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JOURNAL OF MATERIALS SCIENCE 15 ( 1 9 8 0 ) 3057-3065

Mechanical properties of nylon 6
subjected to photodegradation
Y. W. M A I , D. R. H E A D , B. C O T T E R E L L , B. W. R O B E R T S
Department of Mechanical Engineering, University of Sydney, NSW 2006, Australia

The degradation of mechanical properties in nylon 6 films due to both oxidative and
non-oxidative photodegradation is studied. It is shown that in a non-oxygen environment
the rate of degradation is enhanced with rising temperature due to increases in quantum
yield. Experimental results obtained on specimens exposed to natural weathering are
found to be difficult to relate to those obtained by accelerated ageing, tt is proposed and
proven that the specific energy absorption in a tensile test (Wp) is an effective parameter
for characterizing photodegradation in nylon.

1. Introduction on the mechanical properties of nylon 6 which has
Nylon, like many other polymers, suffers consider- been exposed to ultra-violet light ageing in air and
able loss of mechanical properties due to photo- in nitrogen respectively. To provide a basis of
degradation, i.e. the absorption of light in the comparison and an indication of the equivalence
visible and near-ultra-violet range. Although photo- of artificial ageing to natural ageing experimental
degradation can occur in the presence or absence results are also presented for nylon in the as-
of an oxygen environment, previous investigations received condition and exposed to outdoor
[ 1 - 3 ] have been mainly concerned with oxidative weathering.
degradation. There are fewer studies on the Another purpose of the present study is to
deleterious effects of non-oxidative degradation in identify from these initial experimental results a
nylon. Because of our particular interest in nylon more fundamental measure of strength than the
as a parachute material, a research programme has commonly used parameters of elastic modulus (E)
been planned to determine the degradation of and ultimate tensile strength (cru), which would be
mechanical properties when nylon has been exposed sensitive to structural changes induced by photo-
to ultra-violet light both in air and in nitrogen. The degradation. In a recent study on composite
degradation of nylon webbings, ropes and other propellants subjected to accelerated thermal
structures is also of importance. Since temperature ageing Marom et al. [6] suggested that the specific
affects photodegradation in other polymers [4] tearing energy (To) is independent of both test
this variable is included for study in the present configurations and specimen geometries and thus
research. Indeed George and Browne [5] have would be a suitable candidate. The present authors
recently shown that thermal ageing at 80 + 2 ~ C cannot fully agree with the suggestion that Te
in an oven has caused considerable strength loss in is specimen geometry independent although
nylon 6,6 by an oxidation process which results Anderton and Treloar [7] have shown that for
in main chain scissions. However the interaction polyethylene Tc obtained in a "trouser-leg"
effects of heat ageing and light absorption, with or specimen is apparently the same as the cleavage
without oxygen, have not been firmly established specific fracture energy (Ge) determined from a
and further work is needed. The present paper double-cantilever-beam testpiece.* There is a clear
reports some preliminary experimental findings difference between the modes of fracture in a
*There are in fact some doubts as to whether linear elastic fracture mechanics concepts can be applied to some of the
tougher polyethylenes studied in [7] using double-cantilever-beam specimens with beam depths of only 14mm.
Yielding in the beams could have occurred before cracking commenced.

0022-2461/80/123057-09502.90/0 9 1980 Chapman and Hall Ltd. 3057
"trouser-leg" test, which is in predominantly a But for non-oxidative photodegradation, the
sheafing mode, and that in a cleavage test, which irradiation of the nylon sheets was carried out in
is essentially in the opening mode. In ductile frac- an airtight sealed chamber filled with nitrogen gas
ture, it is the deformation and fracture of the at 45 and 65 ~ C respectively. The temperature was
process zone that determines the specific fracture varied by means ofa smaUradiator and fan. Nylon
work [8, 9]. Our recent experiments on ductile sheets were also exposed to natural weathering
fracture of nylon and polyethylene show that, in mounted on frames at 45 ~ to the horizontal and
deep-edge-notched tension testpieces, after the placed on the rooftop of the Mechanical Engin-
process zone is fully developed across the ligament, eering Building facing north so as to receive the
it is cold-drawn as cracking proceeds. However, maximum possible amount of sunlight (Standards
cold-drawing has not been observed to any signifi- ASTM D1435, As CK24.1).
cant extent in the "trouser-leg" tear tests. The Random samples were retrieved from the nylon
thickness reductions on the section near the sheets at regular intervals during the various ageing
fractured surfaces confirm that tearing and cleavage processes and were identified and then placed in
are due to different mechanisms. Thus any agree- separate black plastic bags before they were tested.
ment between Ge and Te must be treated as simply Both tensile and "trouserqeg" tear experiments
fortuitous. In the present work, nevertheless, the were performed on these samples according to the
suitability of Te for characterizing the photo- standards ASTM882-75b and ASTM1938-67
degradation of nylon is assessed. In addition an respectively in an Instron machine. The cross-head
alternative fracture energy absorption parameter, speed for the tensile tests was 10mmmin -1 and
Wp, defined as the area under the tensile stress- that for the tear experiments was 20mmmin -1.
strain curve is studied. This is shown to be a more From the tensile tests the Young's modulus (E),
sensitive property to photodegradation in nylon elongation-to-fracture (ee) and ultimate tensile
than Te which is suggested by Marom et al. [6]. strength (Ou) are obtained. From the "trouser-
If the fracture process zone width (d) can be leg" tear tests, typical records of which are shown
identified as approximately equal to the film in Fig. 1, the specific tear resistance at crack
thickness (B) Hahn etal. [10] have shown that initiation (Ti) and at maximum load (Tra) are
given by
G e = Wpd ~ WpB. (1)
r~ = 2 e i / B (2)
This thus provides an indirect method of measuring and
Ge which is a fundamental material property. T~ = 2P~/8, (3)

