Strain Recovery of Polyester and Nylon 66

Monofilaments under Various Temperature Histories

A. C. L U N N , B-L. LEE and I. V. YANNASO
Department of Mechanical Engineering
Massachusetts Institute of Technology
Cambridge, Mass.

Strain recovery of polyester and nylon 66 monofilaments,

following stress relaxation at constant strain, has been
measured under two types of temperature history. In the
first (experiments here called type A ) , the monofilament,
extended at an elevated temperature, was held at constant
strain at that temperature, and then air-quenched to room
temperature while still under stress. The stress was later
removed with the fiber at ambient temperature, and the
recovery from strain determined. In the second (experiments
of type B), the monofilament was also extended at an
elevated temperature, but it was then allowed to recover,
under zero load, at the same temperature, prior to quench-
ing. A cylindrical heater is described which surrounded the
fiber specimen and which could be removed suddenly to
permit rapid air quenching of the specimen. Recovery was
characterized by the percent of applied strain which was
recovered 100 sec after load removal. The percent recovery,
in type A experiments, decreased to low values with in-
creasing stretch temperature. Recovery in type B experi-
ments, however, was markedly different, and showed a mini-
mum value at stretch temperatures in the vicinity of the
glass transition. At higher temperatures, recovery was high,
but it decreased rapidly as T,v was approached due to the
onset of viscous flow. There was thus a discontinuity in re-
covery behavior as the time of quenching increased through
the time of unloading (transition between type A and type
B conditions). The results were interpreted to show that
the achievement of good heat setting (poor recovery) is
critically dependent on the temperature of the fiber during
both stretching and recovery periods.

