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Increase in elastic modulus of aramide SVM

fibers in tension under stress relaxation regime
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Polymer Science, Ser. B, Vol. 42, Nos. 1112, 2000, pp. 13. Translated from Vysokomolekulyarnye Soedineniya, Ser. B, Vol. 42, No. 12, 2000, pp. 21772180.
Original Russian Text Copyright 2000 by Bazhenov, Rogozinskii.
English Translation Copyright 2000 by MAIK Nauka /Interperiodica (Russia).

Increase in Elastic Modulus of SVM Fibers

in Tension under Stress Relaxation Regime
S. L. Bazhenov and A. K. Rogozinskii
Semenov Institute of Chemical Physics, Russian Academy of Sciences,
ul. Kosygina 4, Moscow, 117334 Russia
Received April 5, 2000;
Revised Manuscript May 22, 2000

AbstractThe behavior of elastic modulus of the loaded SVM aramide fibers was studied under stress relaxation, that is, at the constant length of fibers. The elastic modulus was estimated from the speed of acoustic
wave. At relatively low stresses, stress relaxation is absent, and the elastic modulus is independent of time. At
stress @[sigma] > 1 GPa, stress relaxation appears. A gradual stress relaxation is accompanied by an increase
in the elastic modulus with time. This increase in the elastic modulus is explained by a decrease in the concentration of defects in a polymer crystalline structure; these defects disappear in tension and experience structural
rearrangement from relatively soft fragments of polymer chains to a more rigid state.

under stress. To this end, we advanced a model according to which a polymer chain contains molecular
defects with a reduced rigidity. The increase in the elastic modulus upon creep is explained by the transition of
such defects to a more rigid basic state [3, 4, 10]. This
transition shows the activation character and requires a
certain time. According to [1], all body of experimental
data may hardly be explained neither by the nonlinear
elasticity nor by a decrease in the concentration of
defects under loading. The behavior of fibers may be
explained only by the mutual action of the nonlinear
elasticity and the molecular transitions.
If the concentration of defects actually decreases,
one may anticipate a possible increase in the elastic
modulus of the loaded fibers under stress relaxation
when the length of the sample is constant. Note that, at
a constant length of fibers, their orientation is prevented, and the nonlinear elasticity should lead to a
decrease in the elastic modulus due to the stress drop.
However, the phenomenon of the increase in elastic
modulus at a constant length of fibers was actually discovered in this work; this phenomenon together with
the reversible behavior provides a direct evidence for a
decrease in the concentration of defects upon loading.
The objective of the present work is to study the behavior of the elastic modulus of SVM fibers under the
regime of stress relaxation.

INTRODUCTION
In [1, 2], Rudakov and Bessonov described the phenomenon of the increase in the elastic modulus of oriented polymer fibers in tension. This phenomenon is
very typical of aramide SVM fibers when the elastic
modulus increases both upon tensile drawing at a constant strain rate or creep under the action of a constant
load [35]. In SVM fibers, this phenomenon is well
pronounced, and the elastic modulus increases from the
initial 110120 to ~210 GPa at a tensile strain of 3%.
This effect is reversible and, upon unloading, the elastic
modulus gradually decreases to the initial 120 GPa.
This fact implies that, in the SVM fibers, the increase in
the elastic modulus is not related to orientation which,
at temperatures far below the glass transition temperature Tg , is irreversible. Taking into account this reasoning, one may also understand that the increase in the
elastic modulus of the loaded SVM fibers is not related
to high elasticity. The mechanism of high elasticity
involves the conformational rearrangements of polymer chains [6], which are irreversible at temperatures
far below Tg [7, 8].
Presently, there are several alternative explanations
for the phenomenon of the increase in elastic modulus
with the increasing tensile strain. First, this phenomenon is related to the nonlinear elasticity of fibers. In this
connection, the two alternative models of nonlinear
elasticity were advanced. The nonlinear elasticity is
explained by the anharmonicity of the potential of
interatomic interaction in a polymer chain [1, 2] or by
an elastic decrease in the disorientation angle of microcrystallites or microfibrils under stress [9].
Taking into account the fact that elastic processes
are instant, the nonlinear elasticity may hardly explain
a gradual increase in elastic modulus during creep

EXPERIMENTAL
We studied the SVM yarns composed of 300 fibers;
the linear density was equal to 58 mg/m. The length of
the samples was 600 mm. To provide inlet and outlet
for an ultrasonic signal, the ends of the samples were
decorated with special cone-shaped tips based on a
cured epoxy resin.
1

