JOURNAL OF MATERIALS SCIENCE 5 (1970) 1021-1026

Stress-Relaxation Hardening of Nylon

66 Filaments
W. L. P H I L L I P S , JR, W. O. S T A T T O N *
Engineering Materials Laboratory, E. I. du Pont de Nemours & Co., Inc, Wilmington,
Delaware, USA

It was observed that an additional increment in stress was necessary to continue

deformation in nylon 66 filaments, which had been relaxed, but not unloaded, before
fracture. This stress increment consisted of a small permanent increase in stress, in
addition to a larger temporary increase in stress to yield. Both the temporary and
permanent increments increased as the strain, strain rate, temperature and humidity
increased. Similar effects were observed in other polymers, but not in metals or ceramics.

1. Introduction during boil-off) and taut (held at constant strain

Stress-relaxation studies on polymers have been
carried out by a number of investigators. An
extensive compilation of the available data on
polymers has been made by Tobolsky [1]. In
particular the stress-relaxation behaviour of
nylon 66 has been studied by Hammerle and
Montgomery [2]. It has been shown that the
relaxation is dependent on previous strain,
temperature, humidity, relative viscosity and
strain rate.
In general, the previous work on polymer
systems has been concerned only with the stress-
relaxation behaviour. The present paper de-
scribes an unusual hardening behaviour in poly-
mers. It was observed that an additional incre-
ment in stress was necessary to continue
deformation on reloading filaments which have
been stress-relaxed with time under load. The
effects of strain, strain rate, time of stress-
relaxation, humidity, and temperature on this
hardening are described.
during boil-off) conditions.
3. Experimental Results
3.1. Definition of Terms
Fig. 1 illustrates a typical Instron chart of a
sample which has been strained to a stress, ~rl,
and a strain, q , held at constant strain for a
time varying from t o to t~ during which time
stress relaxation occurs, and then restrained. In
all cases an increment in stress was necessary to
continue deformation after the relaxation under
load. The dashed line in fig. 1 is the cr-E for a
continuous test. We will define era as the amount
06 / - - 0 3
0 ~ o / Op
OTTIV ,./,-%
65 I ,/

2. Experimental Procedure
In this investigation monofilaments of 65 denier Z 3% strain
as-spun and 15 denier machine drawn nylon 66 I I
of normal commercial molecular weight were E1 E1
used. All stress-strain tests were performed on an I I __

Instron tensile testing machine at 25 ~C, 55 % re- ~o ~i

E Strain ~ Strain
lative humidity and a strain rate of 2.0 in/in/rain Time
unless otherwise noted. The machine drawn Figure f Schematic stress-strain curve in which the speci-
samples were also tested after exposure to boiling men is strained to a stress ~ , relaxed for a time, tl, and
water for one minute in the slack (free to relax then restrained.

*Present address : Division of Materials Science and Engineering, University of Utah, Salt Lake City, Utah 84105.
9 1970 Chapman andHallLtd. 1021
 W. L. P H I L L I P S , J r , W. O. S T A T T O N

O.O As Spun 0.0 As Drawn

Strain
0.1 ~~___~ ~ 1~
-~ 0.3 D 15%
&:O. 2
3g%
0.3 0.6
v 400%
o 500%

10 100 10 lOO
Time, sec Time, sec

0.0 Drawn + BOS O.O Drawn + BOT

"~ ~ Strain -'~----~---"-'~"~ Strain

z~ 10% a 5?.
0.3 20% 0.3 e 15%
0 30% 0 2O%
o o 40% o 30%
50%
0.6 0.6

.~ . , .I . . . . I. ,

10 , lOO " 10 100

Time, sec Time, sec

Figure 2 The relaxation stress, ~R, for samples given the indicated pretreatment as a function of time at a variety of
stresses.

].5
~I. 0
/ As Spun ~
3.

As Drawn
v; / 65 d 55% RH ~ 2.1
Continuous test
0.5 ~ Continuous test ~, Hold 30 sec + reload
--- Hold 30 sec + reload 1. s

O.O ' ' ' ' -" ' 0,0 i I l i i i

O 200 400 600 2O 40 60

Strain, percent Strain, percent

3.0 Drawn + BOT As Drawn + BOS

3.

