Accelerated Aging

O3
Ageing of Rubber
Accelerated Weathering and Ozone Test Results
R.P. Brown, T. Butler and S.W. Hawley
Europes leading independent plastics and rubber specialists
Ageing of Rubber
Accelerated Weathering and Ozone Test Results
R.P. Brown, T. Butler and S.W. Hawley Rapra Technology Limited
This report is an output from the Weathering of Elastomers and Sealants project which forms part of the UK governments Department of Trade and Industrys Degradation of Materials in Aggressive Environments Programme.
Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire SY4 NNR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.rapra.net
Practical Guide to Polyethylene
First Published in 2001 by
Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
Copyright 2001 Rapra Technology Limited
A catalogue record for this book is available from the British Library. ISBN: 978-1-85957-264-1 Every effort has been made to contact copyright holders of any material reproduced within the text and the authors and publishers apologise if any have been overlooked.
All rights reserved. Except as permitted under current legislation no part of this publication may be photocopied, reproduced or distributed in any form or by any means or stored in a database or retrieval system, without the prior permission from the copyright holder. The report is published in good faith, but on the basis that no responsibility or liability of any nature shall attach to Rapra Technology Limited arising out of or in connection with any utilisation in any form of any material contained herein
Typeset by Rapra Technology Limited Printed and bound by Lightning Source UK Ltd
Contents
1. Introduction ...................................................................................................................... 1 2. Materials .......................................................................................................................... 1 2.1 Original Materials ..................................................................................................... 1 2.2 New Materials ........................................................................................................... 2 3. Preparation of Test Pieces ................................................................................................. 3 4. Physical Tests .................................................................................................................... 3 5. Exposure of Test Pieces ..................................................................................................... 3 5.1 Weathering ................................................................................................................. 3 5.2 Ozone Exposure......................................................................................................... 4 6. Weathering Results (Appendix 2) ..................................................................................... 4 6.1 Presentation ............................................................................................................... 4 6.2 Uncertainty ................................................................................................................ 5 6.3 Interpretation of results ............................................................................................. 5 7. Ozone Results (Appendix 3) ............................................................................................. 6 8. Discussion ......................................................................................................................... 6 8.1 Weathering ................................................................................................................. 6 8.1.1 General ............................................................................................................. 6 8.1.2 Hardness .......................................................................................................... 7 8.1.3 Modulus ........................................................................................................... 8 8.1.4 Tensile Strength ................................................................................................ 8 8.1.5 Elongation at Break .......................................................................................... 9 8.1.6 Effect of Temperature ....................................................................................... 9 8.2 Ozone ...................................................................................................................... 11 9. Conclusions .................................................................................................................... 12 References ........................................................................................................................... 12 Appendix 1 - Compound Details ......................................................................................... 13 Appendix 2 - Weathering Results ........................................................................................ 25 Compound A - Natural Rubber - Standard .................................................................... 27 Compound B - Natural Rubber - Good Ageing .............................................................. 31 Compound C - Natural Rubber - Mineral Filler Loaded ................................................ 35 Compound D - Natural Rubber - Mineral Filler (Heavy Loaded) .................................. 39
Compound E - Styrene Butadiene Rubber - General Purpose ......................................... 43 Compound F - Styrene Butadiene Rubber - Good Ageing ............................................... 47 Compound G - Styrene Butadiene Rubber - General Purpose ......................................... 51 Compound H - Styrene Butadiene Rubber - Good Ageing .............................................. 55 Compound J - Butyl Rubber - General Purpose .............................................................. 59 Compound K - Butyl Rubber - Good Ageing .................................................................. 63 Compound L - Polychloroprene - General Purpose ........................................................ 67 Compound M - Polychloroprene - Natural Ageing ......................................................... 71 Compound N - Polychloroprene - Heat Ageing .............................................................. 75 Compound P - Nitrile Rubber - General Purpose ........................................................... 79 Compound R - Polychloroprene - Good Ageing ............................................................. 83 Compound S - Miscellaneous - Acrylate Rubber ............................................................ 87 Compound T - Miscellaneous - Chlorosulphonated Polyethylene .................................. 91 Compound W - Miscellaneous - Polysulphide Rubber .................................................... 95 Compound X - Miscellaneous - Silicone Rubber ............................................................ 99 New Compounds Compound N1 - FVMQ ............................................................................................... 103 Compound N2 - HNBR ............................................................................................... 107 Compound N3 - Epoxidised Natural ............................................................................ 111 Compound N4 - Chlorinated Polyethylene ................................................................... 115 Compound N5 - Fluorocarbon ..................................................................................... 119 Compound N6 - Exxpro ............................................................................................... 123 Compound N7 - Epichlorohydrin ................................................................................. 127 Compound N8 - EPDM ................................................................................................ 131 Compound N9 - EVA ................................................................................................... 135 Compound N10 - PU .................................................................................................... 139 Participants Compounds Compound P1 ............................................................................................................... 143 Compound P3 ............................................................................................................... 147 Compound P4 ............................................................................................................... 151 Compound P5 ............................................................................................................... 155 Compound P6 ............................................................................................................... 159 Compound P7 ............................................................................................................... 163 Compound P8 ............................................................................................................... 167 Compound P9 ............................................................................................................... 171 Compound P10 ............................................................................................................. 175 Appendix 3 - Ozone Results .............................................................................................. 181
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Ageing of Rubber - Accelerated Weathering and Ozone Test Results
1 INTRODUCTION
A long-term natural ageing programme was started in 1958 when 19 rubber compounds were exposed at 3 locations. The final sets of test pieces were withdrawn in 1998 giving a total of 40 years of natural ageing. The results of the physical tests carried out at intervals over the 40 years have been published [1]. The 19 compounds were re-mixed in 19992000 in order that accelerated ageing tests could be carried out for direct comparison with the results from natural ageing. A total of 20 new compounds were also mixed to represent polymers not available in 1958 and to reflect changes in compounding practice. Ten of these materials were formulations directly nominated by industry covering materials of current interest to particular companies. The 39 materials were subjected to accelerated heat ageing for a series of times and temperatures, artificial weathering and exposure to ozone. This report details the results of the artificial weathering and ozone exposure tests and makes comparisons with the results after natural ageing. The accelerated heat ageing results will be published separately (Ageing of Rubber Accelerated Heat Ageing Results).
2 MATERIALS
The test pieces used in the programme were produced from compounds with the formulations given in Appendix 1. For reasons of confidentiality, the materials nominated by industry are only described by polymer type. As regards the original 19 materials, it is perhaps surprising that compounding has changed relatively little and most of the formulations are relevant today. The new compounds formulated by Rapra, with advice from the project Industry Steering Group, were selected as being the more commercially important of the many polymers and compounding ingredients introduced since the start of the project in 1958.
2.1 Original Materials

