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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- investigated the recovery of nioaofilaments from a
T m e n s i o n following the removal of an applied load tensile strain applied at elevated temperature. TWO
is a function of the time and magnitude of loading, classes of recovery conditions may be distinguished
the time allowed for recovery, and the temperature in this case. In the first, which w e here call type A,
history during the stressed and recovery periods. In the temperature is reduced to room temperature
many industrial processes (e.g. heat setting or tex- while the fiber remains under stress, and the stress
turing of textile fibers ) these parameters are varied is then released, such that recovery occurs at room
to achieve the particular recovery behavior desired. temperature. This sequence is analogous to common
The temperature history is of special importance in industrial “heat setting” practice. In the second, type
this, and typical industrial processes subject the fi- B, the stress is released while the fiber remains at
ber to one or more changes in temperature concur- the ( elevated) stretch temperature, such that recov-
rent with changing stress and strain conditions. ery occurs isothermally, and the temperature is later
In general, the fiber temperature, stress, and strain reduced to room temperature. This may be termed
will change in complex ways as functions oE time. “isothermal recovery.”
As a first step in the analysis of such complex proc- To simplify the analysis of data, a standardized
esses, we have examined here only step-fiinction history of stress, strain, and temperature was applied
changes in temperature, i.e., an instantaneous change to the fiber specimens. This is shown in Fig. 1. The
fiber was first heated to an elevated temperature. At
* TO whom correspondence should be addressed. time zero, a tensile strain €0 was applied and main-
610 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

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 &
El
v, Company, Plastics Department. The diameter of both
I fibers was 0.05 cm.
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
v, 5 min. The fibers were then annealed under free
shrinkage conditions, in order to stabilize the fiber
0 100 200 structure and to minimize the influence of thermal
Time, set
shrinkage upon the subsequent tensile recovery ex-
Type A recovery Type 8 recovery
periments. The polyester monofilaments were an-
Fig. 1 . Thermal and mechanical histories applied to the nealed at 210°C for 10 min; the nylon 66 monofila-
fiber specimens in this work. In all cases the fiber was ments at 180°C for 10 min, in a nitrogen atmosphere
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 to prevent oxidation. Shrinkages in length of 26 per-
in type A experiments, t l > 100 see in type B experiments. cent in the polyester and 3.5 percent in the nylon
Recovery is measured 100 sec after removal of the load in 66 fibers occurred as a result of this treatment.
both types of experiment. A heating device was constructed which could be
rapidly removed from the specimen, allowing the
fiber to be quenched to room temperature by the
tained for 100 sec (stress relaxation). At 100 sec,
surrounding air. The apparatus is shown in Fig. 2.
the stress was removed and the fiber was allowed
The monofilament specimens were mounted on an
to contract. At 200 sec, the recovered strain cT was
Instron Universal Tester ( Instron Corporation, Can-
measured. The temperature, initially at an elevated
ton, Massachusetts), using extension grips to which
level T , was reduced to room temperature (23°C)
the specimens were clamped at each end. A heating
suddenly, i.e., in a single instantaneous step, at a
chamber surrounded the specimen and the exten-
time tl. In experiments of type A, t, was less than sion grips. It was constructed from a Lux-Therm
100 sec, i.e., the specimen was cooled to room tem- portable infrared heater model LTH206 ( Hi-Shear
perature while still held at strain c0. In type B ex- Corporation, Torrance, California). The heater was
periments, tl was more than 100 sec, thus isothermal built into a housing which surrounded a copper
recovery was allowed to occur for (tl - 100) sec tube, 2 em in diameter and 20 cm in length. The
prior to cooling to room temperature. copper tube was painted matte black on the outside
Isothermal recovery following applied stress has
been studied by others under various mechanical 4 to load c e l l
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- heoter box
ing elongation at a constant strain rate. In the major- bloc kene d
c o p per tube i n f r a r e d heating
ity of these cases, the stretching temperature was element
not a variable of interest and recovery was measured specimen
at ambient temperatures only. However, Brown ( 7 ) heoter support
conducted experiments at different (constant) tem- clomp
peratures, and found a minimum value of the re-
covery at the glass transition temperature in many g r i p extension ___ __ support rod
different textile fibers. rod
In this paper, we have examined the effect of
stretch temperature upon the recovery following lower p o s i t i o n
o f heater
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 crossheod
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 Fig. 2. Movable heating box used in the experiments.

