Swelling of a rubber cylinder

in torsion: Part 2. Experimental

K. M. Loke, M. Dickinson and L. R. G. Treloar
Department of Polymer and Fibre Science, University of Manchester Institute of
Science and Technology, Sackville Street, Manchester M60 1QD, UK
(Received 14 September 1971)

Experiments have been carried out on the effect of torsion on the swelling of a
rubber cylinder in a low molecular-weight liquid, the object being to test the
theory given by Treloar. Both natural rubber and a synthetic poly(cis-isoprene)
were used, with toluene as the swelling liquid. Application of torsion resulted
in a reduction in the swelling by an amount approximately proportional to the
square of the torsion, as predicted theoretically. The values of this reduction,
however, were less than the predicted values by amounts varying from 12% to
23%, depending to some extent on the type of rubber and on the degree of
crosslinking. These discrepancies are believed to arise mainly from experimental
difficulties.

INTRODUCTION o! a dumbbell having substantial conical ends terminated

by square blocks for the application of the torsional stress
In the previous paper z the theory of the effect of torsion (Figure 1). The junction between the central cylindrical
on the equilibrium swelling of a crosslinked rubber was portion and the conical end was rounded off to avoid a
developed. It was shown that the expected effect is a stress concentration in this region. The internal dimen-
reduction of the degree of swelling by an amount which is sions of the clamp (Figure 2) were larger than the cor-
approximately proportional to the square of the torsion. responding dimensions of the unswollen test-piece, but
The present paper is concerned with the experimental smaller than its freely swollen dimensions; this, together
examination of this problem in relation to the theory
developed.
Since the expected effect depends on the square of the
torsional strain, it is important for the purpose of obtain-
ing an accurate result that this torsional strain shall be as
large as possible. This involves considerable practical
difficulty, since under conditions of prolonged loading in
the highly swollen state the strength of the rubber is
greatly diminished. Also, in order to avoid buckling in the
twisted state it is necessary to apply some extension in the
axial direction, and this further increases the total stress
to be borne. In practice the maximum torsion which could
be applied before the specimen ruptured corresponded to a
value of the parameter ~a (surface shear strain) of about 112mm
0-8, which yielded a change of swelling due to twist of
about 8 ~ . This, although not as large as it had been
hoped to obtain, was sufficient to provide a fair basis for 96mm
comparison with the theory.
The experiments were carried out on both natural 71mm
rubber (smoked sheet grade I) and 100~o poly(cis-l,4-
isoprene), swollen in toluene (Analar grade). The vul-
canizates were compounded according to the recipes given
in Table 1 using cold mixing on an open mill.
b L 5.Omm diam
The design of the test-piece and of the clamps took into
account the necessity to avoid high stress concentrations
in the region of the clamps. The test-piece was in the form Figure 1 Test-piece dimensions: (a) perspective; (b) elevation

