This document discusses the correlation between natural weathering and artificial weathering tests. It notes that while artificial tests aim to accelerate the weathering process for efficiency, they must still produce degradation through similar mechanisms to natural weathering. The document presents data from a Japanese study that exposed six polymers to natural weathering in four locations and seven artificial test units. The results showed that different test units produced different degradation rates for different polymers compared to natural exposure. Additionally, the rankings of polymer degradation differed depending on whether mechanical properties or color change was measured. The document concludes that while artificial tests can be useful, no single test perfectly simulates all aspects of natural weathering.
This document discusses the correlation between natural weathering and artificial weathering tests. It notes that while artificial tests aim to accelerate the weathering process for efficiency, they must still produce degradation through similar mechanisms to natural weathering. The document presents data from a Japanese study that exposed six polymers to natural weathering in four locations and seven artificial test units. The results showed that different test units produced different degradation rates for different polymers compared to natural exposure. Additionally, the rankings of polymer degradation differed depending on whether mechanical properties or color change was measured. The document concludes that while artificial tests can be useful, no single test perfectly simulates all aspects of natural weathering.
This document discusses the correlation between natural weathering and artificial weathering tests. It notes that while artificial tests aim to accelerate the weathering process for efficiency, they must still produce degradation through similar mechanisms to natural weathering. The document presents data from a Japanese study that exposed six polymers to natural weathering in four locations and seven artificial test units. The results showed that different test units produced different degradation rates for different polymers compared to natural exposure. Additionally, the rankings of polymer degradation differed depending on whether mechanical properties or color change was measured. The document concludes that while artificial tests can be useful, no single test perfectly simulates all aspects of natural weathering.
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 Artificial weathering versus natural exposure 167 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. 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.] 168 G. Wypych Fig. 10.3. PMMA. 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. 10.4. ABS. 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.] Artificial weathering versus natural exposure 169 Fig. 10.5. POM. 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. 10.6. PE. 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.] 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 Artificial weathering versus natural exposure 171 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. [ 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.] 172 G. Wypych Fig. 10.9. ABS. Color difference vs. exposure pe- riod 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. 10.10. POM. Color difference vs. exposure pe- riod 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.] Artificial weathering versus natural exposure 173 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). Artificial weathering versus natural exposure 175 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 Artificial weathering versus natural exposure 177 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. 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[Advances in Polymer Science 240] Erik Wischerhoff, Nezha Badi, André Laschewsky, Jean-François Lutz (auth.), Hans G. Börner, Jean-Francois Lutz (eds.) - Bioactive Surfaces (2011, Springer-Verlag Berlin Heid (1).pdf