7.

3 Measurement of the viscoelastic behavior of polymers

From Strobl,
The Physics
of Polymers.

cone- and plate geometry:

shear rate the same everywhere
viscosity
shear modulus G
shear compliance J
1

modes of measurement:
steady state properties
at constant shear rates
oscillatory shear
shear stress relaxation after
sudden deformation of melt
elastic recovery after unloading

tensile rheometer:
measurement of

From Stribeck,
X-ray Scattering
from Soft Matter.

constant relative
speed of clamps:

= .

Three fundamental experiments

creep experiment:
instantaneous application of constant force
resulting deformation is measured as a function of time
stress relaxation:
instantaneous application of constant elongation
force needed for keeping the elongation
is measured as a function of time
dynamic-mechanical experiments:
oscillatory application of stress
phase-dependent oscillatory elongation is measured
4

Creep experiment
constant force applied starting at time zero

elongation versus time =

instantaneous elastic response +
retarded anelastic part + viscous flow
unloading: irreversible elongation pertains

Instantaneous elastic response:

tensile experiment: =

shear experiment: = 0

Retarded elastic response:

retardation due to the time
required for conformational
changes
Viscous flow:

determines long-time behavior

In general: () = 0 ()
i.e. the modulus is time-dependent

Stress relaxation experiment

instantanous elongation
or shear deformation,
then kept constant
force decreases
first rapidly,
then more slowly

time-dependent moduli:
for a stretch experiment: =

for a shear experiment: () =

()
0

()
0

Dynamic-mechanical experiments
Time-dependence of stress and strain :

measurements over large frequency range required

8

oscillatory deformation of sample,

0
exp()
i.e. shear deformation: =
0
for small values of

the necessary force (stress or shear force)

is also sinusoidal but phase-shifted
the response is split up into the in-phase
and the out-of-phase component

Oscillatory shear measurements

0
=
cos( ) () sin()

: storage modulus (stored elastic energy)

: loss modulus (dissipated energy)

tan

dynamic shear compliance:
0

0 exp = +

dynamic shear modulus:

0

0 exp = +

10

Oscillatory tensile tests

dynamic compliance of elongation:

0

=
= 0 exp() =

dynamic elastic modulus:

=
= () + ()

11

7.4 Modelling of the viscoelastic properties

Maxwell model:
combination of an elastic spring
with a viscous dashpot
elongation: = +
stress: = =
for a tensile experiment:
() 1 () ()
=
+

12

Stress relaxation
= 0 exp

with the relaxation time =

experimental result:

good qualitative agreement with experimental result

13

Creep experiment

experimental result:

= 0 +

immediate rise and linear increase reproduced

retarded anelastic response not recovered
14

Dynamic-mechanical experiment

log(G'/G0), log(G''/G0)

22

= 0
,
1 + 2 2

= 0
1 + 2 2

experimental result:

101
10-1

G '' ~

= 1/

10-3
10-5
10-7
-3

G ' ~ 2
-2

-1

log()

good coincidence with experimental result

for viscoelastic liquid

15

Voigt-Kelvin model
better description of
viscoelastic solid

log(E'/E0), log(E''/E0)

i.e. long-term behavior

determined by elastic solid

104

= 0 = .

102

E'~

10

10-2
10-4
-3

long-term behavior:
viscoelastic solid

E '' ~
-2

-1

log()

16

More realistic description

More realistic description
of polymer melts by
spectrum of relaxation times,
i.e. by serial and parallel
arrangement of elastic springs
and viscous dashpots
principle of superposition:

= +

1 +

17

7.5 Relaxation processes in polymer melts

glassy
transition
rubber plateau:
elastic behavior

terminal flow
viscous liquid

18

Multitude of relaxational processes

fast:
local conformational changes
slower:
conformational changes of longer polymer segments
origin of viscoelasticity
even slower:
conformational changes of the entire chain
molar-mass dependent
determine terminal flow behavior, i.e.
19

Local processes
shear experiment on
poly(cyclohexyl methacrylate)

glass transition
temperature: 104C
i.e. experiment is carried
out in the glassy state

From Strobl, The Physics of Polymers.

ratio between dissipated

()
and stored energy: tan =

position of maximum depends on temperature

()

20

relaxation time decreases

with increasing temperature like
1 [ 1 ]

= 0

follows an Arrhenius law

with an activation energy ,
the energy barrier between
the conformational states.
1 [103 1 ]
The cyclohexyl side group
changes between chair
and boat conformation.
21

The rubber plateau

rubber plateau:
elastic behavior

elastic modulus
independent on
frequency over
a wide range
From Strobl,
The Physics of Polymers.

polystyrene

frequency width of plateau

strongly molar-mass
dependent, but storage modulus
independent of molar mass)

22

Molar-mass dependence
The plateau is due to
entanglements in the polymer melt.
The higher molar mass,
the lower the frequency
(i.e. the longer the time)
before the melt starts to flow.

From the plateau modulus, the entanglement molar mass

can be determined:
=

: mass density of the polymer melt

23

Entanglement molar masses

at 413 K:

polyethylene

0.784

828

poly(ethylene oxide)

1.064

1624

polyisoprene

0.830

5429

polystyrene

0.969

13309

varies in wide range

L.J. Fetters et al., Macromolecules 27, 4639 (1994)

24