INTRODUCTION in the temperature level from TI to T2. W e have

he extent to which a fiber regains its original di-
T m e n s i o n following the removal of an applied load
is a function of the time and magnitude of loading,
the time allowed for recovery, and the temperature
history during the stressed and recovery periods. In
many industrial processes (e.g. heat setting or tex-
turing of textile fibers ) these parameters are varied
to achieve the particular recovery behavior desired.
The temperature history is of special importance in
this, and typical industrial processes subject the fi-
ber to one or more changes in temperature concur-
rent with changing stress and strain conditions.
In general, the fiber temperature, stress, and strain
will change in complex ways as functions oE time.
As a first step in the analysis of such complex proc-
esses, we have examined here only step-fiinction
changes in temperature, i.e., an instantaneous change
* TO whom correspondence should be addressed.
610
investigated the recovery of nioaofilaments from a
tensile strain applied at elevated temperature. TWO
classes of recovery conditions may be distinguished
in this case. In the first, which w e here call type A,
the temperature is reduced to room temperature
while the fiber remains under stress, and the stress
is then released, such that recovery occurs at room
temperature. This sequence is analogous to common
industrial “heat setting” practice. In the second, type
B, the stress is released while the fiber remains at
the ( elevated) stretch temperature, such that recov-
ery occurs isothermally, and the temperature is later
reduced to room temperature. This may be termed
“isothermal recovery.”
To simplify the analysis of data, a standardized
history of stress, strain, and temperature was applied
to the fiber specimens. This is shown in Fig. 1. The
fiber was first heated to an elevated temperature. At
time zero, a tensile strain €0 was applied and main-
POLYMER ENGINFFRING AND SCIENCF, SEPTEMBER, 1974, Vol. 14, No. 9
 Strain Recovery of Polyester and Nylon 66 Monofilaments under Various Temperature Histories
I
4 4 I
El
v,
I fibers was 0.05 cm.
v,
0 100 200
Time, set
Type A recovery Type 8 recovery
Fig. 1 . Thermal and mechanical histories applied to the
fiber specimens in this work. In all cases the fiber was
heated to T " C prior to stretching. The stress is removed
at 100 sec. The fiber is air quenched at time tl. tl < 100 sec
in type A experiments, t l > 100 see in type B experiments.
Recovery is measured 100 sec after removal of the load in
both types of experiment.
tained for 100 sec (stress relaxation). At 100 sec,
the stress was removed and the fiber was allowed
to contract. At 200 sec, the recovered strain cT was
measured. The temperature, initially at an elevated
level T , was reduced to room temperature (23°C)
suddenly, i.e., in a single instantaneous step, at a
time tl. In experiments of type A, t, was less than
100 sec, i.e., the specimen was cooled to room tem-
perature while still held at strain c0. In type B ex-
periments, tl was more than 100 sec, thus isothermal
recovery was allowed to occur for (tl - 100) sec
prior to cooling to room temperature.
Isothermal recovery following applied stress has
been studied by others under various mechanical
regimes. Leaderman ( l ) , Ward and coworkers (2-4),
and Turner ( 5 ) applied a square-pulse stress history,
i.e., a creep and recovery cycle. Susich and Backer
( 6 ) and Brown ( 7 ) measured the recovery follow-
ing elongation at a constant strain rate. In the major-
ity of these cases, the stretching temperature was
not a variable of interest and recovery was measured
at ambient temperatures only. However, Brown ( 7 )
conducted experiments at different (constant) tem-
peratures, and found a minimum value of the re-
covery at the glass transition temperature in many
different textile fibers.
In this paper, we have examined the effect of
stretch temperature upon the recovery following
stress relaxation at constant stress, and we have also
examined the effect of suddenly changing this tem-
perature (by air quenching to ambient) at various
stages of the stress relaxation/recovery cycle. The
loading history was the same in all experiments:
100 sec of stress relaxation, with recovery measured
100 sec after iinloading. These were thus two inde-
