR OF AMORPHOUS POLYMERS
While stress relaxation data
look something like this
Glassy
region

10 Transition

Log E (t) (dynes cm- )

2
Rubbery
8 plateau

Low High
molecular molecular
4 weight weight

- 10 -8 -6 -4 -2 0 +2
Log time (sec)
SIMPLE MODELS OF THE VISCOELASTIC
BEHAVIOUR OF AMORPHOUS POLYMERS

Extension

Hooke's law
l0
σ = Eε
∆l Spring

Model
σ
SIMPLE MODELS OF THE VISCOELASTIC
BEHAVIOUR OF AMORPHOUS POLYMERS
Viscous flow
Newtonian fluid
.
τ xy= ηγ
v0
v
y

Dashpot

Model
STRAIN VS. TIME FOR SIMPLE
MODELS

MODELS
E η

Spring Dashpot

Strain
RESPONSE

t1 t2 t1 t2
 MAXWELL MODEL
Maxwell was interested in creep and stress relaxation and
developed a differential equation to describe these properties

Maxwell started with Hooke’s law σ = Eε

Then allowed σ to vary with time dσ

_ = Ε dε
_
dt dt

Writing for a Newtonian fluid σ = η dε

_
dt

Then assuming that the rate of strain _ = σ

dε _+_
1 dσ
_
is simply a sum of these two contributions dt η Ε dt
MAXWELL MODEL - creep and recovery
A picture representation
of Maxwell’s equation
Strain

Creep and
recovery
_ = σ
E
dε _
dt η 0 t Time

η
Strain

Recall that real viscoelastic

behaviour looks something
like this
0 t Time
 MAXWELL MODEL -stress relaxation
_ = σ
dε _ +_
1 dσ
_
dt η Ε dt
In a stress relaxation experiment
dε
_ = 0
dt

dσ
_ =σ
_ dt 0

σ η -1

Hence
( )
Er -2
log
σ = σ 0 exp[-t/τ t ]
E0
-3
Where -4

τt = η
_ -5
Ε
Relaxation time
-6
-2 -1 0 1
log τt
 MAXWELL MODEL -stress relaxation
0

Maxwell model -1

( )
Er -2
log
E0
-3

-4
Glassy
region -5

10 Transition -6
-2 -1 0 1
log τt
Log E (t) (dynes cm- )
2

Rubbery
8 plateau

Real data looks

6

something like
Low High
molecular molecular
4 weight weight

- 10 -8 -6 -4 -2 0 +2
this
Log time (sec)