An Analysis of the Viscous Behaviour
of Polymeric Solutions
P . 1. CARREAU, D . DE KEE* and M . DAROUX**
Chemical Engineering Department, Ecole Polytechnique, Montrkal, Q d b e c , H3C 3A7
Viscosity data of an aluminum soap solution, a polyisobu-
tylene solution, a polyacrylamide solution, and ten polystyrene
solutions have been analysed using two rheological models:
the Carreau model A and the Ellis model. The model para-
meters were obtained by non-linear regression. The importance
of the zero-shear viscosity for design purposes is illustrated
by observing the appearance of a master curve in the repre-
sentation of the dimensionless viscosity versus the product
of the zero-shear viscosity by the shear rate. A linear relation is
shown to exist between the logarithm of the zero-shear vis-
cosity and the polymer concentration. It is asserted that either
model should replace advantageously the commonly used power-
law expression.
I t is well known that polymer melts or solutions and
highly concentrated solid suspensions do not obey
Newton's law of viscosity. Except for r a r e examples,
these materials are pseudoplastic, i.e. their viscosity
decreases as the rate of shear or the shear stress
increases. Decreases in the viscosity by 2 o r 3 decades
have been commonly observed for high molecular
weight polymer melts"' for shear rates ranging from
10-2 to lo3 s-1.
Recently most efforts in rheology of polymers have
been aimed a t describing elastic effects. Quite a few
phenomena, material functions or theories (see for
examples references 2 and 3 ) have been reported o r
proposed to elucidate the so-called viscoelastic be-
haviour of polymer solutions or melts. Although in
some important industrial processes the time-effect
or elastic properties of these materials cannot be
ignored, the most important material function for
most engineering applications is the viscosity. I n
fact the viscosity is sufficient to characterize rheo-
logically these materials in :
i ) steady simple-shear flow
ii) accelerated, decelerated or complex flows of
polymers of not too high molecular weight.
Various models have been proposed to describe the
viscosity of polymer s01utions'~~~', melts"' suspensions
of solids'", biological fluids@', etc.. . Some of these
equations have theoretical foundations'" but lack
flexibility t o f i t viscositv data f o r a large class of
non-Newtonian fluids. Other models a r e empirical and
their usefulness resides in their ability to correlate
adequately viscosity data of various types of fluids
through a small number of meaningful parameters.
The primary purpose of this work is t o evaluate
extensively two successful empirical models which
are known to f i t adequately viscosity data of various
polymeric materials. These two equations, the Ellis
model and one proposed previously by one of us (re-
ferred to, in this work, as model A) a r e similar in
'Present address : Department of Chemistry and Chemical Engineering,
Royal Military College of Canada, Kingston. Ont.
""Present address: Labratoire des Sciences du GBnie Chimiaue. Ecole
Nationale Superieure des Industnea Chimipues.
640 Nancy. cedex. France.
The Canadian Journal of Chemical Engineering, Vol. 57J A # d J 1979
On a analysk, au nioyen de deux mod&les rhkologiques (le
niodkle A de Carreau et celiii dEllis), les rksultats des viscositks
d'nne solution de savon daluminum, une solution de poly-
isobutylkne e t dix solutions de polystyrhe. On a obtenu les
paramttres des niodhleles par regression non linkaire. On illustre
l'importance pratique de la viscosit6 en l'absence de cisaille
nient, en observant l'apparition d u n e courbe principale dans
la reprksentation de la viscositk a-diniensionnelle en fonction
du produit de la viscositk en l'absence de cisaillement par la
vitesse de cisaillement. On niontre qu'il existe une relation
linhire entre le logarithme de la viscositC en l'absence de
cisaillement et la concentration des polymkes. On soutient que
les deux niodkles pourraient remplacer avantageusement l'ex-
pression de la loi de puissance eniployke communknient.
their form: each contains three parameters. In this
paper we focus attention on the zero-shear region
of viscosity data obtained on the Rheogoniometer.
Our aim i s to show t h a t although the data appear
to be independent of the shear rate at low shear rate,
this is not exactly the case a s predicted by the two
models. The implication of this on falling sphere
data is discussed. We f u r t h e r show t h a t the zero-
shear viscosity can be quite useful t o correlate non-
Newtonian behaviour to the molecular weight and
concentration of a polymer solution.
Rheological models
The non-Newtonian viscosity is described respec-
tively for the two rheological models by
Carreau Model A(1o) q / q o = 1/ [l + ( t ?)2]s.
~ .. . . . . . . . . .(1)
Ellis model ( 1 1 ) : 11/11. = 1/[1 + I*-']. . . . . . . (2)
I712/71/2
where vo is the zero-shear viscosity
tl is a timeconstant I
S, a are dimensionless parameters
T ~ is/ the
~ shear stress for which
11 = 7 0 / 2 .
Both models a r e very similar i n form; for model A
the functional dependence is on the shear rate y where-
as it is on the shear stress 7 1 2 f o r t h e Ellis model.
For characterization purposes, model A appears t o
be more interesting since i t contains a time constant
which is closely related to the elastic time constant
f o r most polymeric materials"o'. However we note
t h a t for the Ellis model t h e ratio of the two para-
meters 7. and rh has the unit of time. The parameters
S and a! a r e associated with the power-law behaviour,
and obviously for pseudoplastic materials S is greater
than zero and a! greater than 1.
At very low s h e a r rates ( (tl 9) << 1and T~~t:- qo9 )
Equation (1) and Equation (2) reduce respectively
to :
7 / q o A 1 - S(tlY')2.. . .. . . . . . . . .. . . . . . . .. . . .. .. .. .(3)
and
71/70 = 1/11 +I 11"+ / 7 1 / 2 l n - ' 1 =
1 - ~ ~ o - y / T l ~ z ~ .* .......
- l . . . . ... . . . ... . . . . ...(4)
135
 I