Four natural rubber compounds were selected. Compound A was selected as it had been used at Rapra for many years as a standard material which loosely represented a tyre tread or high grade conveyor belt cover. Compound B has what became known as an efficient vulcanising system with no elemental sulphur, although the term had not then been coined. Compound C represents a fairly high rubber content, non-black filled material. The final natural rubber compound D was requested by the electrical side of the industry as a highly loaded, low grade insulation material and was said to exhibit good ageing properties in the dark. Compounds E and F are styrene butadiene rubbers (SBR) corresponding to A and B whilst G and H are oil extended versions. Compounds J and K were referred to as general purpose and good ageing butyl compounds, respectively. They represent the extremes of polymer available, with high and low unsaturation, respectively.
The three polychoroprene compounds came from the polymer supplier and were labelled general purpose (L), natural ageing (M) and heat ageing (N). The two nitrile compounds were suggested by the main UK supplier at the time to represent a general purpose material (P) and a good ageing formulation (R). The remaining compounds were also suggested by the relevant suppliers as general purpose materials.
2.2 New Materials

Compound N1 is a fluorosilicone-based on LS 2380U. The hydrogenated nitrile compound N2 is a formulation to give heat resistance. Compound N3 is an epoxidised natural rubber with low black loading used in an acoustic application. The chlorinated polyethylene, compound N4, represents a formulation for hose tube and cover material. Compound N5 is a 70 IRHD fluorocarbon-based material for seal applications. Compound N6 is an Exxpro material (isobutylene p-methylstyrene copolymer) described as general purpose. The epichlorohydrin material, compound N7, is also formulated for general purpose use. The sulphur cured ethylene propylene terpolymer (EPDM), compound N8, is a formulation typically used for radiator hose applications. Compound N9 is an ethylene vinyl acetate cable sheathing material. Compound N10 is a general purpose millable polyurethane. Compounds P1P10 are materials submitted by industry participants: Compound P1 Compound P2 Compound P3 Compound P4 Compound P5 Compound P6 Compound P7 ethylene propylene copolymer siloxane material medium nitrile, carbon black filled with EV sulphur cure nitrile, NF standard 0115/2 EPDM, NF standard 0115/1 Vamac G material, black filled with a Diak/DOTG cure system W type polychloroprene with small amount of SBR, carbon black filled, sulphur/metal oxide cure natural rubber thermoplastic rubberSantoprene 101 55 V185 from AES nitrile
Compound P8 Compound P9 Compound P10
Compound P2 was not tested for weathering and ozone resistance because it was a special purpose cellular material.
3 PREPARATION OF TEST PIECES

Batches of all 39 compounds were mixed. In most cases 2 batches were needed, which were blended. Standard 2 mm sheets were produced by compression moulding. The cure times used in 1958 for the original materials could not be derived from measurements in a curemeter as these instruments were only in the experimental stage. Hence, they were derived from a programme of curing for various times and measuring physical properties. The cure times for the new materials were derived from measurements on a Monsanto rheometer. The cure conditions arrived at are given in Appendix 1.
4 PHYSICAL TESTS
Ideally, the same physical tests as used in the natural ageing programme would have been used to monitor changes but the volume of work that would have entailed was prohibitive. Hence, the following properties were selected for monitoring the artificial weathering exposures: tensile strength, elongation at break, stress at 100% elongation, stress at 300% elongation, and hardness. These properties correspond to properties monitored in the natural ageing programme. It may be noted that for the heat ageing exposures, compression set and dynamic properties were also measured. Monitoring of the effects of ozone exposure was by observation of cracks using a x7 lens. Tests were carried out in general accordance with the current ISO methods [23]. For tensile properties, type 2 dumbbells were used, with 3 dumbbells being tested at each measurement point. Hardness measurements were made by taking 5 readings on one test piece. Ozone exposure test pieces were in the form of T50 dumbbells.
5 EXPOSURE OF TEST PIECES

5.1 Weathering
Test pieces were exposed in QUV fluorescent tube apparatus using UVA 340A lamps with a black panel temperature of 45 C and a cycle of 4 hours condensation and 4 hours dry (3 cycles per day) [4]. By agreement with the supplier of material P2, it was not tested for weathering resistance.
Seven sets of 3 dumbbells and a piece of sheet for hardness measurements were exposed. Sets of test pieces were removed and tested at approximately 30 day intervals up to 6 months (leaving 1 set spare). Test pieces were conditioned for a minimum of 16 hours at 23 C and 50% relative humidity prior to test.
5.2 Ozone Exposure

Test pieces were strained to 5, 10, 15, 20 and 30%. After conditioning for 72 hours, they were exposed to ozone at 23 C [5]. All materials were exposed to 50 pphm of ozone for up to 1 month. The exposure was repeated at 200 pphm of ozone but excluding those materials that had cracked to grade 3 most rapidly at 50 pphm (E, F, G, H, N3 and P3). By agreement with the supplier of material P2, it was not tested for ozone resistance. The test pieces were examined after nominally 2, 4, 8, 16 and 24 hours and daily thereafter and any cracking noted.
6 WEATHERING RESULTS (APPENDIX 2)

6.1 Presentation
The results for each property after artificial weathering were plotted as a function of exposure time. The tensile properties are the mean of results on 3 test pieces and the hardness result is the median of 5 readings. A best fit line was then constructed by computer for each graph using proprietary software which selects from hundreds of functions. Hence, the function in each case was selected on an empirical basis and there is no a priori reason to suppose that the same function would be valid for extrapolations. Alternative functions might be considered preferable. The initial and 6 month values for each property were then read off the best fit lines. This means that these values are not necessarily the same as the initial and final plotted data points. This treatment gives no special weighting to the initial unaged data, nor to the final 6 month results. From the initial and final values, the differences and the differences expressed as percentage change have been tabulated. Values were generally read to three significant figures and, to avoid misleading rounding errors, the percentage changes are given to two significant figures. This does not imply accuracy to the number of figures recorded. Whenever possible, values are quoted for both 100% and 300% modulus. In some cases, values for 300% were not available for the longer exposure times. This necessitated the extrapolation of the best fit line through the 6 month point in order to produce a comparative percentage change value.
6.2 Uncertainty
In order to make a realistic assessment of the significance of the results, it is necessary to make an estimation of the variability of the test results. An indication of variability is illustrated on the graphs by means of error bars. These were derived from standard deviations for repeatability taken mostly from precision statements in ASTM and ISO test method standards. The repeatability standard deviations were multiplied by 2 to give the 95% confidence intervals. It will be appreciated that these error bars simply give an idea of the degree of scatter which might generally be expected. Comment is made below on the uncertainty of estimates made by extrapolation of the results but no attempts at quantification have been made.
6.3 Interpretation of results

