Journal of Non-Newtonian Fluid Mechanics, 35 (1990) 121-135 121

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

THE SHEAR AND EXTENSIONAL FLOW PROPERTIES OF Ml

D.M. BINDING, D.M. JONES and K. WALTERS

Department of Mathematics, University College of Wales, Aberystwyth SY23 3BZ (Gt. Britain)
(Received May 29, 1989; in revised form August 11, 1989)

Abstract

Steady shear, oscillatory shear and extensional flow experiments are

carried out on the test liquid designated Ml. The steady shear experiments
cover a shear rate range up to 8 X lo4 s-l and the oscillatory shear
experiments involve frequencies up to 40 Hz. Three different extensional
flow experiments are involved, namely contraction flow, spinning and the
open-syphon technique.
A search is made for internal consistency between the various rheometri-
cal tests and the continuum mechanics requirements in the limit of low shear
rates and frequencies are confirmed.

Keywords:contraction flow; extensional viscosity; polymer solution; second-normal stress difference; test
fluid Ml

1. Introduction

As a result of a general discussion at the Chamonix International Con-

ference on Extensional Plow (see Vol. 30, Parts 2 and 3, of this journal) on
the need to establish the utility of a number of extensional viscometers, it
was decided to supply one test liquid to interested researchers and to meet in
1989 to discuss experimental results. The liquid designated Ml was supplied
by Dr. T. Sridhar of Monash University (cf. Ref. 1). It was a 0.244% solution
of polyisobutylene in a solvent consisting of 7% kerosene and 93% poly-
butene. Because of the significant interest aroused by the project, the
original remit of the meeting was extended to cover simple shear and
oscillatory shear and also general complex flows, in addition to the exten-
sional flow envisaged in the original discussion.
In the present paper, we provide rheometrical data on Ml for steady
simple shear flow, oscillatory shear flow and extensional flow.

0377-0257/90/$03.50 0 1990 - Elsevier Science Publishers B.V.

122

2. Steady simple shear and oscillatory shear flows

The instruments available to determine the shear properties of Ml were a

Weissenberg rheogoniometer (WR) (Carrimed, U.K.) a controlled stress
rheometer (CSR) (Carrimed, U.K.) and a capillary rheometer (CR) (Rosand
Precision, U.K.). The rheogoniometer permitted measurements of the ap-
parent viscosity q(+), the first normal stress difference Ni( Jo) and the
second normal stress difference NZ(y) for a steady shear flow with shear rate
3 (see, for example Refs. 2 and 3). In addition, the oscillatory facility of the
rheogoniometer was employed to yield the dynamic viscosity q’(w) and
dynamic rigidity G’(w), relevant to a small amplitude oscillatory shear flow
with applied frequency w.
For reasons that will become apparent later, the steady shear experiments
in the rotational flow generated in the rheogoniometer and the CSR were
limited to modest shear rates (lower than 80 s-l at room temperature). This
shear rate range was extended by the use of the capillary rheometer, which
yielded consistent q(q) data to shear rates up to 8 X lo4 s-l.
The rheogoniometer viscosity data for temperatures between 20 and 70 o C
are given in Fig. 1. There is a clear indication of a substantial shear rate
range where the viscosity is essentially constant and the behaviour is typical
of a so-called Boger [4] fluid. It is clearly possible to associate a (zero shear)
viscosity q,, with each temperature and the ( qO, 7’) data obey the “Arrhenius”
relationship (see Fig. 2):
77= (y efljT 9 (1)
where (Y= 3.7 X lOA Pa s and /3= 6000 K.

10’

ln
x x x x xxx#xx~x
:I
F
v vvvvvv
loo -
0~00000 0000
%AAAAAA

Fig. 1. Shear viscosity TJvs. shear rate 9 data for fluid Ml from the WR. Temperature: X
20°C; v 30OC; o, 40OC; A, 50°C; 0, 60°C; 0, 70°C.
 123

10'-

,fO
*’
100- I’
III
,’
,’
,P’
,’
,Y”
,d”
10-l * ’
02029
a 0.0031 0.0033
I

0.0035
l/T (K-l1
Fig. 2. Zero-shear viscosity q0 vs. temperature T for fluid Ml. 0, experimental data. - - - - - -,
Arrhenius law v0 = eyes/*; OL = 3.7 X 10v9 Pa s; j3 = 6000 K.