0= I 5 % SEPARAN

@ : 2 X PIE
_ .. MODEL A

: E L L I S MODEL

I I I 1 1 1 , 1 1 , 1 I !,,Ud I ,,1,,,,1 ,
10- 10-2 10-1 100 10' 102
y, SEC.1

Figure 1 -Viscosity of the aluminum soap (E.L.), Separau, Figure 2 - Viscosity of the polystyrene solutions.
and polyisobutyleue (P.I.B.) solutions.

mers in Aroclor 1248 solvent (chlorinated diphenyls

Except for the case of a = 3, the functional de- with a viscosity of 0.3 Pa*s a t 25°C). The poly-
pendence in the low shear rate region is different. styrene solutions investigated are listed in Table 1.
For model A, the viscosity is a linear function of The P.I.B. solution was a 2% solution (by weight)
the second invariant 05 the rate-of-strain tensor, in Primol 355, a pharmaceutical grade white oil with
I1 = 2 y 2 The differences in behaviour are brought a viscosity of about 0.15 Pa's a t 25°C. The P.I.B. was
out by differentiating the respective expressions for a well fractionated cut having a molecular weight
7) with respect to 11: of 1.5 x 10' g/mol.
The polyacrylamide solution consisted of 1.5%
Model A aq / ,311 = - Sqe 1: / 2 . . . . . . ... . . . . . . . . . . . .(5) (by weight) of Dow Chemical Separan AP-30 in a
50/50 mixture by weight of water and glycerine. The
Ellis model aluminum soap solution was made of 70 g of alu-
minum laurate in 1000 ml of decalin and 20 ml of
a -3 m-cresol. A description of the preparation of this
aqiazr = - (a - 1) ( ~ ~ [ 2~ ~1~ 2 7 ~ / ~ 1111
1a--t (6)
solution is given by Huppler et al"*'.
For model A, the derivative is a negative constant
whereas for the Ellis model the derivative is a Eualuation of the models
decreasing or increasing function of the second in- Although the Ellis and the Carreau models are
variant depending on whether a is greater than or strongly non-linear with respect to the parameters,
smaller than 3. In no case is a plateau predicted, i.e. the optimum parameters can still be obtained from a
the viscosity is a decreasing function of the second least-squares method. However, the set of equations
invariant. Although the dependence of q on I1 is resulting from setting the partial derivatives with
weak in the very low shear-rate region, Newtonian respect to each of the parameters equal to zero is
behaviour is not predicted and q,,has to be interpreted difficult to solve. Three methods can be used to
as a limit a t which the viscosity approaches as I1 solve this problem : the Gauss-Newton, the steepest
tends to zero. descent, and the Marquardt methods. The Gauss-
Newton method converges only if the initial guesses
At very high shear rates, the viscosity a s predicted of the parameters are close to the final values"";
by Equations (1) or (2) decreases to zero. This is the steepest descent method converges for any initial
unreasonable, but the models can be easily corrected estimate, but may require a prohibitive computer
by inclusion of a high-shear viscosity term, qm.For time. We chose the Marquardt which is
example, the left member of Equations (1) or (2) a combination of the first two.
may be written as (7 -+>/ (yo- qm>.Equation (2)
so written is referred to as the Meter 3-
has a physical meaning, that is the value of the vis- TABLE1
cosity as the shear rate becomes very large. It is INVESTIGATED SOLUTIONS OF POLYSTYRENE
reasonable to assume that any pseudoplastic material
would behave as a Newtonian fluid a t high enough
shear rates. For polymer solutions, the limiting vis- Molecular
cosity is that of the solvent, but there are indications weight
dmol &?w/Mn wt. %
that ymis larger than q s (solvent viscosity). Never-
theless, for most engineering applications qmis very 411,000 1.06 2.5
small and negligible compared to q. 5.0
7.5
Fluids 860,000 1.15 1.0
The rheological equations are evaluated using vis- 2.5
cosity data published by Ashare''') and Huppler e t 5.0
a1<14)
. Quite a range of rheological behaviour is 7.5
covered by this choice of polystyrene solutions, a
polyisobutylene (P.I.B.) solution, a 1.6% polyacryl-
amide solution, and an aluminum soap solution. The
1,800,000 1.20
I 1.o
2.5
5.0
polystyrene solutions were nearly monodisperse poly-

