VOIGT MODEL

Maxwell mdel essentially assumes a uniform distribution

Of stress.Now assume uniform distribution of strain -
VOIGT MODEL

Picture representation

Equation

σ(t) = Eε(t) +η dε(t)

__
dt
(Strain in both elements of the
model is the same and the total
stress is the sum of the two
contributions)
VOIGT MODEL - creep and stress relaxation
Gives a retarded elastic response
but does not allow for “ideal” stress
relaxation,in that the model cannot
be “instantaneously” deformed to
a given strain.
But in CREEP σ = constant,σ
0

σ(t) = σ 0 = Eε(t) +η dε(t)

__
dt
Strain dε(t)
__ + ε(t)
__ σ
_0
=
dt τ t‘ η
σ
t
ε(t) = _
Ε [1- exp (-t/
0
τ t‘ )]
1
t2 t

τ t‘ - retardation time (η/E)

 SUMMARY

E
η

E
η
η

Maxwell Voigt
Spring Dashpot element element

Strain Spring Dashpot Maxwell Voigt

model model

t1 t2 t1 t2 t1 t2 t1 t2 t
PROBLEMS WITH SIMPLE MODELS
•The maxwell model cannot account for
a retarded elastic response

•The voigt model does not describe stress

relaxation

•Both models are characterized by single

relaxation times - a spectrum of relaxation
times would provide a better description

NEXT - CONSIDER THE FIRST TWO PROBLEMS

THEN -THE PROBLEM OF A SPECTRUM OF
RELAXATION TIMES
 FOUR - PARAMETER MODEL
ELASTIC + VISCOUS FLOW + RETARDED ELASTIC

eg CREEP
E
M

ε =σ
_0 +σ
__0t σ
_ 0 [1- exp (-t/
ΕM ηM + ΕM τ t )] EV η
V

η
M

Strain

Retarded
elastic
response

Elastic
response Permanent
deformation
t1 t2 Time (t)
applied removed
 DISTRIBUTIONS OF RELAXATION AND
RETARDATION TIMES
The Maxwell - Wiechert Model

_ = σ
dε _1+_ 1 dσ
_1
dt η 1 Ε 1dt
σ
E1 E2 E3

= _ 2 _1 dσ
_2
+
η 2 Ε 2dt η1 η2 η3
σ
= _ 3 _1 dσ
_3
+
η 3 Ε 3dt

dε
_ =0
Consider stress relaxation
dt
σ 1 = σ 0 exp[-t/τ t1 ]
σ 2 = σ 0 exp[-t/τ t2 ]
σ 3 = σ 0 exp[-t/τ t3 ]
 DISTRIBUTIONS OF RELAXATION AND
RETARDATION TIMES
Stress relaxation modulus

E(t) = σ(t)/ε 0
E1 E2 E3

η1 η2 η3
σ(t) = σ 1 +σ 2 +σ 3

σ 01 exp (-t/ σ 02 σ 03
E(t) =__ τ ) +__ τ02 ) +__
exp (-t/ exp (-t/
τ03 )
ε0 01 ε0 ε 0
Or, in general
σ 0n
__
E(t) = Σ E n exp (-t/τtn ) where En = ε
0

SIMILARLY, FOR CREEP COMPLIANCE COMBINE VOIGT ELEMENTS

TO OBTAIN
D(t) =ΣDn [1- exp (-t/
τ tn‘ )]
 DISTRIBUTIONS OF RELAXATION AND
RETARDATION TIMES
Example - The Maxwell - Wiechert Model with n =
E(t) = Σ E n exp (-t/τtn ) 10

n = 2 8

Log E(t) (Pa)

Glassy 6
region

Transition 4
10
Log E (t) (dynes cm- )
2

Rubbery 2
8 plateau

0
-2 -1 0 1 2 3 4
6
Log time (min)
Low High
molecular molecular
4 weight weight

- 10 -8 -6 -4 -2 0 +2
Log time (sec)
 TIME - TEMPERATURE
SUPERPOSITION PRINCIPLE
Recall that we have seen that there is a time - temperature
equivalence in behaviour
Glassy
region
Log E
(Pa) Glassy
region Transition
10 10

Log E (t) (dynes cm- )

2
9 Rubbery
8 plateau
8

7 6
Cross-linked
6 elastomers Low High
molecular molecular
Rubbery 4 weight weight
5 plateau

4 Low - 10 -8 -6 -4 -2 0 +2
molecular Melt Log time (sec)
weight
3
Temperature

This can be expressed formally in terms of a suprposition principle

 TIME TEMPERATURE SUPERPOSITION
PRINCIPLE - creep

T3 > T2 > T1

ε(t) T
σ0 T3 T2 T1

Log t

ε(t) T log aT
σ0

T0
log t - log aT T
TIME TEMPERATURE SUPERPOSITION
PRINCIPLE - stress relaxation
SIGNIFICANCE OF SHIFT FACTOR
What is the significance of the log scale forT a ,and what does
this tell us about the temperature dependence of relaxation
behaviour in amorphous polymers ?
Consider stress relaxation:

E(t) = Σ E n exp (-t/τ t )

n
Let a particular mode of relaxation have a characteristic time
τ t0 at T
0 , and a characteristic time
τ t1 at T
1 . Then
DEFINE

τ t1 t t
aT = __ So that the exponential __ ___
τ t0 term can be written τ t1 = aT τ t0

Hence, taking logs

log (t/τ t1 ) = log (t/

τt0 ) + log Ta
SIGNIFICANCE OF SHIFT FACTOR

log (t/τ t1 ) = log (t/

τt0 ) + log Ta

•ie relaxation behaviour at one temperature can be

superimposed on that at another by shifting an
amount aT along a log scale.

•BUT ,real behaviour is characterized by a distribution

of relaxation times and relaxation mechanisms vary
and have different length scales as a function of
temperature

•This implies that all the relaxation processes involved

have (more or less) the same temperature dependence
RELAXATION PROCESSES ABOVE Tg
- THE WLF EQUATION
From empirical observation

-C1 (T -s T )
_________
Log aT = For Tg > T < ~Tg + 0100 C
C2 + (T -s T )

Originally thought that C1 and2 C were universal constants,

= 17.44 and 51.6, respectively,whens
T = Tg .Now known
that these vary from polymer to polymer.
Homework problem - show how the WLF equation can be
obtained from the relationship of viscosity to free
volume as expressed in the Doolittle equation
 DYNAMICS OF POLYMER CHAINS
An advanced topic that we will not discuss in detail

Rouse - Bouche model

A chain as a string of
Beads linked by springs

chain

Reptation,scaling concepts
And other advanced theories

obstacles