pendent variables: the elevated temperature T and
the time of air quenching t l ; there is one dependent
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER, 1974, Vol. 14, No. 9
variable, the recovery measured 100 sec after un-
loading.
EXPERIMENTAL
Monofilaments of nylon 66 and of Dacron poly-
ester were supplied by E. I. du Pont de Nemours &
Company, Plastics Department. The diameter of both
Curvature in the polyester fibers as removed from
the spool was eliminated by annealing short lengths
of the fibers under a light load (10 g ) at 70°C for
5 min. The fibers were then annealed under free
shrinkage conditions, in order to stabilize the fiber
structure and to minimize the influence of thermal
shrinkage upon the subsequent tensile recovery ex-
periments. The polyester monofilaments were an-
nealed at 210°C for 10 min; the nylon 66 monofila-
ments at 180°C for 10 min, in a nitrogen atmosphere
to prevent oxidation. Shrinkages in length of 26 per-
cent in the polyester and 3.5 percent in the nylon
66 fibers occurred as a result of this treatment.
A heating device was constructed which could be
rapidly removed from the specimen, allowing the
fiber to be quenched to room temperature by the
surrounding air. The apparatus is shown in Fig. 2.
The monofilament specimens were mounted on an
Instron Universal Tester ( Instron Corporation, Can-
ton, Massachusetts), using extension grips to which
the specimens were clamped at each end. A heating
chamber surrounded the specimen and the exten-
sion grips. It was constructed from a Lux-Therm
portable infrared heater model LTH206 ( Hi-Shear
Corporation, Torrance, California). The heater was
built into a housing which surrounded a copper
tube, 2 em in diameter and 20 cm in length. The
copper tube was painted matte black on the outside
4 to load c e l l
heoter box
bloc kene d
c o p per tube i n f r a r e d heating
element
specimen
heoter support
clomp
g r i p extension ___ __ support rod
rod
lower p o s i t i o n
o f heater
crossheod
\
\\\\\\\\\\\\\\'
Fig. 2. Movable heating box used in the experiments.
61 1
 A. C.Lunn, B-L. Lee and I . V.Yannas
to absorb the infrared radiation efficiently. The fiber
specimen was inside the tube.
In use, the infrared radiation heated the copper
tube, which itself heated the air surrounding the
specimen. The specimen was thus heated by air
convection. The copper tube was employed to pre-
vent direct radiative heating of the specimen, which
would have made it difficult to determine the ac-
tual specimen temperature. The heater box could
be moved up and down manually, and clamped in
either position. In its upper position the heater sur-
rounded the specimen. To effect a step jump from an
elevated temperature to room temperature, the heater
was rapidly moved to its lower position, thus ex-
posing the fiber specimen to air at room temperature
almost instantaneously.
Temperature stability was provided by propor-
tional control feedback with a thermistor probe.
Specimen temperature was measured with a ther-
mocouple which touched the specimen. Tempera-
ture fluctuations with time at a given point on the
specimen were less than -t- 2°C during the experi-
ment. Temperature gradients with position along
the specimen were greater than this: k 5°C from
top to bottom of the 10 cm gauge length at 100°C
and +- 8°C at 180°C.
Ideally, the temperature drop from T to 23°C
during the experiment is an instantaneous change,
or step jump. In fact, a finite time was required
for specimen cooling when the heater was removed.
The cooling time was estimated to be approximately
5 sec. This was estimated by data from experiments
of type A in which the temperature drop closely
preceded the release of load from the specimen. If
the specimen has not cooled completely prior to re-
lease of the load, anomalously high recovery will be
found. Such anomalous recovery was found in the
polyester when the heater was removed 5 sec before
release of load (tl = 95 sec), but not when 10 sec
elapsed (tl = 90 sec). Measurements were there-
fore not obtained here for 90 sec <tl < 100 sec.
A fresh specimen was used for each experiment.
After 5 min of thermal equilibration at T"C under
no load, the zero strain condition was established by
moving the crosshead of the tensile tester to induce
a small load (20 g ) across the specimen. Use of this
small load, rather than a zero load, was found to