A quick snapshot view of the changes which have taken place over 6 months exposure is given by Table 1 for each material. However, the figures giving change and percentage change need to be viewed in context with the level of the property measured and the uncertainty. For example, the 100% modulus figures are generally small so that a relatively minor change may appear as a large percentage change and the experimental uncertainty is large. The graphical presentation allows at least a subjective assessment to be made of the significance of the recorded changes. In most cases, a clear trend is apparent with little masking by scatter of results. It is appreciated that, in general, the change of property with time is not linear and, hence, it is not strictly correct to make predictions based on the change over 6 months. Using this simplified approach is justified on the grounds that: the prime object of the artificial weathering trials was to obtain the order of magnitude of the effects of weathering in comparison to those from heat ageing, and the uncertainties of subtracting the effect of heat alone and extrapolating to ambient weathering conditions are in any case very large. Estimates of the expected changes in properties over 6 months from exposure to a temperature of 45 C were obtained by making Williams Landel Ferry (WLF) transforms of the accelerated ageing results reported separately. By subtraction of these figures from the weathering results, the effect due to light (and possibly moisture) over 6 months can be estimated. These effects are tabulated in Table 2 for each material. Missing figures are due to the raw data being insufficient or very highly variable. If an acceleration factor due to the higher irradiance in the weathering apparatus compared to natural sunlight is assumed, it is possible to estimate the effects of weathering at 23 C under natural exposure to light. It is appreciated that such acceleration factors are generally regarded as invalid because of the variation in solar radiation and the differences in distributions of the wavelengths of the light. However, to give an estimate of the order of magnitude of change that might be expected from weathering, acceleration factors were derived from quoted irradiance
and annual solar radiation figures. The factors derived for the UVA 340 lamps were Arizona 6.0, Florida 7.1 and London 14.0. Estimates for 10 years exposure in London are given in the same table, calculated from: C 10 1 0.5 14
where C is the net change due to weathering after 6 months. The 10-year period is equivalent to only a relatively modest extrapolation of the 6 month exposure graphs but, because of the uncertainty in the acceleration factor, the figures can at best be considered as tentative.
7 OZONE RESULTS (APPENDIX 3)

The times to first observed cracking (Grade 1 cracking) as a function of strain are given for results at 50 pphm and at 200 pphm, along with the times to reach Grade 3 cracking (Tables 1 4). Compounds which did not crack have been omitted. Graphical representations of the times to first cracking are given in Figures 1 and 3 and of times to Grade 3 cracking in Figures 2 and 4. The times to first observed cracking were plotted as a function of strain and an exponential function fitted. Selected graphs are given in Figures 57. It is not sensible to attempt to interpret accelerated ozone exposure tests in terms of times to cracking under ambient conditions. Clearly, the best result is for there to be no cracking, and compounds which have not cracked after 1 month at 200 pphm can be considered totally resistant. Distinction between materials that have cracked can be made on the basis of the length of time to cracking at a given ozone concentration, the maximum strain without cracking and the severity of cracking. As an indication of performance in relation to service, a material passing a typical specification requiring no cracking after 7 days at 50 pphm and 20% strain would be expected to give at least 5 years service without cracks under typical ambient conditions.
8 DISCUSSION
8.1 Weathering 8.1.1 General
Comment is made for each property on the trends seen during accelerated weathering, rather than attempting a detailed analysis of each compound property by property.
For the original 19 compounds, the trends are compared to the natural ageing results, always bearing in mind that they were in the absence of light. Then the estimated contributions due to temperature (obtained from accelerated heat ageing tests) and UV light are discussed, and comment made on the magnitude of the estimated net change due to weathering. Several overall observations can be made. Weathering and shelf or heat ageing differ because of the presence of UV light in the former, and it is perhaps not surprising that there are many observed differences in behaviour between the two. However, the direction of change is generally similar with only relatively few cases where there is total conflict. The traditional view has been that weathering, UV light in particular, has minor effect on rubbers. These results show that in many cases accelerated weathering produces quite large changes in properties. Adjusting the results for the effect of temperature often made a big difference to individual properties but overall the effects due to weathering were still found to be very significant. There are considerable differences in the magnitude of the response to weathering as measured by different properties, which illustrates the generally held view that preferably several relevant properties should be investigated in any exposure trial. The ranking of materials is not consistent across different properties which reinforces the need to consider more than one property when characterising or selecting materials. The natural rubber compounds C and D showed significant surface cracking (Appendix 2, Figures 1 and 2), which is illustrated in Figures 1 and 2. The pattern of cracks is reminiscent of alligatoring which has been observed on polymeric roof membranes used in hot climates with high UV exposure and intermittent rainfall. This has been attributed to localised stresses due to wetting and drying coupled with degradation due to temperature and UV light. It is perhaps significant that these two compounds (especially D) have high loadings of calcium carbonate.
8.1.2 Hardness
For all materials, there was either an increase in hardness or the hardness was very little changed over the six months. For the majority of compounds, the increase was less than 10% and for 15 compounds below 5%. Compounds D, N, T, W, P7 and P8 had increases above 10% with natural rubber D and Hypalon T above 20%. In many cases, there is a tendency for the rise in hardness to be more rapid at the beginning and then to plateau out. This is significant for compounds D, E, F, M, N, T, W, N10 and P10 with the effect being very large in the case of natural rubber D and Hypalon T. These were the two materials that showed the greatest total rise. One important implication of this is that linear extrapolation would be very misleading. It would be reasonable to suppose that the rapid increase was largely a surface effect.
Compounds N2, N4, N9, P1 and P4 apparently exhibit slightly more complex behaviour with P1 and P4 possibly reducing in hardness towards the end of the 6 months (P1 also showing a minimum) and N2, N4, and N9 possibly increasing towards the end of the 6 months. These changes are, however, relatively small. Compounds N5 and N6 show a tendency for the rate of hardness increase to rise over the exposure period. The natural ageing behaviour was similar in that all materials either increased in hardness or were very little changed. A plateau effect was seen in natural ageing for compounds E, F, G, H, K, P and R, and hence does not correspond exactly with the plateaux in weathering.
8.1.3 Modulus
For the modulus at 100%, there were no cases of a really sharp initial rise, although the curve fitting for compounds D, E and N10 show a small step. For most materials, there was either a rise in modulus or little change. However, in a number of cases there was a tendency for a modest decrease, notably compounds C, D, H, S, X, P5, N1, N5 and P9. Compound N6 showed a large initial drop in modulus and then a plateau. Also, in several cases there was some evidence for a maximum in the modulustime curve. Most changes in modulus were fairly low with only compounds E, G, T, W and N10 having rises of over 20% and A, N, and P8 of over 40%. The drop in modulus for N6 was over 20%. The 100% modulus results are not entirely consistent with hardness in that there were some decreases and there is not good correlation for materials showing the greatest changes. There were no cases of 300% modulus showing a significant sharp initial rise. Only P1 and P10 had an appreciable tendency to have a maximum. Generally, the results were reasonably consistent with the 100% figures but at 300% A, M, and P8 had rather less modulus increase, and N had much lower increase. C and P1 showed a larger decrease, L no decrease and P, R and N3 a larger increase. The Hypalon T was completely inconsistent with 100% modulus increasing but 300% modulus decreased. The nitrile P10 was apparently inconsistent but at both levels it exhibited the same shaped curve with a maximum. It can be argued that good correlation between hardness and modulus would not be expected because of the effect of UV being confined to the surface. This would also affect correlation with the natural ageing.
8.1.4 Tensile Strength

The great majority of materials show a decrease or are little changed in tensile strength over the 6 months. However, compounds S, N9, P5 and P6 show a tendency for tensile strength to increase. Compounds N1, N3, N10, P1, P7, P9 and P10 apparently exhibit slightly more complex behaviour. N1, N10 and P1 have a maximum in tensile strength whereas P7, P9 and P10 possibly have an inflexion and N3 a minimum. There is strong indication of a plateau effect in several of the materials, notably compounds B, C, D, F, G, L, R, and T which means that linear extrapolation would be misleading, as it could be for those with more complex behaviour.
For more than half the compounds the change in tensile strength is appreciable, with A, B, C, D, F, W, N, R, T, N10, P7, P8, P9 and P10 having over 20% decrease. The natural rubbers C and D and the nitrile P10 suffer very large decreases. There is significant rise in strength for EPDM P5. There are clearly some anomalies in comparison with the natural results, notably the reverse behaviour of the polysulphide W. A plateau effect was not seen in natural ageing.
8.1.5 Elongation at Break

