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Module 2: Lecture 5

Viscoelastic models complex modulus

CHEE3301 Polymer Engineering 1st Semester 2016

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
Strain is additive

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

where is Relaxation time

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
Leads to d
dt h
Which is Newtonian viscous flow
Not the right form for creep in polymers

CHEE3301 Polymer Engineering 1st Semester 2016

Kelvin-Voigt (parallel) Model


Spring and Dashpot in parallel
Strain is the same
Stresses are additive

E h

d
dt

Consider stress relaxation d 0


dt

Leads to E
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

This does has right form for creep in polymers

CHEE3301 Polymer Engineering 1st Semester 2016

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

CHEE3301 Polymer Engineering 1st Semester 2016

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

CHEE3301 Polymer Engineering 1st Semester 2016

time

time
10

Complex modulus
W d

Response to sinusoidal strain:

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

d
dt
dt

0 E sin t E cos t 0 cos t dt

0
2

0
2

E sin t cos t E cos

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

Can also use dielectric measurements

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

CHEE3301 Polymer Engineering 1st Semester 2016

13

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

CHEE3301 Polymer Engineering 1st Semester 2016

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