ensure accuracy and repeatability of the strain mea-
surements. The specimen was then rapidly extended
at time zero to a strain eo (measured by a dial gauge
contacting the crosshead) and held at fixed length. At
100 sec the crosshead was rapidly moved up to
reduce the stress level to zero, and then moved up
a little further so that the specimen buckled slightly,
thus ensuring that the stress remained zero even as
the specimen continued to contract with time. At
200 sec the residual strain was determined by once
again lowering the crosshead to induce a load of 20 g,
and measuring the crosshead position with a dial
gauge. During the experiment, at time tl, the heater
612 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER, 1974, Vol. 74, No. 9
was removed from the specimen as described above,
to effect the temperature drop to 23°C.
The initial and extended length of the specimen
were both measured at the elevated temperature
T"C; the length after recovery was measured at
23°C. It was therefore necessary to make a correc-
tion for length changes due to thermal expansion
effects. Calibration measurements were made using
specimens under only the small (20 g ) load used to
establish the zero strain position; the length was
first measured at T"C, and then at 23°C. Thermal
contraction during cooling was calculated from the
change in length. All recovered lengths measured
experimentally were corrected for thermal contrac-
tion bv these calibration measurements. The polyester
monofilament was found to decrease in length on
cooling, by an amount which increased with initial
temperature level. The greatest shrinltage measured
was 0.45 percent, when cooled from lS0"C to 23°C.
The nvlon 66 monofilament, on the other hand, was
found. to increase in length when cooled from tem-
peratures above 80°C to room temperature. The max-
imum length increase occurred after cooling from
the highest temperature used, 18O"C, when the fiber
extended by 0.9 percent on cooling to 23°C. The
oriented nylon 66 examined here thus has a negative
linear coefficient of thermal expansion. This effect in
oriented nylon was reported by Leaderman ( 1) .
Errors in strain measurement arose from uncer-
tainty in dial gauge readings of' the crosshead dis-
placement, and are low. Uncertainty in strain is
estimated to be -i: 0.02 percent strain. Slippage of
the specimen in the grips war, negligible. Strain un-
certainty contributes to errors in percent recovery R,
but temperature gradients in the specimen are more
significant, and the resultant uncertainty in percent
recovery is estimated to be t- 3 percent R.
RESULTS
Polyester and nylon 66 monofilaments were sub-
jected to a standardized mechanical history: they
were maintained at a constant strain level for 100
sec, and then allowed to recover under no load for
a further 100 sec. Initially, the fiber was at an elevated
temperature, but at a time t , it was rapidly air-
quenched to room temperature. When tl < 100 sec,
(i.e. quench time < unloading time) the fiber was
thus cooled while still under load (experiments of
type A, Fig. 1 ). When tl > 100 sec, (quench time
> unloading time) the fiber was able to recover
lor a variable period of time, ( tl - 100) sec, before
being cooled under no load (experiments of type B,
Fig. 1 ) ,
The extent of recovery may be conveniently char-
acterized by the percent recovery, R:
R = - x 100 percent
€7
(1)
€0
where L,, is the applied strain level and E,. is the
 Strain Recovery of Polyester and Nylon 66 Monofilaments under Various Temperature Histories
/ I / / I / I /
strain that has been recovered following removal
of the stress (cf. Fig. I ) , at the particular time of
measurement (100 sec after time of load removal
in the data reported here). Thus, R has the value
180 percent if the fiber returns to its original dimen- e
,/' Polyester
sions, and zero if it does not recover from its stretched
length at all. The parameter has been used by Susich
and Backer ( 6) and by Brown ( 7 ) .
The percent recovery of polyester monofilament t, = 105 sec
I I 0 sec A
from a strain c0 of 2.1 percent is shown in Fig. 3 150 sec o
for experiments of type A, in which the fiber, 190 sec
stretched at an elevated temperature T at time zero,
is rapidly cooled to room temperature at a time tl,
while StrlI under load. The load is released at 100
a
20
c Eo = 2.1%

