Cap 10

10
ARTIFICIAL WEATHERING VERSUS

NATURAL EXPOSURE
How many hours of natural weathering equal one year of natural exposure? This is one
of the most frequently asked questions a person working on weathering is asked. Is
there any answer to this question? Think of the question: What is the durability of your
product? If you say, I do not know, one starts to wonder why you spend money to con-
duct weathering studies. If you say, Because this product withstands 2000 hours in a
Weather-O-Meter and its going to last 5 years, many people will questionyour truthful-
ness and perhaps even your qualifications. Endless discussions continue; every partici-
pant has some reason for his point of view, but the fact is that some products available in
the market today, are expected to last a minimum of 20 years and nobody is willing to
wait for another quarter of a century to approve an updated versions of the product.
Several groups of factors determine the result of weathering studies in natural con-
ditions and accelerated tests. These groups are discussed in individual chapters of this
book (chapters 4, 5, 7 through 11 and 13). If the conditions of each experiment are well
defined and, if the mechanism and kinetics of degradation are well understood, then
there is a high probability that the results of various experiments will correlate with
each other. The use of artificial weathering is feasible when it offers:
acceleration
control over conditions.
We want to perform studies in the minimum possible time and in well controlled,
repeatable conditions. It is not reasonable to expect that accelerated weathering condi-
tions will simulate natural weathering conditions. Similarly, testing materials ina trop-
ical climate (Florida) does not expose them to the proper natural conditions if the
material will be used in Alaska. The accelerated weathering conditions should be se-
lected to give the highest possible accelerating factor. However, the conditions selected
must produce degradation mechanisms which are as similar as possible to the way in
Artificial weathering versus natural exposure 165
which the material would degrade in natural conditions. The method of evaluating deg-
radation in these conditions must also be chosen carefully to ensure identification of the
same factors that are changed in natural exposure.
This discussion was intended to deflect any further debate as to whether or not
there is correlationbetweenthe data obtained under natural and under artificial weath-
ering conditions and to help the reader to remain objective as he or she reads the follow-
ing literature review. If there is no correlation, the experiment was not designed
properly or the details of experiment are not known or the tools used in the experiment
were not adequate and so on. As we look at the data, we should try to determine if the
modes of acceleration selected actually prevent correlation with the changes that occur
under natural conditions.
Part of the data presented in this chapter comes from a series of Japanese publica-
tions.
1-8
Alarge group of scientists dedicated their efforts to a coordinated study of six of
the most commonly used polymers. These were exposed to natural weather conditions in
four Japanese locations and also subjected to artificial weathering in seven test units.
The progress of degradationwas monitored by measuring the basic physical-mechanical
properties of the polymers. These efforts created a broad base of data, which was ob-
tainedincomparable conditions andis worthy of more extensive attention(these studies
provided additional information for other parts of this book).