The 20° C data from the WR and CSR were complemented by results
from the capillary rheometer. This made use of two capillaries (one having a
diameter of 1 mm and an L/D ratio of 20 : 1, the other having a diameter of
0.5 mm and an L/D ratio of 40 : 1 as well as two orifice dies of the same
diameters). The so-called Bagley correction was applied to remove unwanted
entry and exit pressure losses (see Ref. 3 and cf. section 3). The q(q) data
for 20” C are given in Fig. 3, where it is seen that there is internal
consistency between the data obtained from the various rheometers, with
measurable shear thinning evident at the higher shear rates. We remark that
the viscosity of the solvent at 20 o C is approximately 1.6 Pa s and we would
expect this to provide a lower bound for the viscosity of the polymer
solution. Further, we remark that the breakdown in structure reported by

I_
loL

IO3

2
- 102 -
f

-00
00
00
OO- 10’

I I I I
loo ’
loo 10’ 102 lo3 loL lo5
9 (s-1)
Fig. 3. Rheometric data for fluid Ml from various instruments, at 20” C. Viscosity 7: q,
CSR; X, WR; 0, o, CR. First normal stress difference N,: A, WR.
124

10’ - ,lO‘

b *N’ - lo3
: x x x x” ,8”
8
In - rl CI

N _ ,*2 5
I2 - A
z’
F

- 10’

,000
loo 10’ IO2 lo3 loL lo5
f (S“)
Fig. 4. Same as Fig. 3 but for a temperature of 50’ C.

others workers in the project (e.g. Lodge) (for slit flow) could not be
substantiated in the single throughput involved in the available capillary
rheometer. Recycling the test liquid as quickly as possible did not lead to
any drop in viscosity outside experimental error.
Also included in Fig. 3 are the normal stress Ni(q) data for Ml. Over
most of the available shear rate range on the WR, Nr exhibited a quadratic
dependence on 3, which together with the constant viscosity over the same
shear rate range is characteristic of so-called “second-order” behaviour.
Viscometric data at 50” C are given in Fig. 4. It has been possible to
combine the viscosity data at 20 o C and 50 ’ C by plotting n/n0 against nO+

10-l 4
IO0 IO2 IO1 106
qrl()(Pa I

Fig. 5. Viscosity ratio TJ/Q vs. reduced shear-rate jqO for fluid Ml. Temperature: A, 20 o C;
q, 5o”c.
 125
lOJ-
(a)

2
a
0

1 (b)

I I 1 I

O30 LO 50 60
i, W’l
Fig. 6. (a) Shear stress vs. shear rate for fluid Ml, obtained using the stress sweep facility of
the CSR (temperature, 20 QC); . . . , upward sweep; -, downward sweep. (b) Enlarged
view of the instability in (a).

as in Fig. 5. The data can be fitted by the so-called Cross model (see, for
example, ref. 3)

1
-=
9
(2)
770 1+ (w?o)n ’

with K= 3 X 10m6 Pa-’ and n = 0.385. Since q. is known as a function of

temperature from eqn. (l), it is clear that the viscosity behaviour over a wide
range of shear rates and a reasonable temperature range is now available.
In both the WR and CSR, a build-up of structure occurred once a critical
condition was exceeded (see Figs. 6 and 7). In the case of the 50” C
experiments in the CSR, this resulted in the provocative build-up-break-
down pattern shown in Fig. 7. This was obtained using the shear stress
sweep facility of the CSR. Interestingly, on the downward sweep from the
126

Fig. 7. Same as Fig. 6 but for a temperature of 50 o C.