The great majority of materials show a decline in elongation at break or change little over the 6 months. Compounds S, X, N5, N6 and P1 possibly increase. Compounds J, N1, N4, N8, N9, P5 and P6 can be said to change relatively little. Also, the majority apparently decline to a plateau level. Compounds K and N5 appear to have a cyclic pattern but this could easily be an effect of variability. P8 follows the typical decrease but there is indication of a plateau being reached. The scatter for N2 is unusually large and it is difficult to see a definite trend. As for tensile strength, over half the materials exhibit considerable change although the elongation at break performance is perhaps not quite as bad. Compounds A, B, D, E, G, N, R, T, N7 and P8 decline by more than 20% with Hypalon T the worst. As a general rule, the tensile strength and elongation changes are not dissimilar. The only real exceptions are for compounds C, N7 and P1. C has a very much greater drop in strength than elongation, N7 a large drop in elongation but no change in strength, whilst for P1 the changes are significantly in opposite directions. Generally, the changes are not in conflict with the natural ageing results, but the latter did not show a plateau effect.
8.1.6 Effect of Temperature

The estimates of change due to temperature over 6 months at 45 C obtained by extrapolation from accelerated ageing (Appendix 2, Table 2) are subject to large uncertainty and may not even be valid. Taking them at face value (accelerated ageing results will be analysed in more detail in a subsequent report), the changes seen on weathering are very similar to the changes predicted for temperature effects in about 37% of the cases (each compound and property equals 1 case). In about 22% of the cases, the change predicted for temperature is significantly smaller or very much smaller than the changes seen in weathering, whilst in about 27%, the change predicted for temperature is significantly larger or very much larger than changes seen in weathering. In about 22% of the cases, there is complete disagreement in that the changes after weathering and predicted for temperature are in opposite directions. Very simplistically, this could be taken to indicate that in about 37% of the cases temperature accounts for all of the changes seen after weathering, that in 22% there is a significant weathering effect in addition to a temperature effect, but that in approaching 50% of the cases the temperature and weathering effects are different. It is highly unlikely that this is totally correct but it does indicate that in the majority of cases there is evidence of a significant effect due to UV and or moisture.
When the estimates of net change due to weathering are taken and converted to change after 10 years under UK radiation conditions, the prediction is that in about 65% of the cases the weathering change would be significant (greater than 10%). Whilst again repeating that these predictions are somewhat speculative, there appears to be sufficient evidence to suggest that the effect of weathering alone should not be ignored and may be quite large for some materials. It is interesting to note differences between properties in respect of the weathering changes predicted. The modulus predictions show the most instances of significant weathering change (~83%) and the hardness least (~26%). Tensile strength and elongation show about 62% and 76%, respectively. Modulus results are probably the least reliable because of the uncertainty arising from the relatively low levels of force being measured but no explanation is offered as to why hardness shows the least change. Natural rubber compounds C and D exhibited very obvious surface cracking after the weathering exposure which was not seen in heat ageing tests. Hence, it is logical to conclude that there is firm evidence of a UV (and/or water) effect in these cases. The net weathering predictions for all properties of these materials is 10% or greater. The same is true for natural P8 and epoxidised natural rubber N3 other than hardness. Because of the uncertainties, it would be unwise to be very specific as to which materials are particularly prone to UV degradation. However, the predictions do show significant apparent dependence on formulation, for example, the polychloroprenes L, M and N, and very few materials were little affected for all properties. Elongation at break was reduced by heat ageing for almost all compounds, and in the remaining cases the change was small. For acrylate S, silicone X, fluorocarbon N5, Exxpro N6 and EPDMs P1 and P5, elongation at break increased on weathering. For hydrogenated nitrile N2, chlorinated PE N4 and Vamac P6, change in elongation at break after weathering and heat ageing were in opposite directions. This would imply different reactions for these materials in the two types of exposure. In some cases at least, the weathering effect might involve moisture. The changes in opposing directions are added to obtain the net weathering predictions and, hence, make these figures much larger than the individual results for weathering or heat ageing. The same additive effect applies to the other properties when changes are in opposite directions. This is significant in raising the net weathering predictions for hardness in the cases of fluorocarbon N5 and polyurethane N10, and for tensile strength in the cases of nitrile P, acrylate S and Hypalon T. Also, when the change from weathering is smaller than the change from heat ageing (in the same direction) it results in the predicted net effect being in the opposite direction to the total weathering change, and in some cases larger numerically than the total weathering change. If one was sceptical of predictions from accelerated heat ageing results and argued that the changes during weathering exposure had little contribution from temperature effects, it is interesting to see that there would then be approximately 61% of cases with a predicted weathering change of greater than 10% after 10 years in the UK. This is fractionally smaller than the figure after the temperature effect adjustment had been made and one would again conclude that it would be wise not to ignore weathering effects.
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8.2 Ozone
At 50 pphm (Appendix 3, Tables 1 and 2), compounds L, M, N, N1, N2, N4, N5, N6, N8, N9, N10, P1, P5, P6, P7, P9, S, T and X showed no cracking after 28 days. Compounds J and N7 had only Grade 1 cracks at the highest strains after 24 days. Compound P8 only cracked at the highest strain but rapidly developed Grade 3 cracks at 11 days and broke after 15 days. At 200 pphm (Appendix 3, Tables 3 and 4), compounds N1, N2, N4, N5, N6, N7, N8, N9, N10, P1, P5, P6, P7, P9 S, T and X showed no cracking after 28 days. Compound J had only Grade 1 cracks at the higher strains. It is a little curious that compound N7 showed cracking only at the highest strain at 50 pphm and that compound P8, although again very rapidly developing larger cracks, did not break. Hence, only compounds N1, N2, N4, N5, N6, N8, N9, N10, P1, P5, P6, P7, P9 S, T and X can be said to be completely ozone resistant. N7 is very close to being totally resistant and J and K perform extremely well. The results were generally not surprising. All the natural rubber and SBR compounds cracked relatively quickly, although the natural rubber compound P8 was notable for the improvement that is possible through compounding. The butyl rubbers J and K did crack but only at higher strains and longer times. All the polychloroprene compounds were clear at 50 pphm but the older compounds cracked at 200 pphm. The nitriles, except for the hydrogenated material N2, all cracked at 50 pphm, as did the polysulphide W. The epichlorohydrin N7 barely cracked at 50 pphm and was clear at 200 pphm. The remaining polymers appear to be totally resistant. The performance of polymers with relatively poor ozone resistance is very dependent on the formulation and, in particular, whether an effective antiozonant has been included. This is well illustrated by the difference between compounds AD and compound P8. It should be noted that for many of the materials in this programme, ozone resistance was not a prime consideration and in consequence they were not well protected. The ranking in terms of the times to first cracking is conveniently seen in Figures 1 and 3 in Appendix 3. At 50 pphm compounds A, C, D, E, F, G, H, P, N3 and P3 had cracked at all strains in under 1 week. Similarly, the ranking in terms of times to grade 3 cracking is shown in Figures 2 and 4. The comparison of the two pairs of diagrams also shows the effect of increasing ozone concentration. In the context of this programme, the most important point to note from these ozone results is that cracking could be a rather more critical factor for the less resistant materials than, for example, heat ageing, if they were used in applications and under conditions conducive to ozone attack. It should also be noted that very little evidence of ozone attack was seen on the samples naturally aged for 40 years. With the exception of compression set, test pieces were not strained and in the shelf ageing conditions used, ambient ozone levels were probably very low. Hence, in contrast to the statement in the previous paragraph, in suitable conditions ozone will not be an important consideration. In thick articles, cracking confined to the surface has no more than cosmetic significance.
11
If cracking does occur its severity, or the rate at which it progresses, is of interest. A very simple measure of the rate of crack growth can be deduced by comparing Figure 1 with Figure 2, and Figure 3 with Figure 4 (in Appendix 3). As an example, there is a clear difference between the natural rubber compounds AD and the SBR compounds EH. They all reach first cracking quickly but the SBRs reach grade 3 much more quickly than the natural rubbers. It is also interesting to note the pattern of cracking with strain level for non-resistant compounds. In some cases, a plot of time to cracking against strain appears to show a threshold strain below which cracking does not occur even at long times. A fairly good example is material P4 (Appendix 3, Figure 5). However, in the majority of cases in this work the possibility of a threshold strain is less clear. In the case of material W (Appendix 3, Figure 6), the exposures would need to be continued for longer times and for the least resistant materials tests at strains below 5% would be needed. Where there was some evidence for a threshold strain, it was generally about 5% or even lower which might be difficult to avoid in many applications. Occasionally, such as for material P10 (Appendix 3, Figure 7), it was significantly higher and this could be worth investigating more carefully.
9 CONCLUSIONS
An accelerated weathering and ozone exposure programme involving a total of 38 rubber compounds has been successfully completed. The weathering results indicate that the effect of UV light may be significant for many rubbers and in some cases quite large, despite the presence of carbon black. Hence, it would be wise not to ignore the effect of weathering when estimating service life. The well-known fact that polymers vary greatly in their ozone resistance has again been demonstrated. Where non-resistant materials are involved, the likelihood of ozone attack being a problem in service should be carefully considered before undertaking long-term evaluation of thermal ageing performance.
REFERENCES
1. R.P. Brown and T. Butler, Natural Ageing of RubberChanges in Physical Properties over 40 Years, Rapra Technology Limited, 2000. ISO 37 1994 Rubber, vulcanised or thermoplasticDetermination of tensile stressstrain properties. ISO 48 1994 Rubber, vulcanised or thermoplasticDetermination of hardness (Hardness between 10 IRHD and 1000 IRHD). ISO 4665 1998 Rubber, vulcanisedResistance to weathering. ISO 1431-1 1989 Rubber, vulcanised or thermoplasticResistance to ozone cracking Static strain test.
2.
3.
4. 5.
12
APPENDIX 1 COMPOUND DETAILS
13
Appendix 1
14
Natural Rubber
Natural Rubber
Ingredient Compound A Standard Curing conditions: 35' @ 141 C Smoked sheet HAF black Stearic acid Pine tar Zinc oxide CBS PBN Sulphur Compound B - Good Ageing Curing conditions: 30' @ 148 C Smoked sheet HAF black Stearic acid Pine tar Zinc oxide TMTD PBN MBT Compound C - Mineral Filler Loaded Curing conditions: 20' @ 141 C Smoked sheet Stearic acid Petroleum-based softener Zinc oxide CBS PBN Sulphur Precipitated calcium carbonate Compound D - Mineral Filler (Heavy Loaded) Curing conditions: 20' @ 141 C Smoked sheet Stearic acid Petroleum-based softener Zinc oxide CBS PBN Sulphur Precipitated calcium carbonate Amount (pphr) 100 50 2.5 4.5 5 0.5 1.0 2.5 100 50 0.5 4.5 5 2.5 1.0 1.0 100 1.5 5 5 0.5 1.0 2.5 80 100 1.5 25 5 0.6 1.0 3.2 200
15
Appendix 1
Styrene Butadiene Rubber