2. E x p e r i m e n t a l w o r k where Pi and Pm are the initiation and maximum
The material used in this work was nylon 6 supplied loads respectively. In addition the average specific
by Cadillac Hastics Pty. Ltd. (Australia) in the tear resistance (Te) defined as the ratio of the total
form of 1 mm thick films. The nylon 6 had no u.v. work required to completely tear the specimen
stabilizers or any other additives. For photodegra- (i.e. the work area under the load-displacement
dation experiments rectangular sheets measuring diagram as shown in Fig~ la to c) and the newly
500 mm x 1000 mm were erected in racks exposed created fracture surfaces is obtained.
to tungsten mercury sunlamps (Philips model MLU
300W) at a distance of 500ram. The relative 3. Results and discussion
spectral energy distribution, at 500mm is given 3.1. Tensile properties and
in Table I. For oxidative photodegradation the photodegradation
irradiation experiments were conducted in the The change in the tensile properties, E, Ou and ef
open atmosphere Of the laboratory at 25 +- 2 ~ C. with sunlamp exposure time up to 1700 h in air
and in nitrogen are shown in Figs 2 to 4. It was
TABLE I U.v. radiation at 500ram from the lamp not possible to retrieve samples from the nylon
Wave Radiation sheets exposed at 65 ~ C in nitrogen exceeding
length (nm) (mW cm -2) 400 h because upon cutting the sheet it shattered
UV-A 400-315 1.69 indicating that significant embrittlement had
UV-B 315-280 0.88 occurred. In the non-oxygen environment light-
UV-C < 280 0.01 induced degradation is not an oxidative but rather

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70 70

60 ~ light offected surface [oyer 60

5O -' ~ ~ // . . . . ~-~ 50

z
40

J
L~
30
__ AS-RECEIVED __ AS - RECEIVED

(9 - -- 241 h
Z 20 -- 333 h
E: 2O
<
/ ~ INIrlATION
10
/ ' ~ INITIATION,Pi

[ I f
10

/ J J I
20 40 60 0 20 40 60

(a) GRIP SEPARATION, 6 (ram) (b) GRIP SEPARATION, 8 (ram)

70 Figure 1 Typical load-displacement records for tear tests
on nylon 6 subjected to sunlamp exposure ( a ) i n air at
25 ~ C, (b) nitrogen at 65 ~ C and (c) natural weathering.
60
,%
A ~ #./"\
with ageing time, a phenomenon compatible with