136 The Canadian Journal of Chemical Engineering, VoZ. 57, A f i l , 1979

 100

FLUID REFERENCE @
8

r
E 30 -
"
0
YI
-

I
00 005 0 10 0 15 0 20
2 7 2 :t

Figure 3 - Low-shear-rate viscosity

------ predictions of model A
- - -- _ - - predictions of the Ellis model.

The criterion for parameter value selection was

that the following quantity be a minimum:
N
n = .z wi (712iE - 71ZiC)2.. ...................(7)
2= 1
where N is the number of data, wi the weight associated
with each datum, and ~ ~ and 2 8T ~ respectively
~ ~ C the .OO DI .02 .03 .04 .OS .06 .07 .O 8 .09 .I0
experimental and calculated values of the shear stress (the
Polymer weight fraction, w
dependent variable as experimentally measured on a cone-
and-plate viscometer). To give equal importance to the Figure 4-Correlations of the zero-shear viscosity for the
deviations in the low shear stress region as well as in the polystyrene solutions.
high shear stress region, the weight was taken to be:
%
w i = (1/71ziE)'. ................................. .(8)
The principle of the non-linear least-squares method
is to expand the model into Taylor series, about the

TABLE
2
RHEOLOGICAL
PARAMETERS

I I Model A Parameters
Ellis Model
Parameters I Variance
T o
Pa s
7i/z
Pa I Model A Ellis
7% Alum. Soap
1.5% Separan
2% P.I.B.
171
1
211.7
I 3 1 876.0 1
91.8
1 169
1.061
45.2 ~

1
0.39
0.33
0.32
89.8
253.2
846.0
63.8
4.33
4.16
5.08
3.04
2.60
3.3 x 10-3
3.7 x 10-3
1.3 x
1.12
4.43
2.2
x
x
x
10-3
10-3
lo+
I I 1 I 1.32 X 10-4
P.S. 5.0 - 411
P.S. 1.0 - 1800
P.S. 2.5 - 411
1713.31
4

I 6 I 3.49 I
24.6
1 0.06
0.20
0.01
1I 0.17
0.11
0.15
24.6
3.84
3.53 1I
1230.1
109.0
1159.4 11
2.61
1.52
2.25 1I
1.7 X
1.9
2.7 X
x
lo-'
10-4
1I 2.1
9.6 X
x 10-3

P.S. 7.5 - 411 1 7 I 118.0 I 0.34 I 0.13 118.7 1654.0 2.36 6.3 x 5.2 x 10-4
1 I I I 4.7
P.S. 5.0 - 1800
P.S. 2.5 - 1800
P.S. 1.0 - 860
17132.4
8

I 10 1 2.05 1
746.0
I 6.95
0.81
0.05
1I 0.30
0.21
0.10
746.0
34.4
2.11 1
158.7
102.0
579.0 1
2.85
2.14
1.71 1
3.3
2.6
4.7
x
x
x
10-4
10-4 I 1.7
4.8
x
x
x
10-3
10-4
P.S. 2.5 - 860 I 11 1 10.2 I 0.07 I 0.20 11.2 1 401.9 1 2.13 I 2.5 X low3 I 3.1 X lo-'