maximum stress to zero, the corresponding shear rates exhibited a mono-

tonic drop, consistently taking the minimum value experienced on the
upward sweep. The possibility of a build-up of structure in Boger fluids is
well known (see, for example, Refs. 5 and 6) but the behaviour shown in Fig.
7 is certainly a provocative manifestation of the phenomenon.
If we plot the first normal stress difference Ni as a functionSof shear stress
u over a range of temperatures, we obtain the behaviour shown in Fig. 8.
The data are sensibly independent of temperature and fall on a reasonably
straight line of slope near 2 (cf. Ref. 3).
Considerable difficulty was obtained in determining N2 for the test liquid
using the total force technique in the cone-and-plate and parallel-plate
geometries (cf. Ref. 2). In order to make any sense of the data, we found it
essential to use shear stress as the independent variable rather than the
customary shear rate. In view of Fig. 8 and the reasonable expectation that
Ni - N2 against u would also be independent of temperature, such a
 127

10” -

lo3 -

2
- lo2
5

10’
A

I I I
100’
loo 10’ lo2 lo3
a (Pa)
Fig. 8. First normal stress difference NI vs. shear stress u for fluid Ml. Temperature:4
20°C; v, 30°C; l, 40°C; 0, 50°C; o, 60°C; x, 70°C.

procedure at least removed one troublesome influence on the raw data,

namely the effect of even very small temperature changes between the
cone-and-plate and parallel-plate experiments which were needed to de-
termine N2.
The most trustworthy results of the many experiments on N2 are given in
Fig. 9, where it is seen that N2 < 0 with [cf. Refs. 7 and 81

141
- = 0.07.
Nl

.
..A. . . . . . . . . . . ..

+ :i__
10’ lo2 0 (Pa) 103

Fig. 9. - N,/N, vs. shear stress r~ for fluid Ml. Plate separation: Cl, 0.3 mm; A, 0.4 mm; V,
0.5 mm.
128

I 02

1
10'

;;
d 0
a
a
‘F ‘a

100 0'

Fig. 10. Dynamic viscosity q’ and dynamic rigidity G’ vs. frequency w for fluid Ml.
Temperature, 20 o C.

Oscillatory data for Ml at 20 o C are given in Fig. 10. These are compared
with the steady shear results in Figs. 11 and 12. It is clear that the
continuum mechanics requirements, i.e.

(3)

are not violated by the data of Fig. 12, although the G’(w) data could not be
determined at sufficiently low o to confirm eqn. (4).

Fig. 11. Comparison of steady and oscillatory shear viscosities at 2O’C. X, steady shear
viscosity q(y); A, dynamic viscosity 17’ (0); o, modulus of complete viscosity 1q*(w) I.
 129

10-21 I I

IO0 10' f.w (S“l 10'

Fig. 12. Comparison of N,/2y2 and G’/w2 for fluid Ml at 20 o C.

Figure 11 also shows that Ml does not satisfy the Cox-Merz rule (see for
example ref. 3). Recall that, for many polymeric liquids, n as a function of
shear rate is found to be very similar to 1q* ) as a function of frequency w,
where

b*I= ($)4’“.
[($j2+
Quite simply, the “size” of G’ is not sufficient to accommodate the
difference between n and q’ at the same values of their arguments.

3. The extensional viscosity of Ml

Three different techniques have been used to estimate the extensional

viscosity of Ml.

3.1. Contraction flow

The pressure drop in an axisymmetric contraction flow is one possible

method of estimating the extensional viscosity nn. The pioneering work of
Cogswell [9] has recently been re-interpreted by Binding [lo] and Binding
and Walters [ll].
Specifically, the flow is modelled as if the fluid were flowing through a
circular pipe or stream tube with a slowly varying radius that reduces from
R, upstream to a downstream value of R, (refer to Fig. 13). The kinematics
130

1
r--------1

T1-
“I”
____________-. -.----
\ /
\ /
\
\ /I
\\ I/ (5

0
.,

___.I -___--
I I

Fig. 13. Schematic diagram of flow through a contraction.

are obtained by assuming the flow to be locally fully - developed Poiseuille

flow and the stress field is interpreted approximately in terms of the fluid’s
viscometric properties. Hence, the irrecoverable rate of viscous dissipation is
evaluated and minimized to determine the precise shape of the stream tube.
Finally, an energy balance is applied to the flow in order to relate the
pressure drop and flow rate.
If the shear and extensional viscosity functions are expressed as “power-
laws” of their kinematic variables, as follows,
rl = ,j,“-‘. ) ?#lE= IF’, (6)

then the pressure drop P between planes “1” and “O”, for a given volumet-
ric flow rate Q is given by

p = 2k(l + t)* 1(3n + l)tnil,, *t(n+l)/(l+t)