/ -)
5O
If-- -~-/ - ~ \
polymer embrittlement. As the temperature was
Q. 4O raised to 65~ the photodegradation effect
became more obvious. Young's modulus (E)
o 3e intitially increased to twice its original value at
// ____ AS -RECEIVED
about 3 0 0 h exposure time and then decreased;
Ou and e~ both decreased significantly with ageing
20
< period when compared with the corresponding
results at 45 ~ C. Since temperature does not affect
10
'1- IINITIATION, Pi I I light absorption rate [4], but light4nduced degra-
dation is worse at higher temperatures, it seems
0 20 40 60 that the quantum yield for chain scission must
have increased with temperature. This suggestion
(c) GRIP SEPARATIONj 6 (mini
is certainly not new as Guillet [11] has shown
previously that in the photolysis of MMA-MVK
a photolytic effect. It is possible for nylon 6 to (3%) co-polymer and indeed in some other polymers
undergo structural changes by cross4inking or by the rate of degradation by chain scissioning
main chain scissioning by photon absorption, the increases with temperature.
effectiveness of which can be measured by the In an oxygen environment the ultra-violet light
quantum yield. From the results shown in these acts as an initiator to an oxidation process that
figures it is clear that at 45 ~ C in nitrogen both the occurs in nylon as a free-radical chain reaction
ultimate tensile strength and Young's modulus [2, 5]. Oxidation leads to chain scissioning which
increase with exposure time up to 1000 h due to in turn lowers the molecular weight and reduces
a plausible light4nduced cross4inking mechanism. the strength of the polymer. If ultra-violet radiation
However there is a tendency for these mechanical is excluded, the degradation process is slowed
properties to decrease for exposure periods over down [3 ]. As shown in Figs 2 and 3, the Young's
lO00h as the main chain scission mechanism modulus remains essentially constant and there
assisted by thermal effects becomes predominant. is only a slight trend for ou to decrease with
The elongation-to-fracture decreases continuously irradiation time in the laboratory. However the

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Figure 2 Variation of elastic modulus with sun-
O SUNLAMP EXPOSURE IN AIR AT 25~ lamp exposure time, Bars indicate one standard
O SUNLAMP EXPOSURE IN NITROGENAl" 45~ deviation, sample size of 8.
SUNLAMP EXPOSURE IN NITROGENAT 65~

o 3
C
u4

=,
g

-r

I I I I I I [ I
200 400 600 800 1000 1200 1400 1600 1800
EXPOSURE TIME, t (h)

60

50
A

[M
~r
~D/J3

Z
w
r

~n 30

z
w O SUNLAMP EXPOSURE IN AIR AT 25~
F-

W
O SUNLAMP EXPOSURE IN NITROGEN AT 45~

SUNLAMP EXPOSURE IN NITROGEN AT 85~

0 AS- RECEIVED
10

I I I I I I I I
Figure 3 Variation of ultimate tensile strength
200 400 600 800 1000 1200 1400 1600 1800
with sunlamp exposure time. Bars indicate one
standard deviation and sample size of 8. EXPOSURE TIME~, t (h)

3060
Figure 4 Variation of elongation to break
AIR AT 2S~ with sunlamp exposure time. Bars indicate
180
NITROGEN AT 45~ one standard deviation and sample size of 8.
NITROGEN AT 65~
160

140

120

to~ 100

I..d
n-"
,-. 8C
s
z
2 ~
0
Z

-~______

b , 1 I I I
200 400 600 800 1000 1200 1400 1600 1800

TIME OF EXPOSURE ~t (h)

160

ELONGATION

--2o_
~ 70 140

120

100
z

Z
80 2
bJ

60

20 40

YOUNG S MOOULUS

10 - 20
Figure 5 Variation of elastic modulus,
ultimate tensile strength and elon-
gation to break with natural ageing f I / I I, 0
time. Bars indicate one standard 50 100 150 200 250 300
deviation and sample size of 8. EXPOSURE TIME ~,t (DAYS)

3061
"160: Figure 6 Variation of specific tearing energy at
initiation (Ti), maximum load (Tin) and work of
fracture (Te) with sunlamp exposure time. Bars
140 indicate one standard deviation and sample size
of 5.
E
"~ 120

~"
n,-
8o Ti Tin Tc CONDITION
I,m
z
W
9 O AS- RECEIVED
_ ~ 9 O 25~ U V EXPOSURE IN AIR
7
Ill 9 [] 45~ U V EXPOSURE IN NITROGEN
9 Z~ 65~ UV EXPOSURE IN NITROGEN
N
40
M
h

W
~ 20

I I I 1 I I I I
200 400 600 800 1000 1200 1400 1600 1800

TIME OF EXPOSURE,t (hi

elongation-to-break (el), Fig. 4, has provided some oxidation induced chain scission effect will be
definite evidence of degradation in the material. enhanced.
We have' not yet completed experiments at other Fig. 5 shows the results for nylon samples
elevated temperatures but it is expected that the subjected to natural weathering during the period

140

A 120

IO0
ku

~- 80

w
z
w 60
0
z
W

~ 40

n
Ti

20

Figure 7 Variation of specific tearing
I I I I I
energies, Ti, Tm and Te, with natural ageing 50 100 150 200 250 300
time. Bars indicate one standard deviation
EXPOSURE TIME ~s (DAYS)
and sample size of 5.