Ingredient Compound E - General Purpose Curing conditions: 40' @ 153 C SBR 1500 HAF black Stearic acid Petroleum-based softener Zinc oxide CBS PBN Sulphur Compound F - Good Ageing Curing conditions: 40' @ 153 C SBR 1500 HAF black Stearic acid Petroleum-based softener Zinc oxide TMTD PBN MBTS Compound G - General Purpose Curing conditions: 40' @ 153 C SBR 1710 HAF black Stearic acid Petroleum-based softener Zinc oxide CBS PBN Sulphur Compound H - Good Ageing Curing conditions: 50' @ 153 C SBR 1710 HAF black Stearic acid Petroleum-based softener Zinc oxide TMTD PBN MBTS Amount (pphr) 100 50 2 4.5 3 1.0 1.0 1.75 100 50 2 4.5 3 3 1.0 1.0 100 50 2 4.5 3 1.0 1.0 1.75 100 50 2 4.5 3 3 1.0 1.0
16
Butyl Rubber
Butyl Rubber
Ingredient Compound J - General Purpose Curing conditions: 40' @ 153 C Polysar 301 (high unsaturation) FEF black Zinc oxide Stearic acid MBT TMT Sulphur Compound K - Good Ageing Curing conditions: 90' @ 153 C Amount (pphr) 100 50 5 2 0.5 1.0 2 50 25 2 4 2
Polysar 100 butyl (low unsaturation) 100 HAF black Zinc oxide Sulphur MBTS GMF
17
Appendix 1
Polychloroprene
Ingredient Compound L - General Purpose Curing conditions: 60' @ 153 C Neoprene type WRT Light calcined magnesia PBN Stearic acid SRF black Petroleum-based softener Robac 22 Zinc oxide Compound M - Natural Ageing Curing conditions: 60' @ 153 C Neoprene type WRT Light calcined magnesia Akroflex CD Stearic acid SRF black Petroleum-based softener DOTG TMT-MS Sulphur Zinc oxide Compound N - Heat Ageing Curing conditions: 60' @ 153 C Neoprene type WRT Light calcined magnesia Aranox Akroflex CD Octamine Stearic acid SRF black Precipitated calcium carbonate Low volatile process oil Robac 22 Zinc oxide Amount (pphr) 100 4 2 0.5 40 5 0.75 5 100 4 2 0.5 50 5 0.75 0.75 0.75 5 100 4 0.5 2 3.5 0.5 30 90 8 1 25
18
Nitrile Rubber
Nitrile Rubber
Ingredient Compound P - General Purpose Curing conditions: 40' @ 153 C Nitrile rubber ca. 32-34% acrylonitrile) SRF black DOP Zinc oxide Stearic acid PBN MBTS Sulphur Compound R - Good Ageing Curing conditions: 30' @ 153 C Nitrile rubber (ca. 35% acrylonitrile) SRF black DOP Polypropylene adipate Zinc oxide Stearic acid Flectol H TMTD CBS 50 10 10 5 1 2 3 3 50 20 5 1 1 1.5 1.5 100 Amount (pphr) 100
19
Appendix 1
Miscellaneous
Ingredient Compound S - Acrylate Rubber Curing conditions: 90' @ 153 C Hycar 4021 SRF black Stearic acid Triethylene tetramine TMTM Sulphur Compound T Chlorosulphonated polyethylene Curing conditions: 30' @ 153 C Hypalon 20 Precipitated calcium carbonate Hydrogenated wood rosin Litharge MBTS Flectol H Process oil Robac P25 Light calcined magnesia Compound W - Polysulphide Rubber Curing conditions: 30' @ 141 C Thiokol St SRF black Stearic acid GMF Zinc oxide Compound X - Silicone Rubber Curing conditions: 10' @ 135 C Post cure 1 h @ 150 C, 24 h @ 250 C in air Dimethyl silicone gum (slightly unsaturated) Diatomaceous silica Fine silica Ferric oxide 2,4-dichlorobenzoyl peroxide in silicone fluid Amount (pphr) 100 50 1 2 1 3 100 45 5 20 0.5 2 10 0.75 10 100 60 3 1.5 0.5 100 45 36 1 2
20
New Compounds
New Compounds
Ingredient Compound N1 - FVMQ Curing conditions: 10' @ 171 C, Post cure 4 h @ 200 C in air Compound N2 - HNBR Curing conditions: 30' @ 180 C Silastic LS 238 OU Slastic HT-1 DHBP (50% silicone oil) Zetpol 2000L Spheron 4000 Naugard 445 Rhenogran ZMMBI 50 Zinc Oxide Active Peroximon F40 Compound N3 - Epoxidised natural Curing conditions: 23.5' @ 141 C Based on Epoxyprene 50, low black loading, sulphur, TMTD, CBS and stabilised. Details confidential. Compound N4 - Chlorinated polyethylene Curing conditions: 30' @ 180 C Tyrin CM 3630 Flectol pastilles Maglite DE SRF N772 black FEF N550 black Britomya BSH Bisoflex TOT Drapex 39 Perkadox 14/40 Rhenogran TAC 50 Compound N5 - Fluorocarbon Curing conditions: 20' @ 170 C, Post cure 24 h @ 225 C in air Compound N6 - Exxpro Curing conditions: 45' @ 150 C Viton A-202C MT N990 Black Sturge VE Maglite DE Exxpro MDX90-10 HAF N330 Black Stearic Acid Zinc oxide Tetrone A 100 0.2 10 60 50 20 35 4 6.25 5.6 100 20 6 3 100 50 2 0.5 1 Amount (pphr) 100 1 0.9 100 60 1.5 3 3 8
21
Appendix 1
New Compounds (continued)