2.0

~ u o u s test
1,O --- Hold 30 sec + reload 1.C ~ n u o u s test
/ --- Hold 30 sec + reload
O.O O. 0 i i 1 9 i i

10 20 30 2O 40 60
Strain, percent Strain, percent

Figure 3 Typical stress-strain curves for samples which have been continuously strained to fracture and for samples
which have been strained-relaxed and restrained to fracture,
1022
STRESS RELAXATION HARDENING OF NYLON 66 F I L A M E N T S

As Spun Drawn

O. 10 O. 50

C~p, gld o o
C~p, gld

0.25
o/
O. 05

O. O0 i O. O0 I I I I

0.0 0.1 0.2 0.3 0.4 0.00 O.50 1. O0

OR, gld o R, gld

Drawn BOT Drawn BOS

0.50 o ~ 0.50

Op, gld Op, gld

~o ~

0.25

O. O0 I I I L
0.25

O. O0
o/ I I I I

O. O0 0.50 1. O0 O. O0 O. 50 1. O0

OR, g/d o R, g/d

Figure 4 The permanent hardening as a function of the relaxation stress for samples with the pretreatments indicated,

of stress relaxation ~ = ~1-~, ~r as the per-
manent amount of hardening ere ~ %-% and
a r as the transitory increment in stress a~ =
cr6-a5.
3.2. Stress-Relaxation
Fig. 2 summarises err versus log time plots for
as-spun nylon 66, machine drawn nylon 66, and
machine drawn nylon 66 in the boiled-off slack
(BOS) and boiled-off taut (BOT) conditions. In
all cases over a limited region a linear relation-
ship is observed. The slope of this linear region
increases as the strain increases. It required in
the order of minutes to achieve erR max.
3.3. Reloading Experiments
Fig. 3 is a plot of typical stress-strain curves of
monofilaments in the conditions listed. Also in-
cluded in the figure are stress-strain curves of
samples which have been held at the strains
listed for 30 sec and then reloaded. In all cases a
permanent and a transitory hardening is required
to continue deformation.
The permanent hardening measured after 3 %
strain (a3-a4) is plotted as a function of the
relaxation stress in fig. 4. In all cases ap is
linearly proportional to aR. It was also found
that aT was linearly dependent on eR, fig. 5. In
this case, however, a stress relaxation of 0.2 and
0.5 g/d was necessary to produce a temporary
increment in the as-spun and drawn samples,
respectively.
Although transient and permanent hardening
were observed after relaxation, the final break
tenacity was not significantly different in
samples taken directly to fracture, or samples
1023
 W. L. P H I L L I P S , J r , W. O. S T A T T O N

O. 15
oT, gld

O. 10
As Spun 0. 30
0 T, gld

0.20
Drawn

/
0.05

O.O0
0.0 0.1 0.2 0.3
O. 10

O:O0
O.O0 0.25
I
/
0.50 0. 75 1.00
I

o R, gld o R, g/d

Drawn BOT Drawn BOS

0.30 O. 30
oT,g/d
0.20

O. 10

0.00
// 0 T, g/d
0.20

O. lO

0.00 '
o

S0 0 I
. ~

I
0.00 0.25 0.50 0.75 0.00 0.25 0.50 0.75 1.00
o R, g/d o R, g/d
Figure 5 The temporary hardening as a function of the relaxation stress for samples with the pretreatments indicate d.

given intermediate relaxations before fracture,
fig. 6.
At a constant ~g both ep and crT increased
linearly, as a function of the log strain rate for
as-drawn samples, fig. 7. A similar relationship
was observed in the BOS and BOT samples.
was, etc. The ~ , el~, and cr~ increased as the
number of holds increased. However, erR, err, ~ ,
the strain to fracture, and the tenacity, were not
affected by the number of previous holds for a
given strain. These conclusions were also valid
for the as-drawn, BOT and BOS nylon.

3.4. " C o a x i n g " Test 3.5. Effect of T e m p e r a t u r e and Humidity

In the work described above the samples were
relaxed once and then reloaded to fracture. A
series of tests was carried out in which samples
were relaxed several times before fracture. A
typical series of "coaxing" tests is summarised
in table I for an undrawn fibre. Sample 1 was
relaxed for 30 sec at each 100 ~ strain interval;
sample 2 was strained 2 0 0 ~ and relaxed for
30 sec at each 100~ strain interval; sample 3
1024
Samples of as-spun and as-drawn nylon were
tested at 50 and 90~ at 55 ~ relative humidity.
As the test temperature increased, the modulus
and the yield strength showed the normal de-
crease. For a given strain, an increase in tem-
perature increased the quantity eg/~ (where cr is
the stress at which relaxation began). Although
the quantity ~P/cr was insensitive to temperature,
the quantity efT/o- increased strongly with tern-
STRESS RELAXATION HARDENING OF NYLON 66 FILAMENTS

As Spun As Drawn

A Continuous test 5 A Continuous test

o Relaxation test 1223
o Relaxation test
2.0 -4

~3
c,O

1.0 ~2

L.L

0.0
200 400 600 0 20 40

Strain, percent Strain, percent

As Drawn + BOT As Drawn + BOS

A Continuous test A Continuous test
~4 o Relaxation test - 4 o Relaxation test
~3 ~3

I.L.
i,
I I I I l 0

0 20 40 2O 40 60

Strain, percent Strain, percent

Figure 6 The fracture stress as a function of strain for samples with the pretreatments indicated.