Figs. 10.1 to 10.6 showthe thickness of the degraded layer versus time for both nat-
ural and artificial weathering. Samples exposed in a dew-cycle weathering tester have
completely different degradation characteristics from that generated by other acceler-
ated tests. The degradation of PVC, PMMA, ABS in a dew-cycle tester occurs much
faster than in other testers. But three other polymers (PS, POM, PE), initially degrade
as fast in the dew-cycle tester as they do in other testers and it is only in the last 1000
hours that the degradation of POMand PEis accelerated. This shows that the accelera-
tion factor of dew-cycle weathering apparatus is higher for some materials than for oth-
ers when compared with natural weathering or with other testers. In most cases, the
xenon arc weatherometer and the fadeometer give a lower degradation rate than do any
of the four carbon arc units used in the experiments. Comparison of the microphoto-
graphs of surface deterioration of specimens weathered both outdoors and in test equip-
ment shows that the crack pattern of specimens exposed outdoors most closely
resembles the crack pattern produced in a xenon arc weatherometer. When specimens
weathered in a xenon arc weatherometer are ranked according to their degree of degra-
dation, the order is closer to the rankings of specimens weathered outdoors than it is to
the ranking of specimens weathered in most of the carbon arc units (Table 10.1). Rank-
ing by the thickness of the degraded layer shows that, as is known frompractice, PMMA
is the clearly superior polymer. Both natural and artificial exposures confirm its stabil-
ity.
166 G. Wypych
Fig. 10.1. PS. Thickness of degradation layer vs.
exposure time. [SW-Sunshine weatherometer,
XW-xenon weatherometer, UVW-UV-carbon
weatherometer, DW-dewcycle weatherometer,
SF-Sunshine fadeometer, XF-xenon fadeometer].
[Adapted, by permission, from O. Nishimura,
H. Kubota, and S. Suzuki, Kenkyu Hokoku-Kogyo
Gijutsuin, 1981(2)115.]
Fig. 10.2. PVC. Thickness of degradation layer vs.
Gijutsuin, 1981(2)115.]
168 G. Wypych
Fig. 10.3. PMMA. Thickness of degradation layer
vs. exposure time. [SW-Sunshine weatherometer,
Gijutsuin, 1981(2)115.]
Fig. 10.4. ABS. Thickness of degradation layer vs.
Gijutsuin, 1981(2)115.]
Fig. 10.5. POM. Thickness of degradation layer vs.
Gijutsuin, 1981(2)115.]
Fig. 10.6. PE. Thickness of degradation layer vs.
Gijutsuin, 1981(2)115.]
The problems with some weathering equipment become apparent when we start to
compare the artificial weathering data on polymers which are competing for the second
and third ranked positions with that obtained for these polymers in outdoor exposure.
The distinctions made in artificial weathering data are not apparent in the data from
samples exposed outdoors which is almost identical for each. Different weathering sites
have different accelerating effects on the degradation of various polymers. For example,
PSdegrades twice as fast inNaha thanit does inSapporo whereas PEhas similar degra-
dation rates in both locations. This is most likely due to the fact that Naha has more rain
and humidity than Sapporo and that PEis less affected by exposure to water than is PS.
Figs. 10.7 to 10.11 showthe effect of different weathering conditions on the color change
of five polymers. Table 10.2 summarizes this experiment by comparing the ranking of
polymers exposed in different sites and equipment. If tables 10.1 and 10.2 are compared
it can be seen that the polymers are ranked differently. Not one polymer has the same
rank. This might be thought of as surprising but, in fact, a change of color is seldom
caused by the same mechanismwhich leads to a deterioration in mechanical properties.