1 1 1 1 1 1
~

P.S. 5.0 - 860 12 98.2 0.05 0.26 98.7 444.0 2.86 4.2 x 10-4 3.1 x 10-4
P.S. 7.5 - 860 ~ 1
7
1 617.3 1.30 0.33 594.4 652.0 3.75 2.2 x 10-4 7.5 x 10-4

The Canadiun Journal of Chemical Engineering, Vol. 57, A @ d , 1979 137

F
, FLUID R E F E R E N C E
F k
NUMBER
1011
b
L L L - L L A _iL
I0 ' 00 10' 102
y 71, pa
I
Figure 5 - Master curve for the polystyrene solutions with
M, = 411000 g/mol.
initial value of the parameters, retaining only the f i r s t
order terms :
P Using principles of continuum mechanics, Dealy"*'
~ 1 2 , ' = 7 1 z i C (Ti, b l o ) 2 + j= 1
( d r i 2 , l d b j ) Abj, i = I, 2 . . . .N..
where P is the number of parameters ( 3 in our case).
The correction vector A b appears linearly in t h i s
equation; hence it can be solved by a linear least-
squares method. The convergence criterion proposed
by Marquardt"", is defined as
IAb,fI / ( r + lb,"] < E , j = 1, 2, 3 .. . . . . . . . . ... ..(lo)
For this work, E was set equal to lo5 and r equal
to low3,which assures convergence even when a para-
meter bj approaches zero.
I n all cases only a few seconds of computer time
on a n IBM 360/75 were necessary to reach con-
vergence, even for inaccurate initial estimates of t h e
parameters. For the Ellis model, which is implicit
in the shear stress, slightly more computer time was
required.
The fits obtained with the two models a r e shown
in Figures 1 and 2. The solid and dashed lines a r e
respectively the predictions of model A and of t h e
Ellis model. The optimum parameters and the vari-
ances are presented in Table 2. A s indicated by t h e
values of the parameters, the various fluids, labeled
from 1 to 13, cover a wide range of viscous prop-
erties. Overall, both models a r e quite successful i n
describing the data. We should point out that t h e
large deviations observed at high shear rates f o r
the 2% P.I.B. (fluid number 3) could be considerably
reduced by including in the models a fourth para-
meter, qm (an infinite shear viscosity), as men-
tioned previously.
In all cases, the variances of t h e parameters f o r
both models were found to be very small. For ex-
ample, the intervals of the parameters of Model A, at
95% confidence, for t h e 1.6% Separan data are:
211.1 < qo < 212.4 Pa
45.0 < t , < 45.4 s
0.3352 < S C 0.3353
I n Model A, there is a strong correlation between
the parameters 7. and tl. For the Ellis model, a
similar correlation is observed between t h e para-
meter 7. and m2. This is not surprising, since t h e
power-law regions (the straight lines on the log-log
plots of Figs. 1 and 2) can be adequately represented
by a two-parameter model and most of the data
are in those regions.
138
10'
...... . . . ... . . . .(9)
s fluid obeys Stokes' law and the zero-shear viscosity is
The Canadian Journal of Chemical Engineering, Vol. 57, April, 1979
FLU 3 REFERENCE
UUMBER
I 10
v 11
0 12
A 1 3
101 100 101 10 ' 10' 10'
Y 7). pa
Figure 6 -Master curve for the polystyrene solutions with
M, = 860000 g/mol.
Low-shear-rate region
has shown that the concept of a perfectly Newtonian
fluid is inconsistent with that of a "simple fluid",
i.e. if the viscosity of any pseudoplastic fluid can
be described by a simple polynomial expansion of
terms ( t j j ) " this
, material cannot exhibit a New-
tonian behaviour in the low-shear-rate region.
Although the low-shear-rate viscosity data obtained
on the Weissenberg Rheogoniometer a r e not very
accurate (+ 10% f o r some data according to Huppler
e t al(I4), we have analysed the data of every fluid
which appear to be, on a log-log basis of Figures 1
and 2, in a plateau region. Polynomial regressions
were tested N i t h each set of data and a best f i t
was obtained, in all cases, with a linear expression
of the viscosity versus the second invariant of the
rate-of-strain tensor. This is in agreement with the
predictions of model A a s given by Equation ( 3 ) .
The behaviour in the low-shear-rate region is shown
for three different fluids i n Figure 3. The solid
lines a r e the predictions of model A whereas the
dashed lines a r e those of the Ellis model. Both models
predict an increasing viscosity as the second invariant
of the rate-of-strain tensor (I1 =.i/') decreases to
zero. Although the scattering in the data is too large
to be conclusive, model A appears to be more satis-
factory. The differences in behaviour predicted by
the Ellis model f o r various values of ~y is striking.
For a! much greater than 3 (fluid reference number 1
on Figure 3 with a! = 5.08), t h e viscosity is almost
constant in the low-shear-rate region. For a! smaller
than 3, a s f o r fluid reference number 9, the Ellis
model predicts a rather rapid decrease of viscosity
in the vicinity of zero shear. This is unlikely, but
more accurate data are required to prove this point.
Our findings confirm the observations of various
researchers with t h e experiment of falling spheres.
I n order to obtain the low or zero-shear viscosity
from falling-sphere data, one has to assume t h a t the
determined by extrapolating the apparent viscosity so
obtained to the zero apparent shear rate or apparent
shear stress. I n all cases reported, the data f o r poly-
meric fluids, even a f t e r corrections f o r wall effects
(see reference"') f o r example), show a clear depend-
ence on either t h e shear rate or t h e shear stress.
The assumption of Newtonian behaviour i n t h e low
shear rate region is not correct, and since t h e t r u e
shear stress o r shear rate cannot be determined f o r
the analysis of the flow about a sphere, t h e zero-
 101 , , , ,,, / , , , , , I I , , ., I 1 I
' " i ' " "
TABLE3
PARAMETERS
FOR THE SOLUTIONS.
POLYSTYRENE