POLYMER, 1972, Vol 13, May 283

Swelling of a rubber cylinder in torsion (2): K. M. Loke et al.
with a rounding-off of the edge of the clamp from which
the rubber emerged, was intended to reduce the stresses at
the edge of the clamp, while retaining a positive pressure
on the conical region of the sample.
The degree of swelling of the cylinder in torsion was
obtained from measurements of axial length and diameter
obtained by means of a Pye 2-way travelling microscope
reading to 0.005 mm. The accuracy of the swelling mea-
surement was limited by the accuracy with which the
diameter of the specimen could be measured. For the
highest accuracy it is desirable that this diameter should
be as large as possible; however, the greater the diameter
the longer is the time required to attain equilibrium
swelling and the greater, therefore, the probability of
fracture. The diameter chosen (Smm) represented a
practical compromise, and gave a time to reach equili-
brium of between 10 and 20 hours.
The moulding presented a problem. The mould was
split in the diametral plane of the cylinder. Closure of the
two halves caused the trapping of a variable amount of
rubber in the 'bite'; this resulted in a non-circular section
of the final test-piece. To overcome this difficulty mould-
ing was carried out by a transfer moulding process which
involved injection of the rubber into the closed mould
through a small hole in the end-plate, excess 'flash' being
extruded through a similar hole at the other end. Even
with the precaution, however, significant deviations from
circularity of the cross-section were not entirely eliminated
and the experimental procedure had to be designed to
minimize their effects (see below).
METHOD OF MEASUREMENT
The specimen was mounted between clamps A and B
attached to the apparatus shown in Figure 2. This
I_.
-
377mm
C ' A B
j
r--'-.. !
_ ::~]~1~111/111/11,1111111111111111~11111~111~111
a
c•C A B
1--J . ~ . ~ . . - ~IDlli111111tI111lllIl,l,]llIIl~IIi~11tlll
b
Figure 2 Apparatus for combined torsion and extension: (a) plan; (b) elevation
204 POLYMER, 1972, V o l 13, M a y
enabled the required amount of torsion and axial exten-
sion to be applied while the specimen was immersed in
the swelling liquid. Rotation of the clamp A was effected
by means of the worm-gear mechanism C, and changes in
axial length by the bevel gear D, which enabled the car-
riage B to be shifted horizontally (by rotation of the
threaded shaft F). The assembly was mounted in a metal
trough filled with the swelling liquid up to a level at which
the clamps were immersed. The trough was covered with a
sheet of glass to reduce evaporation, and stood in an outer
water bath thermostatically controlled at 25 _+0.05 °C.
The measurements of axial length were obtained from
reference marks 3 to 4 cm apart inscribed on the surface
of the specimen as shown in Figure 1. A rubber embossing
ink was used for the natural rubber/sulphur vulcanizates,
whilst for the dicumyl peroxide cured samples of both
natural rubber and Natsyn an ordinary 'biro' ink proved
satisfactory.
The specimen was allowed to swell for 2 to 3 days, with
periodic adjustments of axial length, in order to achieve
swelling equilibrium without 'buckling' of the cylinder.
This procedure was adopted after it has been found that
stretching of the unswollen cylinder to the final length
followed by immersion in liquid resulted in early rupture.
A considerable tension was required to achieve the
desired extension of the dry rubber, and in the presence of
the liquid the strength was so much reduced that rupture
occurred before this tension could be sufficiently relieved
by swelling. In the method used here elongation proceeded
concurrently with swelling and high stresses were avoided.
(A similar principle was adopted by Flory and Rehner3 to
overcome this difficulty.)
After a final measurement of dimensions the torsion
was then applied, keeping the length between clamps
constant. Because of the slight irregularity in shape of the
cross-section of the sample already referred to, the
-]
..j
E ,_
"
F
I(o
I
~11~1~1/11111111111/111/111111111/111/1/111~111~11111111111~J
T
76 mm
E l
D
I |~I111111111111lI11111111111111111111lI111111lI1111~I111111~II
E
 Swelling of a rubber cylinder in torsion (2) : K. M. Loke et al.

Table 1 Rubber compounding ingredients (parts by weight)

Sample A B C D E F G

Smoked sheet, Grade 1 100 100 100 100

Natsyn 100 100 100
Dicumyl peroxide 3-2 3.5 3-0 3"0 3"0 3"0
M.B.T.S. Vulcafor (accelerator) 0'5
Zinc oxide 0.5 2 0.5 0.5
Stearic acid 0"5
Carbon black 0.25
N-phenyl-2-naphthylamine (antioxidant) 0.5
Sulphur 6
Cure time (min) at platen temp. of 140°C 35 30 33 55 30 32 30
Mc (swelling) 8891 8184 12 380 8313 11 294 11 312 14 566