Ingredient Compound N7 - Epichlorohydrin Curing conditions: 37' @ 165 C Hydrin C65 SRF N772 black Winnofil S Paraplex G50 DOP Vulkanox MB Stearic acid Span 60 Zisnet F DPG Maglite DE Compound N8 - EPDM Curing conditions: 17.5' @ 165 C Vistalon 7000 Zinc Oxide Stearic Acid SRF N772 Black FEF N550 Black Strukpar 2280 Sulphur TMTD ZDMC NDBC Sulfasan R Compound N9 - EVA Curing conditions: 30' @ 165 C Post cure 2 h @ 165 C in steam Levapren 400 Staboxal PCD Zinc stearate Vulkanox DDA FEF N550 Black Mistron Vapour Perkadox 14/40 TAC Compound N10 - PU Curing conditions: 7.5' @ 165 C Adiprene FM FEF N550 Black DBP Stearic Acid Dicup 40C Rhenogran TAC50 Amount (pphr) 100 70 5 5 5 1 1 1 1 0.3 5 100 10 2 45 60 59 1 2.5 2.67 2 1.7 100 3 2 1 30 50 6 4 100 40 5 1 3 2
22
Participants Compounds
Participant's Compounds
Details of most of the formulations are not disclosed. Compound P1 Blend of two EPDM copolymers, one with high ethylene content and medium Mooney viscosity, the other with medium ethylene content and low Mooney viscosity. Contains carbon black, zinc oxide, TMQ, paraffinic process oil, dicumyl peroxide and a sulphur donor. Silicone gum blended to give a methylvinylsiloxane content of 0.31% Silicone processing aid Precipitated silica Fumed silica Vinyl specific peroxide Urea Natural rubber Activators Fillers Process aids 6PPD TMQ Antiozonant wax Sulphenamide TMTM Sulphur NBR (28% ACN) Mineral fillers Silica Zinc oxide Stearic acid Antioxidants Sulphur cure system 100 7 105 50 3 2 4 0.75 0.1 1.5 100 100 25 10 1 (pphr)
Compound P2
Compound P8
Compound P10
(pphr)
23
24
APPENDIX 2 WEATHERING RESULTS
25
26
Natural Rubber - Standard
Compound A (natural rubber - standard)

Table 1. Property changes after 6 months' exposure
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 29.3 516 3.38 15.7 21.7 32 7 5.03 20.2 -7.6 -189 1.65 4.5 -26 -37 49 29 75 Weathering Period After 6 months' exposure 81 Difference 5.8 % Change 8
Compound A (natural rubber - standard)

Table 2. Estimated changes after 6 months at 45 C
Property % Change after 6 months of weathering 7.7 % Change after 6 months at 45 C 10.7 % Change due to weathering effects alone -3 % Change due to 10 years in UK -4
Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa)
-25.9 -36.6 48.8 28.7
-15.7 -42.4 11.2 10.8
-10 6 38 18
-1 5 8 54 26
27
Compound A
Hardness Compound A
86
84
82
Hardness (Micro-IRHD)
80
78
76
74
72
70 0 30 60 90 Weathering Period (Days) 120 150 180
Tensile Strength Compound A

32.0
30.0
28.0
Tensile Strength (MPa)
26.0
24.0
22.0
20.0
18.0 0 30 60 90 Weathering Period (Days) 120 150 180
28
Natural Rubber - Standard
Elongation at Break Compound A

650
600
550
Elongation at Break (%)
500
450
400
350
300
Modulus at 100% Compound A

10.00
8.00
Modulus at 100% (MPa)
6.00
4.00
2.00
29
Compound A
Modulus at 300% Compound A

30.0
25.0
20.0
15.0
10.0
5.0
30
Natural Rubber - Good Ageing
Compound B (natural rubber - good ageing)

Compound B (natural rubber - good ageing)

Property % Change after 6 months of weathering 6.2 % Change after 6 months at 45 C 5. 9 % Change due to weathering effects alone 0 % Change due to 10 years in UK 0
-20.9 -22.4 8.3 8.9
0.4 -24.8 67.2 17.4
-21 2 -59 -8
-3 0 3 -8 4 -1 2
31
Compound B
Hardness Compound B
76
74
72
70
68
66
64
62
Tensile Strength Compound B

30.0
28.0
26.0
24.0
22.0
20.0
32
Natural Rubber - Good Ageing
Elongation at Break Compound B

750
700
650
600
550
500
450
400
Modulus at 100% Compound B

4.00
3.00
2.00
1.00
33
Compound B
Modulus at 300% Compound B

20.0
15.0
10.0
5.0
34
Natural Rubber - Mineral Filler Loaded
Compound C (natural rubber - mineral filler loaded)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 24.2 644 1.41 4.63 11.8 54 0 1.30 3.82 -12.4 -104 -0.11 -0.81 -51 -16 -8 -17 54 Weathering Period After 6 months' exposure 58 Difference 3.8 % Change 7
Compound C (natural rubber - mineral filler loaded)