t I -
M, 1
I

Fluid Reference
I

g/mol Number I s

F t
411 000
860000
1800000 1 ::z:
10, 11, 12, 13
1 405.0
1 0.206
0.279
0.315

.-I
FLUID REFERENCE
NUMBER
I I I
* 5
m a The values of the parameters of Table 3 differ from those pre-
A 9 sented in Table 2 ( T ~ v,/tl) since 7 1 and S are not really inde-
pendent of concentration.
2 ,-&d u 1 1 1 ' l i 1 L ' d l L U I LIillLLi
lo1 100 10' 102 10' I 0'
Y 77.. PO

Figure 7 -Master curve for the polystyrene solutions with
M, = 1800000 g/mol.
shear viscosity obtained by extrapolation is probably
erroneous. Evidence of this was shown by Huppler
e t a1114)who reported large discrepancies between
values of zero-shear viscosity determined from falling-
sphere data and those measured on the Weissenberg
Rheogoniometer. Although these discrepancies can be
explained by the non-existence of a viscosity plateau
at low shear rate, the elastic nature of the fluids
may also interefere in the flow of falling spheres
since the strain history is not uniform across the
fluid for this flow. We suggest t h a t a complete
ana1,ysis of falling-sphere data with model A be made
to clarify the importance of the slightly non-New-
tonian behaviour in the determination of t h e zero-
shear viscosity.
Correlations with the zero-shear viscosity
We have investigated various possible correlations
for Model A with the parameters reported i n Table 2.
The following two observations are of particular in-
terest. In Figure 4, we show t h a t there exists a
linear relationship between log (zero-shear vis-
cosity) and w,the weight fraction of the polymer
in solution. This set of data however does not verify
the well-known correlation of Fox and F10ry"~':
IKM,
where M , is a critical molecular weight. This cor-
relation has been verified mostly for melts and its
validity for polymer solutions is questionable.
As suggested by Vinogradov et al. (in ref. 20) for
polyethylene melts, the viscosity data of the various
polystyrene solutions for each molecular weight can
be correlated approximately with the apparent shear
stress defined by
7]Z0 = -y Qa * . . , . , . . , . . . . . . . , . . . . . . . . . . , , . , . . . .(12)
The master curves of 11/71. vs. y 11. so obtained
ar e presented in Figures 5 to 7 for the three mole-
cular weights. Although there a r e important devia-
tions a t large values of 9 yo, the influence of the
polymer concentration is almost eliminated, i.e. the
effect of the concentration is accounted for by the
apparent shear stress. This is useful for design pur-
poses; from one set of data for a given polymer
weight one can predict approximately, with the help
of correlations such as those presented in Figures 4
to 7, the viscous behaviour of polymer solutions of
various concentrations.
The viscosity master curves can be described by
model A rewritten in t h e form
7 /?. = 1/ [l + 70/71)*Is.. .. . . . . . . . . . ... . .. . .(13)
where r1 has the units of stress and is independent
of the polymer Concentration. The predictions of
Equation (13) a r e presented by the solid lines on
Figures 5 to 7. The parameters r1 and S for t h e
three molecular weights a r e given in Table 3.
Similar results have been observed recently by
Parrini et al(*') for molten aliphatic polyamides.
Conclusions
Two rheological equations have been evaluated with
viscosity data of 13 different polymer solutions.
These pseudoplastic fluids have a wide range of
viscous properties. Both the Carreau model A and
the Ellis model a r e quite successful in describing t h e
viscosity data in terms of three parameters. There
is some indication t h a t in the very low shear-rate
region the viscosity is not constant, but increases
slowly a s t h e second invariant of t h e rate-of-strain
tensor decreases to zero.
For the polystyrene solutions, the zero-shear vis-
cosity was correlated with the polymer concentration
and master curves of the dimensionless viscosity (q/
q o ) versus the product of the zero-shear viscosity by
the shear rate were obtained.
There exist in the literature many other rheological
,Fw< M, equations. However, the two equations evaluated here
a r e believed to be the most flexible and capable of
characterizing any non-Newtonian fluids. These two
models should replace advantageously the commonly
used power-law expression, since they contain mean-
ingful parameters that can be easily determined. It
is true t h a t the use of the simple power-law model
leads to analytical solutions for a number of flow
problems of practical importance. These solutions
may become quite complex when a three parameter
model is used. However, a s computers become more
accessible, analytical solutions will be of decreasing
importance in comparison with more realistic solu-
tions obtained with models describing adequately t h e
fluid behaviour.
Acknowledgments
The authors wish to acknowledge financial assistance from the
Canadian National Research Council ( g r a n t A-6817).
Nomenclature
= any of the parameters of both models
= proportionality constant in Equation (13)
= critical molecular weight
= number averaged molecular weight
= weight averaged molecular weight