TABLE I As-spun 66 nylon, 65d 55% RH, ~ = 2.0 injin/min

Sam p le Strain Relaxation Time cr~ ep c~r Strain to Te na c i t y

stress sec g m / d x l O -2 g m / d x l O -~ g m / d x l O -2 fracture gm
grams
1 100 19 30 8.5 3.0 0 -- --
200 31 30 11 3.5 0.2 -- --
300 44 30 14 4.7 0.7 600 89
400 65 30 15 5.5 1.3 -- --
500 80 30 16 6.0 2.0 -- --

2 200 29 30 12 3.2 0 -- --
300 42 30 14.5 4.2 0.7 -- --
400 59 30 15 5.5 1.2 580 86
500 78 30 16 6.5 1.8 -- --

3 300 42 30 14 4.5 1.0 -- --

400 58 30 15 6.0 1.5 670 91
500 76 30 16 6.4 2.0 -- --

4 400 57 30 15 5.5 1.0 570 85

500 74 30 16.5 6.0 1.8 -- --

5 500 73 30 16 6.0 2.0 550 85

1025
 W . L. P H I L L I P S , J r , W . O. S T A T T O N

As Spun
As Drawn
0.5 o R = 0. S g l d 0.6 - Op aT
C0ntinuoustest / / 25~ ~- ~ 0.22, ~- = 0.024
C) Op --- Hold 30 see + reload i""

/
~
0.4

!/ Op o+
i 0.4! ,,', , 50~ ~- = 0.25, ~- = 0.12"

0.2

0.2
1 cr oT
0.1 i" ............ ",,, ', ~ o.25, ? = 0.5o

';-,............. : /
0.0 I
0.2 2,0 20.0 O.O I I j/ t I I
Strain Rate, in./ in. 100 200 200 300 400
Strain, percent
Time
Figure 7 The permanent and temporary hardening as a
function of strain ratefor as-drawn yarns which have been Figure 8 Effect of temperature on the stress-strain-
relaxed 0.5 g/d, relaxation behaviourof as-spun fibres.

perature. A typical series of curves is shown in

fig. 8. In samples tested at 25~ and 72 ~ rela-
tive humidity, the stress to achieve a given strain
decreased, but (ra, (rT and (re increased in com-
parison to the tests at 55 ~ relative humidity.
3.6. Effect of Sample Size
Samples of nylon 66 were cast into I in. diameter
rods, machined into ~ in. diameter tensile
samples and then tested in tension. The same
type of behaviour was observed in bulk spheru-
litic nylon as in fibres, i.e. on holding at strain
the stress decreased, on reloading a temporary
and permanent increase in stress was necessary
to continue deformation. (rT, however, required
a longer strain interval at the same strain to
decay out.
3.7, O t h e r Fibres
To determine if the increment in stress after
relaxation without unloading was unique to
nylon 66, drawn fibres of other polyamides and
polyesters were tested. A measurable crT and (re
was observed, but insufficient results were
obtained for detailed discussion here.
3.8. M e t a l s a n d C e r a m i c s
To determine if the temporary and permanent
hardening were unique to polymer systems, wire
samples of zinc, aluminium, brass, 316 stainless
steel, Hastelloy C, alumina, and zirconia were
relaxed after straining and then restrained
without unloading. In all cases (rT or (r], were not
observed.
4. S u m m a r y
The significant features of foregoing results are.
(i) In room temperature tests on nylon 66 mono-
filaments which are stress-relaxed and reloaded,
both a transitory and a permanent increment in
stress was required to continue deformation.
This observation was made on as-spun, drawn,
and drawn samples after boiling off slack or taut
in water. In all cases aT and (rp were linearly
dependent on an. A relaxation of 0.2 and 0.5 g/d
was necessary to produce aT in the as-spun and
drawn samples, respectively.
(ii) Relaxation before reloading had no sig-
nificant effect on the tenacity.
(iii) a~/~ and (rR/~ increased as the humidity and
the test temperature increased. The temporary
and permanent hardening were not affected by
the previous mechanical history, i.e. number of
holds.
(iv) (rT and (re are observed in rods and other
polymeric fibres, but not in metal or ceramic
wires. This phenomenon is apparently limited to
polymeric systems.
References
1. A. V. TOBOLSKY, "Properties and Structure of
Polymers" (New York, John Wiley & Sons, Inc.)
(1960).
2. w . G . H A M M E R L E and D. ~. M O N T G O M E R Y , Text.
Res. jr. 23 (1953) 595.
Received 2 July and accepted 14 September 1970

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