Actually, with some polyurethanes, a color change during exposure indicates that the
polymer will retain its mechanical properties. It is not surprising that PE rates highest
with respect to color retention because there are practically no mechanisms which can
cause a change color during the initial degradation (as determined in this study). The
first three weathering devices do a good job of simulating the degradation which causes
color changes outdoors. There is just one exception (PVC). It is difficult to explain why
PVC consistently performs more poorly than PS in artificial weathering devices when,
innatural exposure, it performs muchbetter. Strangely enough, fadeometers, whichare
supposed to be capable of determining color stability, perform very poorly in this appli-
cation.
170 G. Wypych
Table 10.1: Thickness ranking
PS PVC PMMA ABS POM PE score
Sapporo 5 3 1 2 4 6
Choshi 6 3 1 2 4 5
Yokohama 5 3 1 2 4 6
Naha 6 2 1 3 4 5
Average 5 or 6 3 1 2 4 5 or 6
S-W 5 3 1 2 6 4 3
X-W 6 3 1 2 5 4 2
UV-W 6 4 1 2 5 3 4
D-W 3 6 1 2 4 5 5
S-F 5 6 1 2 3 4 5
X-F 6 5 1 2 4 3 4
Fig. 10.7. PS. Color difference vs. exposure period
in various sites and weathering equipment.
[ SW-Sunshi ne weat heromet er, XW-xenon
weatherometer, UVW-UV-carbon weatherometer,
DW-dewcycle weatherometer, SF-Sunshine
fadeometer, XF-xenon fadeometer]. [Adapted, by
per mi ssi on, f r om H. Kubot a, S. Suzuki ,
O. Nishimura, I. Tamura, K. Yoshikawa, and
T. Shirota, Hokkaido Kogyo Kaihatsu Shikensho
Hokoku, 24(1981)96.]
Fig. 10.8. PVC. Color difference vs. exposure pe-
riod in various sites and weathering equipment.
Hokoku, 24(1981)96.]
172 G. Wypych
Fig. 10.9. ABS. Color difference vs. exposure pe-
Hokoku, 24(1981)96.]
Fig. 10.10. POM. Color difference vs. exposure pe-
Hokoku, 24(1981)96.]
Fig. 10.11. PE. Color difference vs. exposure period in various sites and weathering equipment. [SW-Sunshine
weatherometer, XW-xenon weatherometer, UVW-UV-carbon weatherometer, DW-dewcycle weatherometer,
SF-Sunshine fadeometer, XF-xenon fadeometer]. [Adapted, by permission, fromH. Kubota, S. Suzuki, O. Nishimura,
I. Tamura, K. Yoshikawa, and T. Shirota, Hokkaido Kogyo Kaihatsu Shikensho Hokoku, 24(1981)96.]
Table 10.2: Color difference ranking
PS PVC ABS POM PE score
Sapporo 5 4 2 3 1
Choshi 5 4 2 3 1
Yokohama 5 4 2 3 1
Naha 5 4 3 2 1
Average 5 4 2 3 1
S-W 4 5 2 3 1 2
X-W 4 5 2 3 1 2
UV-W 4 5 2 3 1 2
D-W 4 5 1 3 2 4
S-F 4 5 3 2 1 4
X-F 3 5 4 2 1 6
174 G. Wypych
Fig. 10.12. PVC elongation retention vs. exposure
period outdoor and in weathering equipment.
[ XW-xenon weat heromet er, SW-Sunshi ne
weatherometer]. [Adapted, by permission, from H.
Kubota, S. Suzuki, O. Nishimura, S. Hattari, K.
Yoshikawa, and T. Shirota, Kenkyu Hokoku-Kogyo
Gijutsuin, 1981(2)23.]
Fig. 10.13. ABS elongation retention vs. exposure
period outdoor and in weathering equipment.
[ XW-xenon weat heromet er, SW-Sunshi ne
weatherometer]. [Adapted, by permission, from H.
Kubota, S. Suzuki, O. Nishimura, S. Hattari, K.
Yoshikawa, and T. Shirota, Kenkyu Hokoku-Kogyo
Gijutsuin, 1981(2)23.]
Figs. 10.12 and 10.13 show elonga-
tion retention during natural and artifi-
cial weathering of PVC and ABS. Table
10.3 compares the numerical data. A
prediction of weathering rate based on
changes in elongation agrees with the
findings obtained by two other methods
(ABS has better performance than
PVC). The relative rates of degradation
of each polymer in xenon arc are very
similar to that which is observed out-
doors.
The general conclusions from the Japanese studies are: both sunshine carbon arc
and xenonarc apparatus are useful to predict the service life of materials; the carbonarc
lamp accelerates degradation more than other methods. (It is probably for this reason