The Canadian Journal of Chemical Engineering, Vol. 57, AM.1, 1979 139
N = number of data ( 6 ) Ree, F. H., Ree, T. and Eyring, H., Ind. Eng. Chem.
P = number of parameters 50, 1036 (1958).
S = dimensionless parameter in Equation (1) (6) Chu, K. K. and Rudin, A., Trans. SOC. Rheol. 18:1,
t1 = time constant in Equation (l),s 103 (1974).
wi = weight associated with each data, defined by Equation
(8)
(7) Dawson, R., Tans. SOC. Rheol. 19:2, 229 (1975).
zu =polymer weight fraction. (8) Whitmore, R. L., Biorheology I, 201 (1967).
a! = dimensionless parameter in Equation (2) (9) Graessley, W. W., J. Chem. Phys. 54, 5143 (1971).
= shear rate, s-l (10) Carreau, P. J., Trans. SOC. Rheol. 16:1, 99 (1972).
A = squares of deviations, defined by Equation (7) (11) Bird, R. B., Armstrong, R. C. and Hassager, O.,
?) = viscosity, Pa . s “Dynamics of Polymeric Liquids: Volume I, Fluid
T~ = zero-shear viscosity, Pa . s
qrn = infinite-shear viscosity, Pa s
7
-
= convergence parameter defined by Equation (10)
Mechanics”. Wiley, New York (1977).
(12) Meter, D. M. and Bird, R. B., AIChE J. 10, 878
~~2 = shear stress, Pa
(1964).
~ ~ =
/ 2characteristic shear stress in Equation (2), Pa (13) Ashare, E., Trans. SOC. Rheol. 12:4, 535 (1968).
~ ~ 2= , apparent shear stress, defined by Equation (12), Pa (14) Huppler, J. D., Ashare E. and Holmes, L. A., Trans.
T~ = characteristic shear stress in Equation (13), Pa SOC. Rheol. 11:2, (1967).
I1 = second invariant of the rate-of-strain tensor, s - ~ (15) Marquardt, D. W., J. SOC. Indust. Appl. Math. 11,
431 (1963).
Subscrifit (16) Marquardt, D. W., “Least Squares Estimation of
Nonlinear Parameters, A Computer Program in
i = refers to a data point Fortran IV Language,” IBM SHARE Library, Dis-
3 = refers to a parameter”
0 = refers1to the initial value of a parameter. tribution Number 309401, August (1966).
(17) Cygan, D. A. Caswell, B., Trans. SOC.Rheol. 15:4,
Subsmifit 663 (1971).
(18) Dealy, J. M., Trans. SOC. Rheol. 14:4, 461 (1970).
= refers to a calculated value (19) Fox, T. G. and Flory, P. J., J Phys. Chem. 21, 581
E = refers to an experimental data (1958).
= refers to the final value of a parameter.
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140 The Canadian Journal of Chemical Engineering, Vol. 57, A@il, 1979