Journal of Non-Newtonian Fluid Mechanics, 35 (1990) 197-205 197

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

THE EXTENSIONAL PROPERTIES OF Ml OBTAINED FROM THE

CARRI-MED ELONGATIONAL VISCOMETER

J. FERGUSON and N.E. HUDSON

Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow (Ct. Britain)
(Received May 22, 1989; in revised form September 14, 1989)

Abstract

The extensional flow properties of the “round robin” fluid Ml were

examined using the Carri-Med elongational viscometer at 20” C. With this
particular fluid, use of a spinneret caused flow of a pulsating nature or a
distortion of the filament, or both. Consequently, flow of the fluid was
directly out of the tube. The filament was stretched using the rotating drum
operating at various speeds. The amount of die swell observed depended
upon the take-up speed. The measured diameter profile and the calculated
strain rate curve showed distinct differences from those obtained with most
other polymer solutions previously examined. The apparent extensional
viscosities were determined, and showed Trouton ratios in the range 300-
10000. As a function of total strain, the fluid appeared to strain harden up
to a strain of about 2.5, and then pass through a maximum, before strain
thinning slightly. Average values of stress and strain rate were also de-
termined using a two-point method. The results from this showed the
apparent extensional viscosity to increase as a power law function of strain
rate, although the value of the power law index did depend upon the choice
of the two points selected. The particular collection of flow characteristics
observed in this fluid are, if not unique, then certainly unusual in a number
of aspects. Overall, the material is undoubtedly strain hardening, although
the exact form which this takes, particularly at low strains, would appear to
be a direct consequence of the relaxation time of the fluid.

Keyword: elongationalflow; polymers; rheology; solution; test fluid Ml

1. Introduction

Experiments were performed on the Carri-Med elongational viscometer

(EV) at 20 o C. The EV has been fully described previously [1,2]. The

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

198

instrument is supplied with a number of spinnerets of various internal

diameters. The largest in our set is 1.5 mm. During initial test runs on Ml, it
was noticed that there was a very erratic flow through this spinneret, either
of a pulsating nature or a distortion of the filament, or both. Consequently
spinnerets were not used in the experiments, and flow came directly out of
the tube, of internal diameter 3.96 mm. Using this arrangement, steady flows
and reproducible force measurements were obtained.

2. Procedure

Approximately 300 ml of fluid was slowly and carefully poured into the
reservoir. At least 10 min was allowed for the solution to relax. Fluid was
delivered to the tube by applying a pressure at the reservoir. At a given
pressure, the transducer was zeroed by placing the container immediately
below the tube to catch the issuing fluid. Hence the baseline was not
distorted by gravitational, jet thrust or “Bourdon tube” effects. The flow
rate was measured by a catch and weigh technique, and it was noted that
there was only a small increase (less than 5%) in flow rate at a given pressure
between a filament falling under gravity and one being taken up at the
highest speed. It was also noted that a free jet issuing from the tube
exhibited very little die swell. This was not totally surprising, even though
Ml is a highly elastic liquid, since by using a large internal diameter tube,
wall shear rates at exit were calculated to be less than 20 s-t.
Each run, with a fresh sample, provided several sets of data. Each set
consisted of a flow rate, a force measurement, a take-up speed, a spinline
length and a video image of the filament. This image was then processed
off-line to provide a subsidiary set of data of length and corresponding
diameter.

3. Results

Over the whole series of experiments, spinline lengths were varied be-
tween 30 and 90 mm, take-up speeds from 50 to 800 mm s-t and flow rates
from 13 to 96 mg s-l, and measured loads ranged from 0.9 to 106 mN. As a
general rule a small amount of die swell was observed when take-up speeds
were kept below 200 mm s-l. From this point to about 300 mm s-‘,
extension appeared to start at the tube exit. Above 300 mm s-l, the
extension appeared to start a short way inside the tube. This phenomenon
has been previously observed by Sridhar and Gupta [3], who associate it
with detachment and slip inside the tube. The values given above did change
somewhat with flow rate and spinline length.
 199

I A

A
.
.
150

3- A _j
.

Diameter AA 100
.
(mm) CA Velocity
2- .
A mm.s-’
.
A l
A 50
. A A
I- a A
. A A1
.
..-*
o* ,
0 10 20 30 40 ,

Distance (mm)

Fig. 1. Filament diameter and instantaneous velocity as a function of distance along the
spinline. Flow details: drum position, 50.5 mm; drum velocity, 200 mm s-‘; mass flow rate,
65 mg SK’; measured force, 19.4 mN.

The data were analysed using the full method [2,4]. It was found that
contributions to the extensional force from gravity, surface tension and
inertia were always less than 5% of the measured force. Therefore, these
experiments can be considered to take place under essentially constant force

s- .

Strain

Rate
1
.
I..
.
s-1 .
4

.
.
.