3062-
April to December. Clearly all the tensile proper- does not penetrate deeplY past the surface it
ties, E, au and el, decrease with exposure period as follows that any structural changes and thus
a direct consequence of chain scission. degradation effects will be mainly confined to the
No records were kept of temperature or first few /lm. The inside thickness material may
humidity for the naturally weathered samples and be considered as relatively undegraded. In the
thus only very general comparisons can be made. "trouser-leg" tests, the tearing work as shown in
For example, sunlamp exposure in the open the inset of Fig. la is the sum of those required
atmosphere of the laboratory at 25~ for 1730h to tear the light affected surface layers and the
gives E and au values equivalent to approximately middle undegraded layer. If there is cross-linking
100 days natural ageing but ef values equivalent in the surface layers the tearing force is increased
to 170 to 200 days natural weathering. Another and if chain scissioning predominates the force is
complicated effect is the differential moisture reduced. However since the light affected layers
contents in the samples aged in the laboratory are so thin compared with the undegraded middle
under controlled conditions and those naturally layer the tearing energies, Ti, Tm and Te, are
aged where moisture absorption from precipitation therefore not expected, as shown in this work, to
is uncontrolled. In the light of these difficulties, vary considerably with light ageing or natural
it seems that the non-destructive technique weathering period. This conclusion is confirmed
of phosphorescence spectroscopy developed by upon noting that all fractured surfaces show
George and Browne [5] provides the best solution similar thickness reductions after the tear tests are
to the problem of predicting strength loss from completed. It seems therefore that the suggestion
accelerated ageing test results. It would however by Marom et al. [6] to use Tr or Tm as a material
be useful to confirm whether the technique gives parameter to characterize the extent of photo-
the correct predictions for other mechanical degradation in nylon 6, is inapplicable. In their
properties such as e~, E and Te. work on propellant composites the ageing effect
is throughout the specimen thickness so that
3.2. Specific tear energy and both Tc and Tm are useful material parameters.
photodegradation As shown in Fig. la to c there are two forms
The specific tearing energies, Ti, Tin and Te, for of tearing force curves, one is "smooth" and the
the nylon samples subjected to photodegradation other is "stick-slip". In the "smooth" case the
of various means are given in Figs 6 and 7 respec- cracking is continuous and occurs for nylons in
tively. These results seem very high but they are of the as-received condition and for short periods of
the same order of magnitude as those reported for light exposure. In the "stick-slip" case cracking
polyethylenes [7] and polypropylenes [ 12]. Within proceeds in a series of unstable jumps presumably
experimental limits Ti is independent of ageing caused by the intermittent fracture of the photo-
period, whether exposed to sunlamp in air or in degraded surface layers. The magnitude of "stick-
nitrogen. Under laboratory conditions, both Tm slip" appears to increase with ageing period.
and Te are rather independent of sunlamp exposure
perio d . However in the nitrogen environment, 3.3. Specificenergy absorption as an
these quantities show an initial increase with index of photodegradation
ageing time to maximum followed by a decrease In the previous section it is shown that Te and
for longer periods (see Fig. 6) in agreement with Tm are not sensitive to photodegradation in
the variation of Young's modulus shown in Fig. 2. nylon 6 although they are physically much more
When subjected to natural weathering, Fig. 7, Ti appealing parameters than E, ou and e~, Inspection
shows a 25% reduction after 250 days when of Figs 2 to 4 suggests that e~ is the most effective
compared with the as-received material, however, measure of photodegradation. However in order to
Te only shows an 8% decrease. incorporate the two other tensile properties E and
It may be useful to point out some interesting au it is proposed here to use the area under the
features of the tearing tests and to explain why the stress-strain curve (Wp) (strictly speaking true
tearing energies, whether Ti, Tm or Te, as shown in stress-strain curves should be used in Equation 1,
Figs 6 and 7 are not as sensitive to structural as an effective index of photodegradation. As
changes due to photodegradation as would for 'shown in Figs 8 and 9 this seems promising.
example e~ given in Fig. 4. Since light absorption Anothe r advantage of this parameter (i.e. Wp) is

3063
70

6O 60
SUNLAMP EXPOSURE
1 / I N AIR AT 25~

5O
~~ so 2
O
z"
s o o
E 4O ~o
rY O
0
O0
w
7
SUNLAMP EXPOSURE 30 w
w N NITROGENAT 45~ w
z
w
,<
2o ~
o_ SUNLAMP E X P O S U R E ~ &
w IN N ~ R O G E N AT 65~ ~......~
w
o_
10 m
w

0 I I I I I I 0
200 400 600 800 1000 1200 1400 1600 1800
EXPOSURE TIME~ t (h)
Figure8 Variation o f s p e ~ f i c energy absorption with sunlamp exposure time.

