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# Viscosity Models CHEE 490 29.

1
Steady shear measurements cannot resolve the shear stress into a
storage and loss component, but they remain popular for a number of
reasons.
– Steady-shear instruments are inexpensive relative to oscillatory
devices.
– The deformation mode is often more representative of what the
polymer will experience during processing.
– The range of shear rates provided by steady-shear devices (i.e.
capillary rheometers) can be outside those provided by oscillatory
rheometers.
Viscosity Models CHEE 490 29.2
Constitutive Equations
A constitutive equation relates shear stress (t) to shear rate (¸)
– Examples include Newton’s Law and the Power Law equation
These equations are needed for the modeling of pressure and drag
flows in polymer processing equipment, which apply shear rates in the
following ranges:

If we wish to calculate flow rates, pressure drops, and the shear
stresses at various points in the shaping process, we need constitutive
relations to solve the equations of motion.
.
Viscosity Models CHEE 490 29.3
Constitutive Equations
• For non-Newtonian fluids, a Generalized non-Newtonian fluid (GNF)
constitutive relation can be used to account for shear rate effects,
provided that time-dependent and viscoelastic effects are negligible
– This treats our polymer as purely viscous liquid
s
c
t
De
ì
=
where ì
c
is the characteristic time of the fluid and
t
s
is the characteristic time of the flow, or the
contact time
• Appropriate criterion to assess the importance of elasticity:
– The Deborah number
¸ ¸ q = t
 
) (
For example power-law equation
Viscosity Models CHEE 490 29.4
Constitutive Equations: Power Law
Constitutive relations are expressions relating t, q and .
 Newton’s law is a constitutive relation.
A simple way to fit viscosity data of polymer melts is the
Power-law expression:

where m= consistency index [Pa.s
n
]
typical values 1,000-100,000 Pa.s
n
n = power-law index [dimensionless]
typical values 0.2-0.8

n
m ¸ = t

1 n
m
÷
¸ = q

¸

Viscosity Models CHEE 490 29.5
Constitutive Equations: Power Law
 On a log-log paper q vs. is a straight line and the slope is equal to (n-1)
.
¸

Viscosity Models CHEE 490 29.6
Constitutive Equations: Power Law
Viscosity Models CHEE 490 29.7
Power Law: Temperature Dependence
When the power-law expression is used, a common representation of
the consistency index is:
)] T T ( b [
o
o
e m m
÷ ÷
=
where m
o
is the consistency index at a reference temperature T
o
Typical values of b=0.01-0.1°C
-1
Viscosity Models CHEE 490 29.8
Other Constitutive Equations
The power-law equation applies to moderately high shear rates, but does
not capture the Newtonian-plateau that is very often observed at low
shear rates.
– The polymer viscosity calculated at “zero” shear rate (by extrapolation)
can be an important polymer processing quantity, and it relates to polymer
structure.
– The extent of shear thinning is frequently of interest as well.
η
¸

Narrow MWD
Viscosity Models CHEE 490 29.9
Other Constitutive Equations
Consider the two viscosity-
shear rate profiles illustrated
here.

The untreated polyolefin
behaviour is only modeled
adequately by a power-law
expression at high shear rates.

exhibits Newtonian behaviour
throughout the range of shear
rates studied. In this case, a
power-law with n=1
(Newtonian) is appropriate.
1
10
100
1000
10000
100000
0.01 0.1 1 10 100 1000
Shear Rate: s-1
V
i
s
c
o
s
i
t
y
:

P
a

s
Untreated Polyolefin
Viscosity Models CHEE 490 29.10
Other Constitutive Equations
Carreau model (3 parameter):
( ) | |
2 ) n 1 (
2
o
1
÷
¸ ì +
q
= q

Carreau model (4 parameter):
( ) | |
2 ) n 1 (
2
o 1
1
÷
·
·
¸ ì +
=
q ÷ q
q ÷ q

ì is a time constant or characteristic time
Cross model:
) n 1 (
o
1
÷
¸ ì +
q
= q

P=Power Law
C=Carreau (4 parameter)
M=modified Cross
Viscosity Models CHEE 490 29.11
Introduction to Viscoelasticity
Is “silly putty” a solid or a liquid?
Why do some injection molded parts warp?
What is the source of the die swell phenomena that is often
observed in extrusion processing?

Expansion of a jet
of an 8 wt% solution of
polyisobutylene in decalin

Under what circumstances am I justified in ignoring
viscoelastic effects?
Viscosity Models CHEE 490 29.12
Introduction to Viscoelasticity
Polymers display VISCOELASTIC properties
All viscous liquids deform
continuously under the influence of an
applied stress – They exhibit viscous
behavior.

Solids deform under an applied stress,
but soon reach a position of
equilibrium, in which further
deformation ceases. If the stress is
removed they recover their original
shape – They exhibit elastic behavior.

Viscoelastic fluids can exhibit both
viscosity and elasticity, depending on
the conditions.
Viscous fluid
Viscoelastic fluid
Elastic solid
Viscosity Models CHEE 490 29.13
Introduction to Viscoelasticity
The response of polymeric
liquids, such as melts and
solutions, to an imposed
stress may resemble the
behavior of a solid or a
liquid, depending on the
situation.

S
C
t
stic characteri
De
ì
= ÷
n deformatio the of scale time
time material
Viscosity Models CHEE 490 29.14
Viscoelasticity and Stress Relaxation
Whereas steady-shear measurements probe material responses under a
steady-state condition, creep and stress relaxation monitor material
responses as a function of time.
– Stress relaxation studies the effect of a step-change in strain on stress.

¸ (strain)
time
t (stress)
time
t
o
=0 t
o
=0
¸
o
?
Viscosity Models CHEE 490 29.15
Viscoelasticity and Stress Relaxation
Stress relaxation can be measured by shearing the polymer melt in a
viscometer (for example cone-and-plate or parallel plate). If the
rotation is suddenly stopped, ie. ¸=0, the measured stress will not fall
to zero instantaneously, but will decay in an exponential manner.
.
Relaxation is slower
for Polymer B than for
Polymer A, as a result
of greater elasticity.

These differences may
arise from polymer
microstructure
(molecular weight,
branching).