that carbon arc is the most frequently selected method in Japan.) However, from the
above analysis, the xenonarc gives a more accurate prediction. The viewof the Japanese
researchers is not shared by all scientists
i nvol ved i n weatheri ng studi es.
Gugumus
9
discusses several studies
which show correlations between results
obtained in natural and accelerated
weathering. Very good linear correlation
(r
2
=0.99) was found between weathering
studies conducted in outdoor exposure in
Central Europe andinFlorida (Fig. 10.14)
There was very poor correlation
(r
2
=0.45) between the results from xenon
arc and carbon arc Weather-O-Meters
(Fig. 10.15). There was no correlation be-
tween xenon arc (Xenotest 1200) and
QUV. QUV-weathered specimens did not
correlate with specimens exposed in
Florida (Fig. 10.16). But there is excellent
correlation between the data from the
Weather-O-Meter and the Xenotest 1200
(Fig. 10.17) and between either of the two
xenon arc testers and Florida exposure
(Fig. 10.18).
Table 10.3 Elongation retention, %
PVC ABS ABS/PVC
Sapporo 13.5 29.7 2.2
Choshi 11 25.9 2.35
Naha 6.9 21.8 3.16
S-W 34.2 37.9 1.11
X-W 24.2 41.5 1.71
Fig. 10.14. Comparison of exposure in Florida and
Central Europe based on energy to 50%retained elon-
gation (E
50
) for LDPE blown films. [Adapted, by per-
mission, from F. Gugumus, Dev. Polym. Stab.,
8(1987)239.]
Gugumus
9
presents other results, all of which are for polyolefins, and makes the
clear conclusion that only the xenon arc instrument, when equipped with filters which
176 G. Wypych
Fig. 10.15. Comparison of xenon-arc and car-
bon-arc exposure based on time to 0.5 carbonyl
absorbance (T
0.5
) for PP films. [Adapted, by per-
mission, from F. Gugumus, Dev. Polym. Stab.,
8(1987)239.]
Fig. 10.16. Comparison of QUV and Florida expo-
sure based on time to 0.1 carbonyl absorbance
(T
0.1
) and energy to 50% retained elongation (E
50
)
for LDPE blown films. [Adapted, by permission,
from F. Gugumus, Dev. Polym. Stab., 8(1987)239.]
Fig. 10.17. Comparison of Xenotest 1200 and
Weather-O-Meter based on time to 0.1 carbonyl
absorbance (T
0.1
) for PP film. [Adapted, by permis-
sion, from F. Gugumus, Dev. Polym. Stab.,
8(1987)239.]
Fig. 10.18. Comparison of Xenotest and Florida ex-
posure based on time to 50% retained tensile
strength (T
50
) and elongation (E
50
) for PP
multifilaments. [Adapted, by permission, from F.
Gugumus, Dev. Polym. Stab., 8(1987)239.]
give a spectrumsimilar to that of daylight, is useful for predicting the service life of poly-
mers. Similar conclusions were reached in a review paper
10
where numerous examples
of the use of artificial weathering equipment were discussed. The main conclusion from
these publications is that the xenon arc source does give the best correlation with day-
light exposure.
Several other papers
11-14
discuss the various factors which are critical to achieve a
correlation with data obtained in a natural environment. Some authors
15-16
underline
the deficiencies of QUV weathering in paints, claiming that this method gives accept-
able results for some coatings (acrylic-based) but not for others (phthalate-based polyes-
ter coatings). Industry has accumulated a great deal of data using three types of
weathering equipment (QUV, carbon arc apparatus, and xenon arc apparatus). It is dif-
ficult to replace these methods, since a proper assessment of the replacement method re-
quires that the performance of products, which have been available in the market for a
long time, be re-tested using the proposed replacement method. Fedor and Brennan
used simple tests to evaluate sealants (a visual comparison of cracks, hardness mea-