7. I z
.
.
.
.

it

04
0 10 20 30 40 50

Distance (mm)
Fig. 2. Calculated rate of strain as a function of distance along the spinline. Flow details as in
Fig. 1.
200

conditions. The velocity vs. distance data were curve fitted, and from this
the rate of strain and time of extension could be calculated as functions of
distance down the spinline. Typical examples are shown in Figs. 1 and 2.
Since these are essentially constant force experiments, the force balance used
to determine the stress can be reduced to
u
-=- V
00 v,’ (1)
where u is the stress and V the velocity, and the subscript 0 denotes
conditions at the point at which measurement starts. This can be rewritten
as

(I = u,e’, (4
where z is the Hencky strain (ln( V/V,)).

Fig. 3. Apparent elongational viscosity as a function of Hencky strain. Drum position for
each run was 40 mm. Other flow details are as follows:

n 0 V A 0

Drum velocity (mm s-l) 150 200 300 400 500

Mass flow rate (mg s-‘) 84.9 85.7 86.2 86.7 87.0
Measured force (mN) 18.9 30.8 44.8 74.3 105.0
The number at the end of each curve indicates the time, in seconds, taken by the fluid from
tube to drum.
 201

l .

. .- .
A .
6. .
A.
. A
.

6 i i i i
E
Fig. 4. Apparent elongational viscosity as a function of Hen&y strain. Drum velocity for
each run was 200 mm s-l. Other flow details are as follows:

n A 0 v
Drum position (mm) 50.5 70.0 45.0 45.0
Mass flow rate (mg s-l) 65.0 21.9 35.6 65.4
Measured force (mN) 19.4 6.8 17.5 16.5

All results showed Ino to be a linear function of strain, with slope unity
and intercept dependent upon the initial value of stress.
From the calculated values of stress and strain rate, the apparent elonga-
tional viscosity was determined. Examples are given in Figs. 3-5. In Fig. 3,
the results are from runs in which the flow rate and filament length were
kept virtually constant, and only the drum speed was varied, from 150 to
500 mm s-i. As can be seen, although the trend of the change of nn with
strain is similar between runs, the level increases with drum speed. Above a
strain of about 2.5, qn appears to go through a maximum, and the fluid
begins to strain thin. In Fig. 4, the drum speed was kept constant at 200 mm
S -I, whilst flow rates were varied from 22 to 66 mg s-l, and filament lengths
from 45 to 70 mm. Within the experimental error, there is reasonable
correlation. There appear to be maxima at strains of 0.5 and 2.5, and a
minimum at a strain of 1.0. However, at zero strain, the value of qn is still
100 times no. In Fig. 5, the drum speed has been increased to 500 mm s-l.
Flow rates varied between 29 and 95 mg s-l, and filament lengths from 45
202

A
v
10
P l
.

a*
. .J
‘1, .

P&S .
As
.

. s
b
.
.

. l v

. .

l v
. A
7

1C

6 1 2 3 4

Fig. 5. Apparent elongational viscosity as a function of Hencky strain. Drum velocity for
each run was 500 mm s-‘. Other flow details are as follows:

n 0 A V
Drum position (mm) 59.0 80.0 70.0 45.0
Mass flow rate (mg SC’) 75.4 75.6 28.7 95.3
Measured force (mN) 62.2 31.6 28.8 87.3

to 80 mm. Again, reasonable correlation is found, but the maximum at a

strain of 2.5 has a value nearly three times that shown in Fig. 4. Apart from
one run, the lower maximum and the minimum seem to have disappeared.
In order to gain overall viscosity levels, all results were reassessed using
the method developed at Aberystwyth [5] whereby average stress and aver-
age strain rate are calculated using just two points on the spinline. Firstly,
we took the diameter and velocity at the tube and at the drum (extrapolated
from the curve fit). The results are shown in Fig. 6, and are correlated by the
equation

?jn = 140i’.28. (3)

In order to compare these results with those from Aberystwyth [6], we then
reassessed this method. Use of the drum velocity can overinfluence the
strain rate, leading to higher values than suggested by the data. Using the
 203

IO'
10-l IO0 10'

Strain Rate s’
Fig. 6. Average elongational viscosity as a function of the average strain rate calculated using
two points on the spinline: curve a, using the full spinline; curve b, using part of the spinline.

tube diameter can underestimate the average stress. Consequently, we de-

termined the average stress and strain rate using arbitrary points 5 mm
below the tube and 15 mm above the take-up point on the drum. The results
are also shown in Fig. 6, and are correlated by the equation
nn = 757<‘3’25’. (4)