3t2(1 + n)’ k y&J > (7)

where

(3n + l)Q
+R” =
?l7TRi (8)
and

(9)
In the above, inertia has been neglected and it has been assumed that
R, <=sR,.
Although P has been referred to as the pressure drop, it is, more
correctly, the resultant rate of working of the stresses on the control volume
enclosed by the planes “1” and “0” per unit volumetric flow rate. Therefore,
to determine P, a knowledge of the stresses at the exit is required. However,
 131

these cannot be measured experimentally and accordingly reasonable as-

sumptions need to be made. Let Tl be the measured radial normal stress in
the upstream chamber. Assume that the radial normal stress at the exit is
zero and that the axial normal stress at the exit is that determined by fully
developed Poiseuille flow in a capillary of radius R,. It is not difficult to
show, then, that

p=Tl+%6” (N,u,),rdr - s iR1( N,v,),rdr,

where Ni is the usual first normal stress difference and u, is the axial
velocity. The second normal stress difference in shear has been assumed
zero. Since R, z+ R,, the second integral in eqn. (10) can usually be ignored.
Then, if Ni is written as a power law:
Ni = mjl*, 01)
we obtain

p=T1+
2mn (3n + 1)
(p+2n)(p+3n+l)
[ ""n+!:JQIP. (12)
The extensional viscosity data reported in this paper, for contraction
flows, are based on eqns. (7) and (12).
It should be noted that, for many fluids, including those reported in ref.
11, the contribution of Ni is insignificant and in that case P is simply the
experimentally measured radial normal stress on the boundary wall.
Figure 14 contains data for the Ml fluid; the measured stress data as a
function of flow rates are plotted for two instruments. One instrument was a

I I
103’ -6
10-6 10-7 Q (m3/s) lo
Fig. 14. Measured radial normal stress at the upstream wall of the contraction. Fluid Ml.
Temperature, 20” C; orifice diameter, 1 mm. 0, data from the CR; X, A, q, data from
pressure-driven instrument.
132

commercial capillary rheometer with an orifice die attachment and the other
a “home-made” pressure-driven apparatus. The agreement between the two
sets of data is satisfactory. (Extensional viscosity data inferred from these
experiments are contained in Figs. 16 and 17).

3.2. The spin line rheometer

The spin line rheometer is a commercial instrument manufactured by

Car-rimed, U.K. As its name suggests, it relies on the classical spinning
situation to generate a flow which is dominated by extension. Our customary
data interpretation (see, for example, ref. 5 and 12) relies on a gross
averaging procedure. Specifically, the relevant strain rate in the spinning
experiment is obtained from a knowledge of the flow rate and the dimen-
sions of the threadline at two stations only, i.e. at the position of maximum
die swell and at a station near the take-up device.
The present set of experiments on Ml has also made use of a different
and more conventional method of data interpretation in which the relevant
local strain rate is determined at a number of points along the threadline.
Since the relevant stress at every point is easily determined, the method
supplies a local measure of extensional viscosity. We remark that, over the
range of the present experiments, we did not observe the interesting (non-
monotonic) variation in velocity along the threadline reported by Ferguson
and Hudson [13].

3.3. Open-syphon technique

We made use of an open-syphon technique employing an instrument built

by M.C. Couch [14]. This consisted of a vacuum chamber into which a
vertical thread of test sample was drawn from a containing reservoir, via a
circular orifice. Forces generated in the thread were calculated from the
orifice pressure drop after making appropriate corrections for the contribu-
tions of gravity and inertia. Strain rates were predicted from the flow rate
and the thread dimensions taken at a number of equally spaced stations
along the thread, a polynomial curve fit analysis being used to facilitate the
process. Since the corresponding stress was easily obtained from the cross-
sectional area and force at each station, the extensional viscosity could be
determined over this range of strain rates. A possible advantage this method
possessed over the spin line rheometer is that the sample is drawn from the
reservoir in its “virgin state”.
Results for the Ml fluid are included in Fig. 16.
 I33

Fig. 15. Extensional viscosity data obtained from the SLR for fluid Ml at 20 o C. Symbols
correspond to individual filaments, adopting a local analysis. Dashed line is the envelope of
the set of data obtained using the gross averaging procedure.