surement, and hand flexing). These led to the conclusion that QUV correlates better
with Florida exposure than does a xenon arc Weather-O-Meter.
17
The photodegradation of PVC out-
doors in Brisbane, Australia was com-
pared to the effect of exposure in QUV
equipment withUVBlamps (Fig. 10.19).
18
Note that outdoor weathering was more
severe than QUV. The authors of this pa-
per found that the mechanisms of degra-
dation, as determined by the type of
degradation product formed, were the
same. The difference in degradation rate
is attributed to the influence of the higher
temperature of outdoor exposure on the
dehydrochlorination rate.
It was found
15
that carbon arc expo-
sure causes an unusual oxidation in the
tested coatings. The dilemma of which
test should be used
19
is worst with paints
and coatings since the industries which
make them were among the first to initi-
ate weathering studies and this was done
at a time when only carbon arc instru-
ments were available. Murase et al.
20
used depth profiling analysis to evaluate
Fig. 10.19. Comparison of PVC dehydrochlorination
rate in QUV and outdoor exposure in Brisbane.
[Adapted, by permission, fromD. J. Hill, F. A. Kroesen,
J. H. ODonnell, and P. J. Pomery, Mater. Forum,
14(1990)210.]
the correlation of results between natural exposure and exposure in xenon and carbon
arc devices. Different mechanisms degraded the coating in the carbon arc device.
Gantcheva
21
presents results of studies which showthe data for PVCsheets during nat-
ural and Xenotest 1200 weathering. Factors related to the mechanical and electrical
properties of the materials were measured and the results show that a good simulation
of degradation in natural conditions can be achieved in a short time using the xenon arc
chamber. Rivaton
22
presents results of PC testing using different sources of UV radia-
tion and compares them with exposure in natural conditions. Filtered xenon arc radia-
tion correlates with outdoor exposure (see Fig. 5.4). Carbonyl group formation occurred
in epoxy resins exposed to four different sources of radiation but the rates and the mech-
anisms of degradation were affected by changes in the UV wavelength range.
23
Two papers,
24,25
devoted to the development of methods to compare natural and ar-
tificial weathering, stress different factors. Martin
25
considers the poor correlation be-
tween each method as a result of radiative energy differences. Based on successful
studies in biology, Martin proposes that the results of weathering can be improved only
if the relevant degradation energy for the material is considered. He attributes the poor
correlation to the fact that each material can only absorb and utilize a specific portion of
the total available energy whereas, in the artificial sources, the total radiation or, more
critically, the UV radiation available, may differ significantly fromthat available natu-
rally. If these differences are predominantly in the ranges where the material absorbs
strongly, there will be poor correlation between the degradative effects.
In another paper,
24
the poor correlation is attributed to the assumption that tem-
perature is not an essential factor in degradation. A model was developed in which the
conditions of sample exposure at different temperatures and different radiation energy
can be compared. Data obtained for PEwas used to demonstrate the effectiveness of this
approach. Additionally, the authors of this paper recommend that the conditions should
be chosen such that there will be no radiation wavelength available which is not present
in daylight. This will ensure that there be no degradation mechanisms that would not