4. Discussion

In normal usage, the fluid would be extruded through a spinneret. As was

pointed out in the Introduction, with Ml this resulted in a pulsed, erratic
flow. To overcome this problem, the spinneret was removed and the fluid
flowed directly from the tube exit. This has the advantage that the stresses
that normally would have been generated at the entrance to, and in, the
spinneret, were absent. In comparison with most other polymer solutions
examined by us, Ml appeared to show complicated behaviour in extension,
something that has also been observed in the falling drop experiment [7].
This was revealed in the elongational viscometer by the fluid profile. Two
204

distinct regions could be observed (Fig. 1). In the first, up to about 10 mm

from the tube exit, diameter fell rapidly with distance. From this point to a
point close to the drum, a much reduced rate of thinning could be seen. This
was virtually linear. When the fluid velocity profile was calculated it was
shown to increase over the length of the filament, whereas a more typical
result would have produced a curve with the velocity asymptotic to some
limiting value. There was a distinct change in the velocity curve, which
occurred at a residence time in the range from 0.25 to 0.5 s, for all
experiments.
A consequence of the above is the variation of strain rate with distance
(Fig. 2). Results with other fluids have shown that the strain rate increases
from the tube along the spinline, passes through a maximum, and then starts
to decrease as the change in diameter of the filament tends to zero close to
the take-up drum, as the filament strain hardens. With Ml, although the
initial behaviour was similar, with an increase followed by a decrease in
strain rate, this occurred generally before the mid-point of the spinline;
beyond this the strain rate started to increase again. This was a result of the
rate of change in diameter becoming constant, although non-zero. This
suggests strain thinning, although, at very high take-up speeds, the filament
could be made to break close to the take-up drum, by what appears to be a
cohesive fracture mechanism.
If the rate of strain for any one experiment was constant, then from eqn.
(2) the apparent elongational viscosity would satisfy the equation

~~(4 = 71E@)e”, (5)

where nn( e) is the apparent elongational viscosity at strain 6, and qE(0) is
the value at zero strain, although with the strain rate being non-zero this is
unlikely to have the value 3~. Hence, plotting liar), against E would result
in linear graphs. However, as shown above, rates of strain were not constant,
so such a simple correlation of elongational viscosity with strain is not
possible.
Figure 3 shows five curves of qE as a function of Hencky strain obtained
at different drum speeds, all other conditions being substantially constant.
As a result, the principal difference between the experiments was the
residence time of the fluid in the spinline. These values are shown in the
figure. Previous results would have led us to expect that the points for all
five experiments would lie close to a single curve. That they did not do so on
this occasion may be related to the total residence times in the spinline, and
the relaxation time of the fluid determined from shear experiments (between
0.3 and 0.4 s). In this series, the total residence time increased from 0.4 to
1.1 s. The former value is close to the shear relaxation time and the latter
close to the timescale in the falling drop experiment [7]. At short residence
 205

values, yE showed strain hardening up to a strain value of just less than 3,

and then fell. This was similar in the other four experiments. However, as
the drum speed decreased, a maximum appeared at low strain values,
producing a result not unlike that found in the falling drop experiment.
When drum speeds were kept-constant, and other parameters varied, as
shown in Figs. 4 and 5, the results do lie close to a single curve. The main
differences between these two figures are the level oflthe upper maximum in
qB and the disappearance in Fig. 5 of the lower max@num and minimum
shown in Fig. 4.
A consequence of the two-part diameter profile is that the results ob-
-tainedinllie averaging technique (Fig. 6) are strongly influenced by the
region of filament sampled. This is unusual in our experience. Curve b is
similar to that obtained by Binding et al. [8].
~-
5. Conclusions

The particular collection of flow characteristics observed in this fluid are,

if not unique, then certainly unusual in a number of aspects. Overall, the
material is undoubtedly strain hardening, although the exact form which this
takes, particularly at low strains, would appear to be a direct consequence of
the relaxation time of the fluid.

Acknowledgements

N.E.H. and J.F. thank Mr. Jim Morrow for painstakingly taking the
measurements from the image processing system, and the Ministry of
Defence for research funding.

References

N.E. Hudson, J. Ferguson and P. Mackie, Trans. Sot. Rheol., 18 (1974) 541.
J. Ferguson and N.E. Hudson, J. Phys. E, 8 (1975) 526.
T. Sridhar and R.K. Gupta, J. Non-Newtonian Fluid Mech., 30 (1988) 285.
N.E. Hudson and J. Ferguson, Trans. Sot. Rheol., 20 (1976) 265.
K.P. Jackson, K. Walters and R.W. Williams, J. Non-Newtonian Fluid Mech., 14 (1984)
173.
K. Walters and D.M. Jones, personal communication.
W.M. Jones, N.E. Hudson and J. Ferguson, J. Non-Newtonian Fluid Mech., 35 (1990)
121-135.
D.M. Binding, D.M. Jones and K. Walters, J. Non-Newtonian Fluid Mech., 35 (1990)
263-276.