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER, 1974, Vol. 14, No. 9 61 1
A. C.Lunn, B-L. Lee and I . V.Yannas

to absorb the infrared radiation efficiently. The fiber was removed from the specimen as described above,
specimen was inside the tube. to effect the temperature drop to 23°C.
In use, the infrared radiation heated the copper The initial and extended length of the specimen
tube, which itself heated the air surrounding the were both measured at the elevated temperature
specimen. The specimen was thus heated by air T"C; the length after recovery was measured at
convection. The copper tube was employed to pre- 23°C. It was therefore necessary to make a correc-
vent direct radiative heating of the specimen, which tion for length changes due to thermal expansion
would have made it difficult to determine the ac- effects. Calibration measurements were made using
tual specimen temperature. The heater box could specimens under only the small (20 g ) load used to
be moved up and down manually, and clamped in establish the zero strain position; the length was
either position. In its upper position the heater sur- first measured at T"C, and then at 23°C. Thermal
rounded the specimen. To effect a step jump from an contraction during cooling was calculated from the
elevated temperature to room temperature, the heater change in length. All recovered lengths measured
was rapidly moved to its lower position, thus ex- experimentally were corrected for thermal contrac-
posing the fiber specimen to air at room temperature tion bv these calibration measurements. The polyester
almost instantaneously. monofilament was found to decrease in length on
Temperature stability was provided by propor- cooling, by an amount which increased with initial
tional control feedback with a thermistor probe. temperature level. The greatest shrinltage measured
Specimen temperature was measured with a ther- was 0.45 percent, when cooled from lS0"C to 23°C.
mocouple which touched the specimen. Tempera- The nvlon 66 monofilament, on the other hand, was
ture fluctuations with time at a given point on the found. to increase in length when cooled from tem-
specimen were less than -t- 2°C during the experi- peratures above 80°C to room temperature. The max-
ment. Temperature gradients with position along imum length increase occurred after cooling from
the specimen were greater than this: k 5°C from the highest temperature used, 18O"C, when the fiber
top to bottom of the 10 cm gauge length at 100°C extended by 0.9 percent on cooling to 23°C. The
and +- 8°C at 180°C. oriented nylon 66 examined here thus has a negative
Ideally, the temperature drop from T to 23°C linear coefficient of thermal expansion. This effect in
during the experiment is an instantaneous change, oriented nylon was reported by Leaderman ( 1) .
or step jump. In fact, a finite time was required Errors in strain measurement arose from uncer-
for specimen cooling when the heater was removed. tainty in dial gauge readings of' the crosshead dis-
The cooling time was estimated to be approximately placement, and are low. Uncertainty in strain is
5 sec. This was estimated by data from experiments estimated to be -i: 0.02 percent strain. Slippage of
of type A in which the temperature drop closely the specimen in the grips war, negligible. Strain un-
preceded the release of load from the specimen. If certainty contributes to errors in percent recovery R,
the specimen has not cooled completely prior to re- but temperature gradients in the specimen are more
lease of the load, anomalously high recovery will be significant, and the resultant uncertainty in percent
found. Such anomalous recovery was found in the recovery is estimated to be t- 3 percent R.
polyester when the heater was removed 5 sec before
release of load (tl = 95 sec), but not when 10 sec RESULTS
elapsed (tl = 90 sec). Measurements were there-
fore not obtained here for 90 sec <tl < 100 sec. Polyester and nylon 66 monofilaments were sub-
jected to a standardized mechanical history: they
A fresh specimen was used for each experiment. were maintained at a constant strain level for 100
After 5 min of thermal equilibration at T"C under sec, and then allowed to recover under no load for
no load, the zero strain condition was established by a further 100 sec. Initially, the fiber was at an elevated
moving the crosshead of the tensile tester to induce temperature, but at a time t , it was rapidly air-
a small load (20 g ) across the specimen. Use of this quenched to room temperature. When tl < 100 sec,
small load, rather than a zero load, was found to (i.e. quench time < unloading time) the fiber was
ensure accuracy and repeatability of the strain mea-
thus cooled while still under load (experiments of
surements. The specimen was then rapidly extended type A, Fig. 1 ). When tl > 100 sec, (quench time
at time zero to a strain eo (measured by a dial gauge
contacting the crosshead) and held at fixed length. At
> unloading time) the fiber was able to recover
lor a variable period of time, ( tl - 100) sec, before
100 sec the crosshead was rapidly moved up to
being cooled under no load (experiments of type B,
reduce the stress level to zero, and then moved up Fig. 1 ) ,
a little further so that the specimen buckled slightly,
thus ensuring that the stress remained zero even as The extent of recovery may be conveniently char-
acterized by the percent recovery, R:
the specimen continued to contract with time. At
200 sec the residual strain was determined by once
R = - x 100 percent
€7
again lowering the crosshead to induce a load of 20 g, (1)
€0
and measuring the crosshead position with a dial
gauge. During the experiment, at time tl, the heater where L,, is the applied strain level and E,. is the
612 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER, 1974, Vol. 74, No. 9
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%