sec, and recovery is measured at 200 sec. Recovery
decreases rapidly as the stretching temperature in-
creases. However, an increase in tl (the time of
exposure to the elevated temperature while
stretched) from 10 to 90 sec leads to a very slight
decrease in the recovery.
As stated earlier, the type A experiment is a form
of heat setting, and we may equate low values of
percent recovery with high heat setting efficiency.
Thus, Fig. 3 shows how the heat setting efficiency
increases with higher setting temperature and with
longer setting time.
The recovery of polyester in a type B experiment
is shown in Fig. 4, also from a strain level of 2.1
percent. In this series of experiments, the fiber is
allowed to recover isothermally, at tl = 105 to 190
sec, and is then rapidly quenched to room tempera-
ture. Very little change in fiber length was observed
at room temperature, i.e. between time of quench-
ing and time of recovery measurement (200 sec).
In other words, substantially all of the recovery in
type B experiments has occurred at the elevated
temperature during a recovery time ( tl - 100) sec.
0 0
250
0 50 100 150 200
S t r e t c h T e m p e r a t u r e T. 'C
Fig. 4. Percent recovery as a function of stretching tempera-
ture for polyester monofilament. Fiber released from stress
betore being air quenched at carious times tl ( t y p e B experi-
ment). Initial strain level 2.1 percent.
The percent recovery shows a minimum value in
the vicinity of 8O"C, the glass transition temperature
of PET ( 8 ) . Recovery is also the most time-depen-
dent at this temperature in the time-scale of 5 to 90
sec.
There is a marked difference in recovery behavior
between experiments where quenching precedes load
removal (type A ) and those where quenching occurs
after load removal (type B ) , The difference is most
pronounced at temperatures considerably above T,,
where recovery is very low for the former type
( F i g . 3 ) , but rapid and high for the latter ( F i g . 4 ) .
There is thus a discontinuity in the recovery as the
time tl of quenching the fiber from T"C to 23°C
passes through the unloading time, 100 sec. The
discontinuity is clearly apparent in Fig. 5, which
Unloading

