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JOURNAL

OF

MATERIALS

SCIENCE

5 (1970)

1021-1026

Stress-Relaxation Hardening of Nylon 66 Filaments

W.

L.

PHILLIPS,

JR,

W.

O. STATTON*

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,

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.

but not unloaded, before

1.

Introduction

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.

2. Experimental Procedure

In this investigation monofilaments of 65 denier as-spun and 15 denier machine drawn nylon 66 of normal commercial molecular weight were used. All stress-strain tests were performed on an Instron tensile testing machine at 25 ~C, 55 % re- lative humidity and a strain rate of 2.0 in/in/rain unless otherwise noted. The machine drawn samples were also tested after exposure to boiling water for one minute in the slack (free to relax

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

0

E Strain

E1

I

~o

Time

06 /--03

o/

Op

~

OTTIV ,./,-%

65

I

,/

Z 3%strain

I

E1

I

~i

I

~ Strain

Figure f Schematic stress-strain curve in which the speci- men is strained to a stress ~, relaxed for a time, tl, and then restrained.

*Present address : Division of Materials Science and Engineering, University of Utah, Salt Lake City, Utah 84105.

9 1970 Chapman andHallLtd.

1021

O.O

0.1

&:O. 2

o

0.3

0.0

0.3

0.6

As Spun

v 400%

o 500%

 

10

100

 

Time, sec

Drawn + BOS

"~

~

Strain

 

z~

10%

 

20%

 

0 30%

o

40%

 

50%

 

10

, lOO

Time, sec

W.

L.

PHILLIPS,

Jr,

W.

O.

STATTON

 

0.0

As Drawn

 
 

Strain

 

~~

~

~ 1~

-~

0.3

D 15%

 

3g%

 

0.6

 

10

lOO

 

Time, sec

 

O.O

Drawn + BOT

 

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

Strain

 

a 5?.

 

0.3

e

15%

 

0

2O%

o

30%

 

0.6

 

.~

.

,

.I

I.

,

 

" 10

100

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

v;

0.5

O.O

O

'

/

/

~

---

As Spun

65 d 55% RH

Continuous test

Hold 30 sec + reload

'

'

'

-"

200 400

'

600

Strain, percent

3.0 Drawn + BOT

2.0

1,O

O.O

~uous

test

---

Hold 30 sec + reload

10 20

30

Strain, percent

~

~

~,

3.

2.1

1. s

0,0

i

As Drawn

Continuous test Hold 30 sec + reload

I

2O

l

i

40

i

i

60

Strain, percent

 

As Drawn + BOS

3.

1.C

~nuous

test

O.

0

/

i

---

Hold30 sec + reload

i

2O

1

9

40

i

i

60

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

O.

10

C~p, gld

O. 05

As Spun

o

o

NYLON

O. O0

0.0

0.1

0.2

0.3

OR, gld

i

0.4

66

0.50

Op, gld

0.25

O. O0

O. O0

I

Drawn BOT

o

I

0.50

~

o

I

OR, g/d

L

1. O0

FILAMENTS

O. 50

C~p, gld

0.25

Drawn

o/

O. O0

0.00

I

O.

I

50

o R,

gld

I

Drawn BOS

0.50

Op, gld

~o~

0.25 o/

O. O0

O. O0

I

I

O. 50

o R,

I

g/d

I

1. O0

I

1. O0

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

of stress relaxation ~

manent amount

ar

cr6-a5.

=

~1-~,

as the per- %-% and =

~r

ere

~

stress a~

of hardening

as the

transitory increment in

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

Fig. 3 is a plot of typical stress-strain curves of monofilaments in the conditions listed. Also in-

Experiments

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

O. 15

oT, gld

O. 10

0.05

O. O0

0.0

As Spun

0.1

0.2

o R, gld

0.3

0.30 Drawn BOT

oT,g/d

0.20

O.

10

0.00

0.00

//

0.25

0.50

o R, g/d

0.75

0. 30

0T, gld

0.20

O.

10

W.

L.

PHILLIPS,

Drawn

/

/

Jr,

O: O0

 

I

 

O.

O0

0.25

0.50

0. 75

 

o

R, g/d

O.

30

Drawn BOS

0T, g/d

0.20

O. lO

0.00

0.00

'

0.25

o.~

S0

0.50

o R, g/d

0I

0.75

W.

O.

I

1.00

I

1.00

STATTON

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.

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.

At

3.4.

"Coaxing"

Test

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 200~ and relaxed for 30 sec at each 100~ strain interval; sample 3

1024

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.

3.5.

Effect of Temperature

and Humidity

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

2.0

1.0

0.0

HARDENING

OF

NYLON

A

o

As Spun

Continuous test

Relaxation test

66

FILAMENTS

1223

-4

~3

c,O

~2

5

A

o

As Drawn

Continuous test

Relaxation test

L.L

200

400

600

0

Strain,

percent

20

Strain,

40

percent

As Drawn

+

BOT

 

A

Continuous test

 

~4

o

Relaxation test

 

-

4

~3

~3

I.L.

i,

 

I

I

I

I

l

0

0

20

40

Strain,

percent

As Drawn

+

BOS

A

Continuous test

o

Relaxation test

2O

40

60

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

Sample

Strain

Relaxation

Time

cr~

ep

c~r

Strain to

Tenacity

 

stress

sec

gm/dxlO-2

gm/dxlO -~

gm/dxlO-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.

PHILLIPS,

Jr,

W.

O.

STATTON

0.5

0.4

C) Op

~

0.2

0.1

0.0

I

0.2

As Drawn

oR = 0. Sgld

2,0

Strain Rate, in./ in.

 

0.6

-

C0ntinuoustest

 

---

Hold 30 see + reload

i

0.4!

,,',

0.2

 

i"

",,,

';-,

:

20.0

O.O

I

I

j/

 

100

200

Strain, percent

Time

As Spun

/

i"" /

/

25~

Op

~-

~ 0.22,

aT

~-

= 0.024

!/

Op

o+

,

50~

~-

= 0.25,

~-

= 0.12"

1

cr

oT

',

~ o.25, ?

= 0.5o

/

t

200

I

300

I

400

Figure 7 The permanent and temporary hardening as a

function

of strain ratefor as-drawn yarns which have been

relaxed0.5 g/d,

Figure

8

Effect of temperature on the

stress-strain-

relaxation behaviourof as-spun fibres.

perature. A typical series of curves is shown in

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.

fig. 8. In samples tested at 25~

and 72 ~

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,

Other

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.

Metals

and

Ceramics

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. Summary

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.)

2.

(1960).

w.

G.

HAMMERLE

and D. ~. MONTGOMERY,

Res. jr. 23 (1953)595.

Text.

Received 2 July and accepted 14 September 1970

1026