3.4. Experimental results

Figures 15 and 16 contain a collection of extensional viscosity data for a

temperature of 20°C. It can be concluded from a comparison of Figs. 15
and 16 that the local and averaged methods of data interpretation in the
SLR lead to results which cannot be distinguished within the large data
interpretation envelope which is characteristic of such a technique. We
remark that the use of strain as a variable rather than strain-rate (a

108 -
2

lo6 - I
1

In
--a /
',..*T.
2 IOk - ' .,y .'
,:.>, I
: ;: /
I 'I
f : ',
F” 1'
C/'
,

lo2 -

t----------
1 I t
lOOI
10-l loo 10’ 102
i (s-1)
Fig. 16. Comparison of extensional viscosity data obtained using different techniques for
fluid Ml at 20 o C. Envelope, SLR, A, open syphon; 1, 2, Contraction with 1 mm and 0.5 mm
diameter orifices respectively; - - - - - -, “Trouton” viscosity 3nc.
134

10”-

u, lo1 - /
2
W
I!? q
P q
d+J
F lo*- B

,oOr______________ I 1

loo 10’ 6 ts-‘1 102

Fig. 17. Comparison of extensional viscosity data for fluid Ml at 50 o C. 0, SLR; -,
contraction (0.5 mm diameter orifice); - - - - - -, “Trouton” viscosity 3~,.

technique which sometimes leads to a better correlation of extensional

viscosity data for different operating conditions) did not lead to any
measurable benefit in the present experiments.
We regard the internal consistency between the three techniques for the
20 o C experiments and also for the 50” C experiments shown in Fig. 17 as
important and encouraging. However, there must still be some uncertainty
about the extensional viscosity levels shown in the figures in view of the
much lower values of qn reported by Fuller and co-workers [15] for the
opposing-jet technique and James et al. [16] for his converging flow tech-
nique. However, the important observation of instabilities in the opposing-jet
technique reported by Ode11 and co-workers [17] may go some way to
account for the relatively low values of in suggested by the opposing-jet
technique at relatively high strain rates, and the whole question of which, if
any, technique is providing the most reliable extensional - viscosity data
must remain an open question.

Acknowledgments

We are happy to acknowledge the help and assistance of our colleagues,

Dr. W.M. Jones, Mr. M.C. Couch, Mr. R.E. Evans, Mr. A.Q. Bhatti, Dr.
T.S.R. Al-Hadithi and Mrs. M.R. Walters.

References

1 T. Sridhar, J. Non-Newtonian Fluid Mech., 35 (1990) 85-92.

2 K. Walters, Rheometry, Chapman and Hall, London, 1975.
 135

3 H.A. Barnes, J.F. Hutton and K. Walters, An Introduction to Rheology, Elsevier,

Amsterdam, 1989.
4 D.V. Boger, J. Non-Newtonian Fluid Mech., 3 (1977-1978) 87-91.
5 D.M. Jones, K. Walters and P.R. Williams, Rheol. Acta, 26 (1987) 20-36.
6 J.J. Magda and R.G. Larson, J. Non-Newtonian Fluid Mech., 30 (1988) 1-19.
7 M.L. Chirinos, P. Cram, A.S. Lodge, J.L. Schrag and J. Yaritz, J. Non-Newtonian Fluid
Mech., 35 (1990) 105-119.
8 D.D. Joseph, J. Non-Newtonian Fluid Mech., 35 (1990) 287-307.
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12 D.M. Jones, Ph.D. Thesis, University of Wales, 1989.
13 J. Ferguson and N. Hudson, J. Non-Newtonian Fluid Mech., 35 (1990) 197-205.
14 M.C. Couch, M.Phil. Thesis, University of Wales, 1989.
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(1990) 277-286.
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