swollen volume corresponding to the untwisted state was
obtained from measurements of the dimensions of the
swollen cylinder immediately after application of the
torsion. In the time required to carry out this measure-
ment ( ~ l min) any change of swelling would have been
very small. This was confirmed by checks against the
volume before twisting; the differences (volume after twist-
ing minus volume before twisting) ranged from +0.039
to -0.011 cm a, with an arithmetic mean of +0.0141 or
+0.3%, i.e. in the opposite sense to the subsequent
change of swelling. The important consideration was that
by focusing always on the same diametral section of the
sample (midway between the reference marks) the effects
of any irregularity of section were avoided. Measure-
ments were made periodically until a limiting value of
swelling was reached, after which the twist was removed.
The sample was then allowed to swell overnight to
equilibrium in the untwisted state (at constant axial
length). A new twist was then applied and the above
procedure repeated. The torsional strain was obtained
from measurement of the axial length of one or more
complete turns of twist, using the mould closure line as
reference mark.
A small irreversible increase in swelling occurred over
the entire period of experimentation, lasting from 10 to
14 days. However, this slight irreversibility, in which suc-
cessive equilibrium volumes in the untwisted state dif-
fered by less than 0.5 %, had no significant effect on the
value of relative volume change obtained over a single run
occupying from 8 to 13 hours.
CHARACTERIZATION OF SAMPLES
The mean chain molecular weight Me may be determined
from measurements of either modulus or swelling
equilibrium. Since the relevant problem is concerned with
swelling, it was more appropriate to use the swelling
equilibrium for the purpose. The cylindrical portion of the
rubber sample was cut out and free-swollen in toluene to
equilibrium (2-3 days), after which it was removed,
surface-dried, and weighed. Weighings were then made at
5 h intervals during drying, which required 3 days. These
weighings, together with the measured densities of the dry
rubber and of the toluene, enabled the volume fraction of
rubber (v2) to be obtained (assuming additivity of
volumes). The value of Me was then calculated from the
equation:
i n ( l -- V2)+ v2+XV~ = - ( p V 1 / M c ) v l/3
Values calculated in this way are given in Table 1.
The successive twisted states for any one sample did not
correspond to exactly the same axial length, or axial
extension ratio flz, between reference marks. Since the
objective is to derive the effect of torsion on equilibrium
swelling, at constant axial length, it was necessary to apply
a correction to the measured swollen volume to obtain the
equivalent degree of swelling at a fixed value of/33, for
which the mean over the complete range of torsion values
was taken. The required correction was obtained by dif-
ferentiating the following equation (equivalent to equation
(i 1) of Part 1x) with respect to v2:
ln(1 - vz) + v2 + XVZ~= - p V l / Mcfl8 (2)
and writing ~ V/V= - 8v2/v2. This gives:
.... pVl/Me 3o (3)
v / v - - [2X-Z i i ( l - vz)]v~fl~ p3
This formula is strictly valid only for zero torsion, but
was assumed to be sufficiently accurate for the present
purpose, the corrections involved being quite small
(~V/VxO.6% at most).
TREATMENT OF EXPERIMENTAL DATA
The experiments were carried out on 4 natural rubber
vulcanizates and 3 Natsyn vulcanizates, each group
comprising a range of chain molecular weights Me
(Table 1). Detailed consideration of the data, and of the
methods of calculation employed, will be presented for
one sample only--the Natsyn 'A' sample. Corresponding
results for the remaining samples will be limited to the
comparison of theoretical and experimental volume
changes on twisting.
Derivation of Me
For the Natsyn 'A' vulcanizate the measured free swell-
ing equilibrium at 25°C corresponded to a volume frac-
tion (vz) of rubber of 0.1893. The measured density of the
rubber was 0-9016gcm -3, and of the solvent 0-862. The
molecular weight of toluene being 92.13, this gives a
molar volume (V1) of 106.9. Taking X=0.40 (as for natural
rubber in toluene") substitution of these data in equation
(I) yields the result Me=8891.
Attainment of equilibrium
(I)
Figure 3 shows the course of the volume changes sub-
sequent to the introduction of a particular value of twist,

POLYMER, 1972, Vol 13, May 205

 Swelling of a rubber cylinder in torsion (2): K. M. Loke et al.

Since there is the danger here of a circular argument,

4-26 1 this procedure needs some justification. We note first that
the value of Me is determined from free swelling, hence

~" 4.18
! T the calculation of v2 for the swollen stress-free state is
simply a conversion back to an original swelling measure-
ment. The only truly theoretical part of the calculation is
therefore the effect of the axial extension on the swelling.
~ 4-10 For the case considered the value of v2 in free swelling
was 0.1893, corresponding to a change of linear dimen-
sions in the ratio 1-742 : 1. The relatively small exten-
4"02 sion to fla = 1.938 gives a calculated change of v2 to 0"l 813,
I I I I I
i.e. a reduction in v2 of 4.4%. It is only this 4.4% which
0 2 4 6 8 IO 12
relies on the applicability of the theory, and on the basis
Time (h } of previous experiments on simple extension 4 it would
seem reasonable to assume that this will not be in error by
Figure 3 Change of volume with time after application of torsion. more than, say, 5 % of itself, or 0.2 % of the whole swollen
Natsyn sample A, ~bao=0. 4383 volume. This would produce an error of the same amount
(0.2 %) in ao2, which is practically negligible.

