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Dashpot, viscosity h
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
1 2
d d 1 d 2 1 d
dt
dt
dt
E dt h
d
E
So
dt
d
0
dt
h , , 2
0 exp Et h 0 exp t
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
E h
d
dt
Leads to E
Which is Hookean elastic behaviour
Not the right form for stress relaxation in polymers
CHEE3301 Polymer Engineering 1st Semester 2016
0
dt h
h
This standard differential equation has solution
Et
1
exp
1 exp t
E
h E
where is Retardation time
E1 , 1 ,
1 2
3 2
CHEE3301 Polymer Engineering 1st Semester 2016
h , 2 , 3
E2 , 2 , 2
Viscoelastic response is
0 sin t
time
time
10
Complex modulus
W d
In phase component, E,
Storage modulus
(stored energy returned on
removal of load)
Out of phase, E, loss modulus
d
dt
dt
0
2
0
2
t dt
0 E
2
Define:
tan = E/E (damping)
E*
E"
E'
CHEE3301 Polymer Engineering 1st Semester 2016
11
tan
Can measure E and E in Dynamic
Mechanical Thermal Analysis (DMTA)
Torsional pendulum
3 pt bending
Tension
Etc
12
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
13
a
Tg
In semi-crystalline
polymers a , usually
related to crystalline
region, can split into
two, a11 and a2
tan
a2
14
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
15
DMTA example:
Nylon 6.6
Quenched sample amorphous
large Tg (a peak)
Thermal energy allows it to
crystallise after Tg increase
in G
16