-51.2 -16.1 -7.8 -17.5
-3.3 -3.0 15.6 -0.2
-48 -13 -23 -1 7
-6 8 -1 9 -3 3 -2 5
35
Compound C
Hardness Compound C
66 64 62 60 58 56 54 52 50 48 0 30 60 90 Weathering Period (Days) 120 150 180
Tensile Strength Compound C

30.0
25.0
20.0
15.0
10.0
36
Natural Rubber - Mineral Filler Loaded
Elongation at Break Compound C

750
700
650
600
550
500
450
Modulus at 100% Compound C

3.00
2.50
2.00
1.50
1.00
0.50
37
Compound C
Modulus at 300% Compound C

8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00
38
Natural Rubber - Mineral Filler (Heavy Loaded)
Compound D (natural rubber - mineral filler (heavy loaded))

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 11.3 590 1.57 4.50 5.47 38 5 1.45 3.95 -5.8 -205 -0.12 -0.55 -52 -35 -8 -12 62 Weathering Period After 6 months' exposure 82 Difference 21 % Change 33
Compound D (natural rubber - mineral filler (heavy loaded))

Property % Change after 6 months of weathering 33.4 % Change after 6 months at 45 C -0.3 % Change due to weathering effects alone 34 % Change due to 10 years in UK 48
-51.6 -34.7 -7.6 -12.2
-25.6 -22.7 29.3 12.2
-26 -12 -37 -24
-3 7 -1 7 -5 3 -3 5
39
Compound D
Hardness Compound D
100
95
90
85
80
75
70
65
Tensile Strength Compound D

14.0
12.0
10.0
8.0
6.0
4.0
40
Natural Rubber - Mineral Filler (Heavy Loaded)
Elongation at Break Compound D

Modulus at 100% Compound D

4.00
3.00
2.00
1.00
41
Compound D
Modulus at 300% Compound D

8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00
42
Styrene Butadiene Rubber - General Purpose
Compound E (styrene butadiene rubber - general purpose)

Compound E (styrene butadiene rubber - general purpose)

Property % Change after 6 months of weathering 7.8 % Change after 6 months at 4 5 C 9.4 % Change due to weathering effects alone -2 % Change due to 10 years in UK -2
-12.5 -24.5 30.5 24.3
-4.5 -30.7 60.9 43.9
-8 6 -30 -20
-1 1 9 -4 3 -2 8
43
Compound E
Hardness Compound E
80 78 76 74
72 70 68 66 64 62 60 0 30 60 90 Weathering Period (Days) 120 150 180
Tensile Strength Compound E

32.0
30.0
28.0
26.0
24.0
22.0
44
Elongation at Break Compound E

600
550
500
450
400
350
Modulus at 100% Compound E

6.00
5.00
4.00
3.00
2.00
1.00
45
Compound E
Modulus at 300% Compound E

30.0
25.0
20.0
15.0
10.0
5.0
46
Styrene Butadiene Rubber - Good Ageing
Compound F (styrene butadiene rubber - good ageing)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 27.2 589 1.93 11.3 21.4 48 3 2.00 11.2 -5.8 -106 0.07 -0.10 -21 -18 4 -0.9 64 Weathering Period After 6 months' exposure 66 Difference 1.9 % Change 3
Compound F (styrene butadiene rubber - good ageing)

Property % Change after 6 months of weathering 3.0 % Change after 6 months at 45 C 5. 8 % Change due to weathering effects alone -3 % Change due to 10 years in UK -4
-21.3 -18.0 3.6 -0.9
-8.5 -9.8 37.8 22.1
-13 -8 -34 -23
-1 8 -1 2 -4 9 -3 3
47
Compound F
Hardness Compound F
70 69 68 67
Tensile Strength Compound F

30.0
28.0
26.0
24.0
22.0
20.0
48
Elongation at Break Compound F

700
650
600
550
500
450
Modulus at 100% Compound F

4.00
3.00
2.00
1.00
49
Compound F
Modulus at 300% Compound F

20.0
15.0
10.0
5.0
50
Compound G (styrene butadiene rubber - general purpose)

Compound G (styrene butadiene rubber - general purpose)

-12.4 -23.1 25.5 27.6
-12.4 -28.2 53.3 41.1
0 5 -28 -14
0 7 -4 0 -1 9
51
Compound G
Hardness Compound G
74
72
70
68
66
64
62
Tensile Strength Compound G

24.0
22.0
20.0
18.0
52
Elongation at Break Compound G

700
650
600
550
500
450
400
Modulus at 100% Compound G

4.00
3.00
2.00
1.00
53
Compound G
Modulus at 300% Compound G

20.00
15.00
10.00
5.00
54
Compound H (styrene butadiene rubber - good ageing)

Table 1. Property changes after six months' exposure
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 20.6 604 1.44 8.34 16.0 54 3 1.37 7.64 -4.6 -61 -0.07 -0.70 -22 -10 -5 -8 59 Weathering Period After 6 months' exposure 62 Difference 3.1 % Change 5
Compound H (styrene butadiene rubber - good ageing)

-22.3 -10.1 -4.9 -8.4
-12.3 -42.9 49.3 81.1
-10 33 -54 -89
-1 4 47 -7 7 -12 8
55
Compound H
Hardness Compound H
65 64 63 62
Tensile Strength Compound H

24.0
22.0
20.0
18.0
16.0
14.0
56
Elongation at Break Compound H

750
700
650
600
550
500
450
400
Modulus at 100% Compound H

3.00
2.50
2.00
1.50
1.00
0.50
57
Compound H
Modulus at 300% Compound H

14.00
12.00
10.00
8.00
6.00
4.00
2.00
58
Butyl Rubber - General Purpose
Compound J (butyl rubber - general purpose)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 12.7 419 2.62 9.64 12.3 41 2 2.56 9.52 -0.4 -7 -0.06 -0.12 -3 -2 -2 -1 67 Weathering Period After 6 months' exposure 67 Difference 0.4 % Change 0.6
Compound J (butyl rubber - general purpose)

-3.1 -1.7 -2.3 -1.2
-3.1 -8.1 11.1 0.0
0 6 -13 -1
0 9 -1 9 -2
59
Compound J
Hardness Compound J
72 71 70 69
Tensile Strength Compound J

15.0
14.0
13.0
12.0
11.0
60
Butyl Rubber - General Purpose
Elongation at Break Compound J

500
450
400
350
Modulus at 100% Compound J

5.00
4.00
3.00
2.00
1.00
61
Compound J
Modulus at 300% Compound J

16.00
14.00
12.00
10.00
8.00
6.00
4.00
2.00
62
Butyl Rubber - Good Ageing
Compound K (butyl rubber - good ageing)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 14.0 614 2.12 6.72 13.4 55 9 2.16 6.95 -0.6 -55 0.04 0.23 -4 -9 2 3 79 Weathering Period After 6 months' exposure 80 Difference 0.6 % Change 0.8
Compound K (butyl rubber - good ageing)

