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# Module 2: Lecture 5

## Models of linear viscoelasticity

Elements:
Spring, modulus E

Dashpot, viscosity h

## CHEE3301 Polymer Engineering 1st Semester 2016

d
h h
dt

Components of viscoelastic
behaviour
Recall:
polymers fall on a spectrum of behaviours from the
extremes of linear elastic behaviour to Newtonian viscosity
the relative importance of the two behaviours will depend
on the time frame and the temperature
time relative to molecular relaxations
To model viscoelastic behaviour we will need to combine
these elements of elastic behaviour and flow behaviour.
CHEE3301 Polymer Engineering 1st Semester 2016

## Maxwell (series) model

Spring and dashpot in series
Stress is the same

1 2

## Consider stress relaxation

Model held at constant strain, so

d d 1 d 2 1 d

dt
dt
dt
E dt h
d
E
So
dt

d
0
dt

h , , 2

## Integrate and impose IC t=0, 0

0 exp Et h 0 exp t

## This has right form for stress relaxation in polymers

CHEE3301 Polymer Engineering 1st Semester 2016

## Maxwell model (2)

Consider creep, where stress is constant d 0
dt

d d 1 d 2 1 d

dt
dt
dt
E dt h
dt h
Which is Newtonian viscous flow
Not the right form for creep in polymers

## Kelvin-Voigt (parallel) Model

Spring and Dashpot in parallel
Strain is the same

E h

d
dt

## Consider stress relaxation d 0

dt

Which is Hookean elastic behaviour
Not the right form for stress relaxation in polymers
CHEE3301 Polymer Engineering 1st Semester 2016

## Kelvin-Voigt Model (2)

Consider creep, constant stress, so (dividing through by h and
rearranging):
d E

0
dt h
h
This standard differential equation has solution

Et
1

exp

1 exp t
E
h E
where is Retardation time

## Standard Linear Viscoelastic model

Maxwell model (series) describes stress relaxation, but doesnt fit creep
Kelvin-Voigt Model (parallel) describes creep, but not stress relaxation
Combine two:

E1 , 1 ,
1 2
3 2
CHEE3301 Polymer Engineering 1st Semester 2016

h , 2 , 3
E2 , 2 , 2

## Standard Linear Model (2)

It can be shown (see tutorial question) that this model reduces to the
Kelvin-Voigt model for creep and to the Maxwell model for stress
relaxation
The time scale of both creep and stress relaxation (the relaxation or
retardation time) is the same
Note though that for most polymers we have
a spectrum of relaxation times
non-linear effects

## Standard Linear Model (3)

Apply an oscillating strain to the Standard Linear Model
0 sin t

Viscoelastic response is
0 sin t

## What would pure elastic

or pure viscous response
look like?

## 0 sin t cos 0 cos t sin

0 E sin t E cos t

time

time
10

Complex modulus
W d

## Response to sinusoidal strain:

In phase component, E,
Storage modulus
(stored energy returned on
Out of phase, E, loss modulus

d
dt
dt

0
2

0
2

t dt

0 E
2

## (energy lost in a cycle)

Define:
tan = E/E (damping)

E*
E"

E'
CHEE3301 Polymer Engineering 1st Semester 2016

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tan
Can measure E and E in Dynamic
Mechanical Thermal Analysis (DMTA)

Torsional pendulum
3 pt bending
Tension
Etc

## Constant frequency and ramp temperature

Constant temperature and vary frequency

## CHEE3301 Polymer Engineering 1st Semester 2016

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Torsional pendulum:
Dynamic Mechanical
Thermal Analysis
(DMTA)
Polymer sample set oscillating at set
frequency
Measure decrease in amplitude as forced
oscilation damped out
Can calculate G and G from measuring
the ratio of the amplitude of the motion
from two successive cycles
Ref: Young and Lovell p333

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## Note: molecular transitions

designated by Greek alphabet
Highest temperature relaxation a;
lower T transitions b, g, , etc
b

a
Tg

In semi-crystalline
polymers a , usually
related to crystalline
region, can split into
two, a11 and a2

tan

a2

## CHEE3301 Polymer Engineering 1st Semester 2016

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DMTA examples:
polyethylene
Peaks in tan sensitive to
molecular structure and
microstructure
a peak
present in both samples - splits
in 2 for HDPE
related to crystalline regions
b peak
absent from HDPE
amorphous regions
g peak present in both

## CHEE3301 Polymer Engineering 1st Semester 2016

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DMTA example:
Nylon 6.6
Quenched sample amorphous
large Tg (a peak)
Thermal energy allows it to
crystallise after Tg increase
in G

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