that G e can be approximately calculated from Two points must be mentioned here. Firstly,
Equation 1" if the fracture process zone width is G e ~ Te, e.g. in the as-received condition G e
taken as about l m m , the sheet thickness. Thus (65kJm-2) - 1/2Te(120kJm-2). This meansthat
Figs 8 and 9 also represent the variation of fracture fracture surface energies in ductile materials such
surface energies (Ge) with ageing period. Clearly,- as nylon 6 studied here, are geometry dependent
G e decreases with photodegradation. _because as discussed in Section 1 the process zone_
,~ 100 100

'E
~" 80 NATURAL WEATHERING
8o
g

~ 60 6o
r~
Z
L~
laJ 4O 4o ~
<
oJ u_
a.
m 20 20 -J
<
t.tl

<
I I I I i
0 50 100 150 200 250 300
Figure 9 Variation of specific energy absorp-
EXPOSURE TIME ~t (DAYS) tion with natural ageing time.
* A n exact method of estimating the work absorbed in the fracture process zone is given in [9]. For the present study
since fracture mechanics experiments have not been thoroughly carried out Equation 1 although approximate, will b e
used here.

3064
size depends on the specimen geometry. Secondly, given by the area under the tensile stress-strain
the surface layers that are photodegraded behave curve, provides a better index of photodegradation.
differently in a tensile test to a "trouser-leg" test.
In a tensile test the specimen is like a layered References
composite with two embrittled outside layers and 1. J.W.S. HEARLE and B. LOMAS,J. Appl. Polymer
a middle tough layer of undegraded material. It Sci. 21 (1977) 1103.
2. R.A. COLEMAN and W. H. PEACOCK, Textile Res.
has been shown theoretically b y Atkins and Mai
J. 28 (1958) 784.
[13] and proven experimentally b y Guild e t al. 3. R. F. MOORE,Polymer4 (1963) 493.
[14] and Yap [15] that brittle fracture can occur 4. W. SCHNABEL and J. KIWI, in "Aspects of Degra-
in such a composite system. It is thus suggested dation and Stabilization of Polymers", edited by
that, because of the constraints of the photo- H. H. G. Jellinek (Elsevier, Amsterdam, Oxford and
degraded layers exerted on the middle layer, New York, 1978) pp. 195-246.
5. G. A. GEORGE and N. McM. BROWNE, "Non-
depending on the ageing period, "brittle" fracture destructive evaluation of the degradation of nylon
o f varying degrees occurs in nylon 6 specimens. 6,6 parachute materials", Materials Research Labora-
"Brittle" is used here to mean reduction in ductility tories, Department of Defence, Melbol]rne, Australia,
or toughness. In fact all tensile tests fail beyond Report No. MRL-R-691, June 1977.
the yield strength. 6. G. MAROM, E. HAREL and J. ROSNER, Jr. Appl.
Polymer Sci. 21 (1977) 1629.
7. G. E. ANDERTON and L. R. G. TRELOAR, J.
4. Conclusions Mater. ScL 6 (1971) 562.
The loss o f mechanical properties in nylon 6 due 8. B. COTTERELL and J. K. REDDEL, Inst. J. Fract.
to oxidative and non-oxidative photodegradation 13 (1977) 267.
has been studied in this paper. A t the time o f 9. Y. W. MAI and B. COTTERELL, J. Mater. ScL
15 (1980) 2296.
writing it has not been possible to assess the 10. G. T. HAHN, P. K. DAI and A. R. ROSENFELD,
effects o f oxygen on photodegradation from these Proceedings of the 1st International Conference on
preliminary experiments because the temperatures Fracture, Vol. 1 (1965) 229.
are n o t comparable. In the non-oxygen environ- 11. J.E. GUILLET, in "Degradation and Stabilization of
ment it is however shown that photodegradation Polymers", edited by G. Genskens (Applied Science
Publishers, London, 1975) pp. 181-98.
increases with rising temperature. Experimental 12. G.L.A. SIMS,J. Mater. Sci. 10 (1975) 647.
results are also obtained on nylon specimens 13. A. G. ATKINS and Y. W. MAI, Int. J. Fraet. 12
subjected to natural weathering b u t it is not (1976) 923.
possible to relate them to those b y accelerated 14. F. J. GUILD, A. G. ATKINS and B. HARRIS,
J. Mater. Sci. 13 (1978) 2295.
ageing. The specific tearing energy, Te or Tin, is
15. O.F. YAP, Int. J. Fraet. 15 (1979) R209.
not a suitable candidate for characterizing photo-
degradation in nylon. Instead it is proposed and
shown that Wp, the specific energy absorption Received 31 January and accepted 8 May 1980.

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