You are on page 1of 6

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

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

o

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- cluded in the figure are stress-strain curves of
manent amount of hardening ere ~ %-% and samples which have been held at the strains
a r as the transitory increment in stress a~ = listed for 30 sec and then reloaded. In all cases a
cr6-a5. permanent and a transitory hardening is required
to continue deformation.
3.2. Stress-Relaxation The permanent hardening measured after 3 %
Fig. 2 summarises err versus log time plots for strain (a3-a4) is plotted as a function of the
as-spun nylon 66, machine drawn nylon 66, and relaxation stress in fig. 4. In all cases ap is
machine drawn nylon 66 in the boiled-off slack linearly proportional to aR. It was also found
(BOS) and boiled-off taut (BOT) conditions. In that aT was linearly dependent on eR, fig. 5. In
all cases over a limited region a linear relation- this case, however, a stress relaxation of 0.2 and
ship is observed. The slope of this linear region 0.5 g/d was necessary to produce a temporary
increases as the strain increases. It required in increment in the as-spun and drawn samples,
the order of minutes to achieve erR max. respectively.
Although transient and permanent hardening
3.3. Reloading Experiments were observed after relaxation, the final break
Fig. 3 is a plot of typical stress-strain curves of tenacity was not significantly different in
monofilaments in the conditions listed. Also 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, was, etc. The ~ , el~, and cr~ increased as the
fig. 6. number of holds increased. However, erR, err, ~ ,
At a constant ~g both ep and crT increased the strain to fracture, and the tenacity, were not
linearly, as a function of the log strain rate for affected by the number of previous holds for a
as-drawn samples, fig. 7. A similar relationship given strain. These conclusions were also valid
was observed in the BOS and BOT samples. 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 Samples of as-spun and as-drawn nylon were
relaxed once and then reloaded to fracture. A tested at 50 and 90~ at 55 ~ relative humidity.
series of tests was carried out in which samples As the test temperature increased, the modulus
were relaxed several times before fracture. A and the yield strength showed the normal de-
typical series of "coaxing" tests is summarised crease. For a given strain, an increase in tem-
in table I for an undrawn fibre. Sample 1 was perature increased the quantity eg/~ (where cr is
relaxed for 30 sec at each 100 ~ strain interval; the stress at which relaxation began). Although
sample 2 was strained 2 0 0 ~ and relaxed for the quantity ~P/cr was insensitive to temperature,
30 sec at each 100~ strain interval; sample 3 the quantity efT/o- increased strongly with tern-
1024
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- 4. S u m m a r y
tive humidity, the stress to achieve a given strain The significant features of foregoing results are.
decreased, but (ra, (rT and (re increased in com- (i) In room temperature tests on nylon 66 mono-
parison to the tests at 55 ~ relative humidity. filaments which are stress-relaxed and reloaded,
both a transitory and a permanent increment in
3.6. Effect of Sample Size stress was required to continue deformation.
Samples of nylon 66 were cast into I in. diameter This observation was made on as-spun, drawn,
rods, machined into ~ in. diameter tensile and drawn samples after boiling off slack or taut
samples and then tested in tension. The same in water. In all cases aT and (rp were linearly
type of behaviour was observed in bulk spheru- dependent on an. A relaxation of 0.2 and 0.5 g/d
litic nylon as in fibres, i.e. on holding at strain was necessary to produce aT in the as-spun and
the stress decreased, on reloading a temporary drawn samples, respectively.
and permanent increase in stress was necessary (ii) Relaxation before reloading had no sig-
to continue deformation. (rT, however, required nificant effect on the tenacity.
a longer strain interval at the same strain to (iii) a~/~ and (rR/~ increased as the humidity and
decay out. the test temperature increased. The temporary
and permanent hardening were not affected by
3.7, O t h e r Fibres the previous mechanical history, i.e. number of
To determine if the increment in stress after holds.
relaxation without unloading was unique to (iv) (rT and (re are observed in rods and other
nylon 66, drawn fibres of other polyamides and polymeric fibres, but not in metal or ceramic
polyesters were tested. A measurable crT and (re wires. This phenomenon is apparently limited to
was observed, but insufficient results were polymeric systems.
obtained for detailed discussion here.
References
3.8. M e t a l s a n d C e r a m i c s 1. A. V. TOBOLSKY, "Properties and Structure of
To determine if the temporary and permanent Polymers" (New York, John Wiley & Sons, Inc.)
hardening were unique to polymer systems, wire (1960).
samples of zinc, aluminium, brass, 316 stainless 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.
steel, Hastelloy C, alumina, and zirconia were
relaxed after straining and then restrained
Received 2 July and accepted 14 September 1970
without unloading. In all cases (rT or (r], were not
observed.

1026