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Of stress.Now assume uniform distribution of strain -

VOIGT MODEL

Picture representation

Equation

__

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

__

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

SUMMARY

E

η

E

η

η

Maxwell Voigt

Spring Dashpot element element

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

relaxation

relaxation times - a spectrum of relaxation

times would provide a better description

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

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

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

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

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:

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

τt0 ) + log Ta

SIGNIFICANCE OF SHIFT FACTOR

τt0 ) + log Ta

superimposed on that at another by shifting an

amount aT along a log scale.

of relaxation times and relaxation mechanisms vary

and have different length scales as a function of

temperature

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 )

= 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

A chain as a string of

Beads linked by springs

chain

Reptation,scaling concepts

And other advanced theories

obstacles

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