happenunder natural exposure. David et al.
26
found that the degradationrate of PEwas
higher in Suntest (Heraus) equipment than in outdoor exposure in Brussels. This was
due to a different degradation mechanismcaused by the higher temperature in the arti-
ficial device.
Bauer
27
discusses the use of high energy UV radiation which is used frequently in
automotive tests. Experimental results show that such a method can lead to false pre-
dictions of coating durability. Asmall change inpolymer compositionor the additionof a
stabilizer caused a considerable change in the rate of degradation. Several other
papers
28-34
help to explain differences and similarities between sample testing outdoors
and sample testing in artificial weathering equipment. These approaches are relevant
to the successful studies as discussed in Chapters 5 and 8.
178 G. Wypych
REFERENCES
1. H. Kubota, S. Suzuki, O. Nishimura, S. Hattori, K. Yoshikawa, and T. Shirota, Kenkyu
Hokoku-Kogyo Gijutsuin, 1981,2,23.
2. Y. Nagatsuka, T. Shirota, K. Yoshikawa, S. Suzuki, H. Kubota, and O. Nishimura,
Kenkyu Hokoku-Kogyo Gijutsuin, 1981,2,87.
3. H. Kubota, S. Suzuki, O. Nishimura, K. Yoshikawa, and T. Shirota, Kenkyu
Hokoku-Kogyo Gijutsuin, 1981,2,49.
4. H. Kubota, S. Suzuki, O. Nishimura, I. Tamura, K. Yoshikawa, and T. Shirota,
Hokkaido Kogyo Kaihatsu Shikensho Hokoku, 24(1981)96.
5. O. Nishimura, H. Kubota, and S. Suzuki, Hokkaido Kogyo Kaihatsu Shikensho
Hokoku, 24(1981)115.
6. S. Suzuki, H. Kubota, O. Nishimura, and T. Tsurue, Hokkaido Kogyo Kaihatsu
Shikensho Hokoku, 24(1981)153.
7. E. Takeshima, T. Kawano, H. Takamura, and S. Kato, Shikizai Kyokaishi,
56(1983)457.
8. O. Nishimura, S. Suzuki, H. Kubota, K. Yoshikawa, and T. Shirota, Hokkaido Kogyo
Kaihatsu Shikensho Hokoku, 24(1981)193.
9. F. Gugumus, Dev. Polym. Stab., 8(1987)239.
10. J. N. Patel, JOCCA, (1991)105.
11. D. Waksman, W. E. Roberts, and W. E. Byrd, Durability Building Mater., 3(1985)1.
12. S. G. Croll, Prog. Org. Coat., 15(1987)223.
13. G. P. Bierwagen, Prog. Org. Coat., 15(1987)179.
14. P. Eurin, J. C. Marechal, and R. Cope, NATO ASI Ser., 95E(1985)21.
15. D. R. Bauer, J. L. Gerlock, and R. A. Dickie, Prog. Org. Coat., 15(1987)209.
16. R. R. Blakey, Prog. Org. Coat., 13(1985)279.
17. G. Fedor and P. Brennan, Applicator, 12(1990)2.
18. D. J. Hill, F. A. Kroesen, J. H. ODonnell, and P. J. Pomery, Mater. Forum,
14(1990)210.
19. J. H. Braun, Prog. Org. Coat., 15(1987)249.
20. A. Murase, Y. Esaki, M. Sugiura, and T. Araga, Anal. Sci., 7(1991)1597.
21. T. Gantcheva, A. Marinova, and P. Genova, Angew. Makromol. Chem., 137(1985)49.
22. G. Zhang, W. G. Pitt, S. R. Goates and N. L. Owen, J. Appl. Polym. Sci., 54(1994)419.
23. A. Rivaton, Angew. Makromol. Chem., 216(1994)147.
24. J. J. C. Cruz-Pinto, M. E. S. Carvalho, and J. F. A. Ferreira, Angew. Makromol. Chem.,
216(1994)113.
25. J. W. Martin, Prog. Org. Coat., 23(1993)49.
26. C. David, M. Trojan, A. Daro, and W. Demarteau, Polym. Deg. Stab., 37(1992)233.
27. D. R. Bauer, Prog. Org. Coat., 23(1993)105.
28. A. Tidjani and R. Arnaud, Polym. Deg. Stab., 39(1993)285.
29. M. Sargent, J. L. Koenig, and N. L. Maecker, Polym. Deg. Stab., 39(1993)355.
30. D. R. Bauer, J. L. Gerlock, and D. F. Mielewski, Polym. Deg. Stab., 36(1992)9.
31. A. Wootton, JSDC, 108(1992)239.
32. A. J. Watkins, IEEE Trans. Reliability, 40(1991)98.
33. F. Gugumus, Polym. Deg. Stab., 34(1991)205.
34. I. Narisawa and T. Kuriyama, Angew. Makromol. Chem., 216(1994)87.

Cap 10

Загружено:

Сведения о документе

Исходное описание:

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Cap 10

Загружено:

Авторское право:

Доступные форматы

10

ARTIFICIAL WEATHERING VERSUS

Вам также может понравиться