BAZHENOV, ROGOZINSKII

The mechanical tests of the yarns were performed

on an Instron-1122 tensile machine at a constant strain
rate. During tensile drawing, the sample was exposed to
ultrasonic signals with a carrier frequency of 250 kHz
and a repetition frequency of 900 Hz. The acoustic elastic modulus was estimated through the following relationship [11]
@@,
where @[rho] is the density of fibers and @c is the
speed of ultrasound.
Prior to tests, the fibers were dried at 110C for
30 min. Then, the samples were loaded to a stress of
22.5 GPa, kept under stress for 0.5 h, unloaded, and
annealed at 150C for 1.5 h. After the first loading run,
the length of the fibers was irreversibly increased by
~0.5%, and the elastic modulus increased from the initial 120 to 125128 GPa. Upon further loadingunloading cycles, the tensile strain and the elastic modulus
come back to their initial values when the samples were
annealed for 2 h at 150C. Hence, the first loading cycle
allowed one to prevent irreversible phenomena.
RESULTS AND DISCUSSION
Figure 1 illustrates changes in stress for the SVM
yarn upon tensile drawing at a strain rate of 50 mm/min
and stopping the clamps of the tensile machine. The
time was counted from the instant when the clamps
were stopped. At relatively low stresses (curves 1 and
2), no changes in stress are seen. As the tensile stress is
increased to 1.1 GPa (curve 3), stress relaxation
becomes evident. The relaxation rate increases with
increasing the tensile stress.
Figure 2 demonstrates the behavior of the elastic
modulus of the loaded fibers. At relatively low stress,
when the stress relaxation is absent, the elastic modulus
@E is constant (curves 1 and 2). At higher stresses, @E
increases with time. As far as we know, for the samples
with a fixed length, the phenomenon of the increase in
the elastic modulus of materials, including, polymeric
materials, has not been described yet. The increase in
@E proves the occurrence of the transition of the soft
defects of a polymer chain to a more rigid state [5].
Upon this transition, the polymer chains are extended,
and their length increases.
Changes in the elastic modulus are provided by the
mutual action of two mechanisms, namely, nonlinear
elasticity and molecular transitions [5]. In our experiments, the above factors act in opposite directions.
Stress drop (stress relaxation) leads to a decrease in @E
due to the nonlinear elasticity. However, a decrease in
the concentration of soft defects leads to an increase
in @E. Figure 2 shows an increase in elastic modulus
with time even though stress is decreased. Hence, the
decrease in the concentration of defects is stronger than
the effect of the nonlinear elasticity.
Considering the mutual action of the nonlinear elasticity and the changes in the concentration of defects,

let us note that, depending on the mode of deformation,

each mechanism may lead both to an increase or a
decrease in the elastic modulus. Furthermore, in some
cases, these mechanisms may not come into play. For
example, upon creep at a constant stress, the effect of
the nonlinear elasticity is absent. There are three cases
corresponding to the action of each mechanism and
nine versions of their mutual action. Let us consider all
cases.
1. (++) Tensile drawing at a constant strain rate.
Both mechanisms lead to an increase in @E.
2. () Unloading at a constant unloading rate. Both
mechanisms act in opposite directions, and the elastic
modulus decreases.
3. (+0) Creep under a constant load. The nonlinear
elasticity is absent. The elastic modulus is controlled
only by a decrease in the concentration of defects, and
@E increases.
4. (-0) Length recovery upon an abrupt stress drop.
The nonlinear elasticity is absent. An increase in the
concentration of defects leads to a gradual decrease in
@E [5].
5 and 6. (0+ and 0-) Both cases correspond to the
nonlinear elastic behavior upon loading and unloading,
respectively. Both cases occur at low tensile strains
when creep is absent. As the tensile stress is increased,
the elastic modulus increases and, upon unloading,
decreases.
7. (00) The absence of both mechanisms of changes
in the elastic modulus corresponds to the linear elastic
(Hookean) behavior of material.
Cases 8 and 9 appear to be the most complicated
when the mechanisms of changes in the elastic modulus act in opposite directions.
8. (+-) This case was studied in the present work.
Upon stress relaxation (stress drop), the elastic modulus decreases, whereas a decrease in the concentration
of defects leads to an increase in @E. Figure 2 shows
that @E gradually increases. Hence, the effect of the
transition of defects to a rigid state dominates over
the nonlinear elasticity.
9. (-+) This case was described in [11] when the
behavior of the elastic modulus of SVM fibers with a
fixed length was studied upon an abrupt stress drop. In
this case, one may observe a simultaneous growth in
the tensile stress and elastic modulus with time. As in
case 8, the nonlinear elasticity and the molecular transitions act in opposite directions. A gradual increase in
the tensile stress leads to an increase in @E due to the
nonlinear elasticity. As the concentration of soft
defects is increased, @E decreases. Upon the mutual
action of both mechanisms, the elastic modulus
increases. This fact implies that the effect of the nonlinear elasticity dominates. This result disagrees with conclusion advanced in case 8. Comparing cases 8 and 9
suggests that, at low tensile strains, the nonlinear elasticity dominates whereas, at high tensile strains, the

POLYMER SCIENCE

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INCREASE IN ELASTIC MODULUS OF SVM FIBERS IN TENSION

relaxation transitions prevail. This observation agrees

with the results of [11].
Note that a gradual growth in the rigidity of fibers
conflicts with the assumption that stress relaxation
under load is provided by the breakdown of molecular
chains [12].
Hence, the phenomenon of growth in the elastic
modulus of SVM fibers under stress relaxation, that is,
for the samples with the fixed length, was discovered.
The behavior of the fibers under examination proves
that the increase in the elastic modulus proceeds via a
decrease in the concentration of defects in the polymer
crystalline structure when these defects are transformed into a more rigid state. Note that, in this case,
the orientation of fibers is excluded because the length
of the sample is fixed.
As compared with the nonlinear elasticity, at relatively high tensile strains (@[epsilon] > 1%) and constant length of fibers, the transitions of molecular
defects to a more rigid state appear to have a stronger
effect on elastic modulus. At low tensile strains, a
reverse situation is observed.

FIGURE CAPTIONS
Fig. 1. Stress relaxation at the fixed clamps of tensile
machine. The initial tensile stress @[sigma] = (1)
0.62, (2) 0.86, (3) 1.1, (4) 1.37, and (5) 1.59 GPa.
Key: 1. @[sigma], GPa; 2. Time, min.
Fig. 2. The elastic modulus @E@a of fibers vs. the
stress relaxation time. Tensile stress @[sigma] = (1)
0.62, (2) 0.86, (3) 1.1, (4) 1.37, and (5) 1.59 GPa.
Key: 1. @E@a, GPa; 2. Time, min.

ACKNOWLEDGEMENT
We would like to thank V.G. Grinev for his helpful
assistance in experimental work.
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