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

shows the percent recovery, measured at 200 sec, Nylon 66 shows recovery behavior qualitatively
as a function of the quenching time. At an initial similar to that of polyester in both type A and type
temperature of 80°C ( T si T g ) ,there is only a slight B experiments ( F i g . 8 ) . The type A data, where
discontinuity at tl = 100 sec, but at 150°C ( T > T,) the fiber is cooled to room temperature prior to re-
the recovery increases dramatically as this threshold moval of the load (tl = 90 sec in F i g . 8 ) , show R
from type A to type B experiments is crossed. decreasing with increasing stretching temperature.
The effect of initial strain level c0 on the recovery The type B data ( t l = 110, 200 sec on F i g . 8 ) show
behavior of polyester is shown in Figs. 6 and 7 for a minimum around 60"C, which is in the vicinity of
experiments of type A and type B respectively. The the glass transition temperature for nylon 66 (8).
percent recovery decreases with increasing co. This A decrease in recovery is observed at the highest
contrasts with the prediction of the theory of linear temperatures used in type B experiments, both for
viscoelasticity that R is independent of co for a lin- polyester ( F i g . 4 ) and for nylon 66 ( F i g . 8). Few
ear material ( 9 ) . It is seen from Figs. 5 and 6 that data points were obtained at temperatures above
the nonlinearity of polyester, as evidenced by the 1OO"C, because the fibers ultimately became unable
rate of change of R with increasing strain, is most to sustain the small load which was applied to de-
pronounced at temperatures below about 80°C, the termine the zero strain position: partial melting of
glass transition temperature. Above T , the nonlin- the fiber led to irrecoverable viscous flow. I t is
earity is less marked. therefore concluded that the percent recovery in
type B experiments decreases sharply to zero as the
stretching temperature approaches the melting point,
l o 0 l
approximately 265°C for both nylon 66 and poly-
Pol yes t e r
ester (10). This is indicated by the broken lines in
0
Figs. 4 and 8.
6, = 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-

0 L
0 50 I00 I50 200
bonate ( 11), is considerably more pronounced than
with the semicrystalline polymers used in this work.
The minimum arises from viscoelastic effects. Be-
S t r e t c h Temperoture T, " C low T , most relaxation times of the system are much
Fig. 6. Percent recovery as a function of stretching tempera- longer than the experimental timescale, so that few
ture for polyester monofihment. T y p e A experiment, tl = 90 relaxations occur, and the polymer is stiff and springy.
see, for various initial strain levels.

c
I i
200sec

i
,$ 40 €0 = 2.1 %
3.8 %
0
A 1
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
, , ,
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

see, for various initial strain levels. strain level 1.85 percent.

614 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 leads to a considerable loss of heat-setting efficient!,
times much faster than the experimental timescale, (high recovery), as seen in type B experiments.
so that response to loading or unloading is rapid, These considerations apply at stwtching tempera-
and the polymer behaves in a reversible, highly tures below the melting region. As the stretch tem-
elastic manner. In the vicinity of T,, however, nio- perature approaches Thf,there is an increasing com-
lecular relaxations occur in experimental timescales, ponent of irrecoverable viscous flow, with the result
so that the observed deformation and recovery occur that even if the load is removed prior to cooling
sluggishly. Recovery is slow and highly time-depen- the fiber, recovery is poor.
dent. A good discussion of this phenomenon is given
by Brown ( 7 ) .
The decrease in isothermal recovery at tempera- REFERENCES
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served here in type B experiments, has also been mentous Materials and Other High Polymers,” Textile
Foundation, Washington, D.C. ( 1943).
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shown to arise from irreversible viscous flow at 217 ( 1963) .
temperatures above T,. 3. D. W. Hadley and I. 11. Ward, J. Mcch. Phys. Solids,
The marked difference in recovery behavior be- 13,397 (1965).
-1. C. J. Morgan and I. hl. \Vard, 1. llech. Phys. Solids,
tween experiments in which the fiber is cooled prior 19,165 ( 1971).
to release of load (type A ) and those in which re- 5. S. Turner, P O ~ ~ TEng.
J I . Sci., 6, 306 ( 1966).
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8. N. G. XlcCrum, B. E. Read, and G. \\’illiams, “Anelastic
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achieve good heat setting (poor recovery), the fiber Wiley, London, ( 1967 ) .
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and then must be cooled to near ambient conditions Prepr., 13, 96 (1972).
10. “Modern Plastics Encyclopedia,” Breskin Publications,
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POLYMER ENGINEERING AND SCIENCE, SEPTEMBER, 1974, Vol. 14, No. 9 615