1.00
COMPARISON WITH THEORY

~: o.9a The calculated values of the change of volume due to

torsion (A V/Vo) were based on the theory discussed in the

0"96

a: 0.94

0.92
0 0
Time (h)
4 ~ JD,~ v

Figure 4 Relative change of volume with time for Natsyn A, for

following values of ~bao:A, 0.1806; B, 0.2706; C, 0.3609; D, 0.4383;
E, 0.5157; F, 0.5670 0

represented by 4~a0=0.4383. The volumes shown have # o

been corrected to take account of the small difference of
axial extension ratio fla, which in this case was 1.934, 4
from the mean, 1.938, for all experiments on this sample;
this correction varied from +0.0036 to +0.0038 cm a dur- ? o
ing the course of equilibrium. The total reduction of
volume due to torsion amounted to 0.2207cm a on an
4
original volume of 4.2467 cm a, giving AV/Vo = - 5.20 %,
for this particular twist.
The complete set of curves for the six values of twist 0
employed is shown in Figure 4. These have been plotted,
for ease o f comparison, in terms of relative volume, 4
referred to the untwisted state.
0
Derivation of ao
4
For comparison with the theory, which gives the change
of swelling most conveniently in terms of the dimension- I I I
less parameter ~ba0, it is necessary to determine the un- 0 0-05 0"10 0"15 0"20 0"2.5 0"30
swollen radius a0. Because of the non-circularity of the
cross-section this was obtained not by direct measure- ~2Oo2
ment of the dry rubber, but from the measured diameter in
the swollen untwisted state, at the extension ratio fla, Figure 5 Relative reduction of volume due to torsion for rubbers
together with the calculated value of v~ for this state. listed in Table 1. ~ , Calculated;---, observed

206 POLYMER, 1972, Vol 13, May

 Swelling of a rubber cylinder in torsion (2): K. M. Loke et al.
previous paper 1. For sample A the modification referred
to in Part 1was used, in which the numerical integration
was performed with respect to r 2, and the limit of the
axial region (rl) coincided with the step length 8(r2). For
all the other samples the integration was performed with
respect to r, using a value of 8r of 10-3 and a value of rl
sufficient to give a difference between/31 and/3z of 10-6
(rl ~ 10-z). A check was made, however, to ensure that
these two methods of calculation gave substantially
identical results. The results are shown in Figure 5 in the
form of plots of - A 1I/Vo against ~2ao2.
The experimental results show the expected form of
dependence of swelling on torsional strain, though there is
a consistent quantitative discrepancy from the theoretical
curves. Based on the maximum values of ~a0, this dis-
crepancy ranges from - l l . 7 % (sample A) to - 2 2 . 9 %
(sample F), with a mean of - 17.2 %. The discrepancy was
somewhat lower for the Natsyn samples ( - 14.1%) than
for the natural rubber samples ( - 1 9 . 6 % ) . There was a
slight indication of a correlation with Me, the smaller dis-
crepancies in either group being obtained with the samples
having lower Mc values.
These discrepancies are well outside the experimental
variations. There may, however, be systematic errors. One
possible source of error might be the failure to attain the
true swelling equilibrium after twisting. A compromise is
necessary owing to the gradual upward drift in swelling
referred to previously; after prolonged equilibration the
initial reduction is followed by a slow increase in volume.
(There is a slight indication of this in the top curve of
Figure 4.) The total volume change may on this account
be slightly underestimated. Another error might arise from
the very slight residual buckling in the specimen at high
twists, which could not be entirely eliminated. This also
would have the effect of reducing the true torsional strain
and hence the change of volume.
More generally, it is important to bear in mind that the
effect of torsion on the swelling equilibrium, in contrast to
the effect of extension, is essentially a second-order effect,
proportional to the square of the strain. As a result it is
likely to be affected to a disproportionate extent by any
reduction of the true elastic strain, associated with stress
relaxation or irreversible structural changes, or indeed by
any deviation of the material from the postulated
idealized elastic structure. Any such effects would be in
the direction of a reduction of the magnitude of the change
in swelling, in line with the experimental deviation.
In view of these experimental difficulties the present
observations cannot be regarded as providing conclusive
evidence of a genuine difference between the theoretical
and actual effects of torsion on the equilibrium swelling.
ACKNOWLEDGEMENT
The authors acknowledge with thanks the provision of
maintenance grants by the Malayan Rubber Fund Board
(for K.M.L.) and by the Science Research Council (for
M.D.). They are also indebted to Dr M. D. Heaton and
Dr R. F. T. Stepto for advice and assistance relating to
the computational aspects of the work.
REFERENCES
1 Treloar, L. R. G. Polymer 1972, 13, 195
2 Blanchard, A. F. and Wootton, P. M. J. Polym. Sci. 1959, 34, 627
3 Flory, P. J'. and Rehner, J. J. Chem. Phys. 1944, 12, 412
4 Treloar, L. R. G. Trans. Faraday Soc. 1950, 46, 783
POLYMER, 1972, Vol 13, May 21}7