t i = 10 sec
50 sec A
90 sec o

0 50 100 I50 200

S t r e t c h Temperature T, " C 0 50 I00 150 200
T i m e of quenching t , , sec
Fig. 3. Percent recooery as a function of stretching tempera-
ture for polyester monofilament. Fiber air quenched to Fig. 5. Percent recovery of polyester monofilament as a
ambient temperature while under stress ( t y p e A experi- function of quenching time t l . tl < 100 sec: type A experi-
ment) at carious times t l . Initial strain leuel 2.1 percent. ment. tl > 100 sec: type B experiment. lnitial strain
Recotiery measured 100 sec after removal of the load. letiel 2.1 percent.

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER, 7974, Vol. 74, No. 9 613

shows the percent recovery, measured at 200 sec,
as a function of the quenching time. At an initial
temperature of 80°C ( T si T g ) ,there is only a slight
discontinuity at tl = 100 sec, but at 150°C ( T > T,)
the recovery increases dramatically as this threshold
from type A to type B experiments is crossed.
The effect of initial strain level c0 on the recovery
behavior of polyester is shown in Figs. 6 and 7 for
experiments of type A and type B respectively. The
percent recovery decreases with increasing co. This
contrasts with the prediction of the theory of linear
viscoelasticity that R is independent of co for a lin-
ear material ( 9 ) . It is seen from Figs. 5 and 6 that
the nonlinearity of polyester, as evidenced by the
rate of change of R with increasing strain, is most
pronounced at temperatures below about 80°C, the
glass transition temperature. Above T , the nonlin-
earity is less marked.
l o
Pol yes t e r
0
6, =
0 L
0 50 I00
S t r e t c h Temperoture
Fig. 6. Percent recovery as a function of stretching tempera-
ture for polyester monofihment. T y p e A experiment, tl = 90
see, for various initial strain levels.
c
,$ 40
2
E
20
0 1
0
I ~ 1
= 110 sec
50
, I I I
I00
, I
150
S t r e t c h Ternperoture T, OC
Fig. 7. Percent recovery as a function of stretching tempera-
ture for polyester monofilament. T y p e B experiment, ti = 110
see, for various initial strain levels.
614
A. C . Lunn, B-L. Lee and I . V . Yannas
Nylon 66 shows recovery behavior qualitatively
similar to that of polyester in both type A and type
B experiments ( F i g . 8 ) . The type A data, where
the fiber is cooled to room temperature prior to re-
moval of the load (tl = 90 sec in F i g . 8 ) , show R
decreasing with increasing stretching temperature.
The type B data ( t l = 110, 200 sec on F i g . 8 ) show
a minimum around 60"C, which is in the vicinity of
the glass transition temperature for nylon 66 (8).
A decrease in recovery is observed at the highest
temperatures used in type B experiments, both for
polyester ( F i g . 4 ) and for nylon 66 ( F i g . 8). Few
data points were obtained at temperatures above
1OO"C, because the fibers ultimately became unable
to sustain the small load which was applied to de-
termine the zero strain position: partial melting of
the fiber led to irrecoverable viscous flow. I t is
therefore concluded that the percent recovery in
type B experiments decreases sharply to zero as the
stretching temperature approaches the melting point,
0 l
approximately 265°C for both nylon 66 and poly-
ester (10). This is indicated by the broken lines in
Figs. 4 and 8.
2. I "/" 0 DISCUSSION
The recovery behavior in type B experiments ob-
14.8% 0 served here is closely similar to isothermal recovery
data reported by Brown ( 7 ) for a number of fibers,
including nylon and polyester. Qualitatively similar
behavior was observed in amorphous polycarbonate
sheet by Lunn and Yannas (11). In all cases, a
minimum in the isothermal recovery near T , is ob-
served which, in the case of amorphous polycar-
I50 200
bonate ( 11), is considerably more pronounced than
with the semicrystalline polymers used in this work.
The minimum arises from viscoelastic effects. Be-
T, " C low T , most relaxation times of the system are much
longer than the experimental timescale, so that few
relaxations occur, and the polymer is stiff and springy.
I i
200sec
i
€0 = 2.1 %
3.8 %
0
A 1
, , ,
200
j 0
0
l l l l l
50
l l
Stretch
r l l l
100
l l l l i
150
Temperature T , O C
Fig. 8. Percent recovery as a function of stretching ternpera-
ture for nylon 66 monofilament. Experiments of type A
(tl = 90 sec) and type B ( t l = 110, 200 sec). lnitial
l
\
l l I
200
l r l l
250
strain level 1.85 percent.
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER, 1974, Vol. 14, No. 9
 Strain Recovery of Polyester and Nylon 66 Monofilaments under Various Temperature Histories
Above T,, the amorphous regions have relaxation
times much faster than the experimental timescale,
so that response to loading or unloading is rapid,
and the polymer behaves in a reversible, highly
elastic manner. In the vicinity of T,, however, nio-
lecular relaxations occur in experimental timescales,
so that the observed deformation and recovery occur
sluggishly. Recovery is slow and highly time-depen-
dent. A good discussion of this phenomenon is given
by Brown ( 7 ) .
The decrease in isothermal recovery at tempera-
tures approaching the crystalline melting point, ob-
served here in type B experiments, has also been
observed in amorphous polycarbonate, where it was
shown to arise from irreversible viscous flow at
temperatures above T,.
The marked difference in recovery behavior be-
tween experiments in which the fiber is cooled prior
to release of load (type A ) and those in which re-
covery occurs at the stretch temperature (type B )
demonstrates the critical importance of fiber tem-
perature at the time of release of the stress. To
achieve good heat setting (poor recovery), the fiber
must be stretched at a sufficiently high temperature,
and then must be cooled to near ambient conditions
before release of the load (type A conditions). Even
a short period of recovery a t the stretch temperature
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER, 1974, Vol. 14, No. 9
leads to a considerable loss of heat-setting efficient!,
(high recovery), as seen in type B experiments.
These considerations apply at stwtching tempera-
tures below the melting region. As the stretch tem-
perature approaches Thf,there is an increasing com-
ponent of irrecoverable viscous flow, with the result
that even if the load is removed prior to cooling
the fiber, recovery is poor.
REFERENCES
1. H. Leaderman, “Elastic and Creep Properties of Fila-
mentous Materials and Other High Polymers,” Textile
Foundation, Washington, D.C. ( 1943).
2. I. 14. Ward and E. T. Onat, J. Mech. Phys. Solids, 11,
217 ( 1963) .
3. D. W. Hadley and I. 11. Ward, J. Mcch. Phys. Solids,
13,397 (1965).
-1. C. J. Morgan and I. hl. \Vard, 1. llech. Phys. Solids,
19,165 ( 1971).
5. S. Turner, P O ~ ~ TEng.
J I . Sci., 6, 306 ( 1966).
6. G. Susich and S. Backer, Textile Res. J., 21, 482 (1951).
7. A. Brown, Textile Res. J., 25, 891 ( 1955).
8. N. G. XlcCrum, B. E. Read, and G. \\’illiams, “Anelastic
and Dielectric Effects in Polymeric Solids,” pp. 484, 501,
Wiley, London, ( 1967 ) .
9. I. V. Yannas, A. C. Lunn, and 51. J. I)o).le, ACS Polyin.
Prepr., 13, 96 (1972).
10. “Modern Plastics Encyclopedia,” Breskin Publications,
New York, (1961).
11. A. C. Lunn and I. V. Yaiinas, in preparation.
615