-4.3 -9.0 1.9 3.4
-13.6 -21.8 16.0 0.0
9 13 -14 3
13 18 -2 0 5
63
Compound K
Hardness Compound K
85 84 83 82
Tensile Strength Compound K

17.0
16.0
15.0
14.0
13.0
12.0
11.0
64
Butyl Rubber - Good Ageing
Elongation at Break Compound K

750
700
650
600
550
500
Modulus at 100% Compound K

4.00
3.00
2.00
1.00
65
Compound K
Modulus at 300% Compound K

12.00
10.00
8.00
6.00
4.00
2.00
66
Polychloroprene - General Purpose
Compound L (polychloroprene - general purpose)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 21.6 318 3.91 21.0 18.9 26 9 4.32 20.9 -2.7 -49 0.41 -0.10 -13 -15 10 -0.5 69 Weathering Period After 6 months' exposure 73 Difference 3.6 % Change 5
Compound L (polychloroprene - general purpose)

-12.5 -15.4 10.5 -0.5
0.0 -5.7 -4.1 0.5
-13 -10 15 -1
-1 8 -1 4 21 -1
67
Compound L
Hardness Compound L
80
78
76
74
72
70
68
66
Tensile Strength Compound L

26.0
24.0
22.0
20.0
18.0
16.0
68
Polychloroprene - General Purpose
Elongation at Break Compound L

400
350
300
250
Modulus at 100% Compound L

7.00
6.00
5.00
4.00
3.00
2.00
1.00
69
Compound L
Modulus at 300% Compound L

30.0
25.0
20.0
15.0
10.0
5.0
70
Polychloroprene - Natural Ageing
Compound M (polychloroprene - natural ageing)

Compound M (polychloroprene - natural ageing)

-6.8 -10.8 12.3 5.3
-4.8 -8.1 7. 0 5.9
-2 -3 5 -1
-3 -4 8 -1
71
Compound M
Hardness Compound M
80
78
76
74
72
70
68
66
Tensile Strength Compound M

26.0
24.0
22.0
20.0
18.0
16.0
72
Polychloroprene - Natural Ageing
Elongation at Break Compound M

400
350
300
250
Modulus at 100% Compound M

6.00
5.00
4.00
3.00
2.00
1.00
73
Compound M
Modulus at 300% Compound M

30.0
25.0
20.0
15.0
10.0
5.0
74
Polychloroprene - Heat Ageing
Compound N (polychloroprene - heat ageing)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 10.3 368 2.89 8.28 8.12 28 4 4.19 8.54 -2.2 -84 1.3 0.26 -21 -23 45 3 80 Weathering Period After 6 months' exposure 91 Difference 11 % Change 14
Compound N (polychloroprene - heat ageing)

Property % Change after 6 months of weathering 13.6 % Change after 6 months at 45 C 3.5 % Change due to weathering effects alone 10 % Change due to 10 years in UK 14
-21.2 -22.8 45.0 3.1
0.0 -4.9 27.0 4. 6
-21 -18 18 -1
-3 0 -2 6 26 -2
75
Compound N
Hardness Compound N
96 94 92 90
Tensile Strength Compound N

12.0
11.0
10.0
9.0
8.0
7.0
76
Polychloroprene - Heat Ageing
Elongation at Break Compound N

450
400
350
300
250
Modulus at 100% Compound N

6.00
5.00
4.00
3.00
2.00
1.00
77
Compound N
Modulus at 300% Compound N

14.00
12.00
10.00
8.00
6.00
4.00
2.00
78
Nitrile Rubber - General Purpose
Compound P (nitrile rubber - general purpose)

Compound P (nitrile rubber - general purpose)

Property % Change after 6 months of weathering 6.7 % Change after 6 months at 45 C 11.8 % Change due to weathering effects alone -5 % Change due to 10 years in UK -7
-4.6 -16.4 8.1 21.6
11.5 -32.4 29.6 54.5
-16 16 -22 -33
-2 3 23 -3 1 -4 7
79
Compound P
Hardness Compound P
64
62
60
58
56
54
52
Tensile Strength Compound P

24.0
22.0
20.0
18.0
16.0
14.0
12.0
80
Nitrile Rubber - General Purpose
Elongation at Break Compound P

650
600
550
500
450
400
350
Modulus at 100% Compound P

4.00
3.00
2.00
1.00
81
Compound P
Modulus at 300% Compound P

16.00
14.00
12.00
10.00
8.00
6.00
4.00
2.00
82
Polychloroprene - Good Ageing
Compound R (polychloroprene - good ageing)

Compound R (polychloroprene - good ageing)

Property % Change after 6 months of weathering 9.3 % Change after 6 months at 45 C 17.6 % Change due to weathering effects alone -8 % Change due to 10 years in UK -1 2
-25.5 -21.7 10.8 20.2
-55.1 63.5 34.2
33 -53 -14
48 -7 5 -2 0
83
Compound R
Hardness Compound R
66
64
62
60
58
56
54
Tensile Strength Compound R

26.0
24.0
22.0
20.0
18.0
16.0
84
Nitrile Rubber - Good Ageing
Elongation at Break Compound R

750
700
650
600
550
500
450
Modulus at 100% Compound R

4.00
3.00
2.00
1.00
85
Compound R
Modulus at 300% Compound R

14.00
12.00
10.00
8.00
6.00
4.00
2.00
86
Miscellaneous - Acrylate Rubber
Compound S (miscellaneous - acrylate rubber)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 11.3 223 3.47 11.6 241 3.18 0.3 18 -0.29 3 8 -8 52 Weathering Period After 6 months' exposure 52 Difference 0.4 % Change 0.8
Compound S (miscellaneous - acrylate rubber)

2.7 8.1 -8.4 -
-19.7 -13.5 -0.9 -
22 22 -7 -
32 31 -1 1 -
87
Compound S
Hardness Compound S
60
58
56
54
52
50
48
Tensile Strength Compound S

14.0
13.0
12.0
11.0
10.0
88
Miscellaneous - Acrylate Rubber
Elongation at Break Compound S

300
280
260
240
220
200
180
Modulus at 100% Compound S

6.00
5.00
4.00
3.00
2.00
1.00
89
Compound S
90
Miscellaneous - Chlorosulphonated Polyethylene
Compound T (miscellaneous - chlorosulphonated polyethylene)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 8.00 438 2.88 6.27 6.00 26 3 3.99 5.23 -2.0 -175 1.1 -1.0 -25 -40 39 -17 53 Weathering Period After 6 months' exposure 67 Difference 14 % Change 27
Compound T (miscellaneous - chlorosulphonated polyethylene)

-25.0 -40.0 38.5 -16.6
27.5 -37.4 -2.1 -
-53 -3 41 -
-7 5 -4 58 -
91
Compound T
Hardness Compound T
75
70
65
60
55
Tensile Strength Compound T

10.0
9.0
8.0
7.0
6.0
5.0
92
Miscellaneous - Chlorosulphonated Polyethylene
Elongation at Break Compound T

500
450
400
350
300
250
Modulus at 100% Compound T

6.00
5.00
4.00
3.00
2.00
1.00
93
Compound T
Modulus at 300% Compound T

10.0 9.0 8.0 7.0
6.0 5.0 4.0 3.0 2.0 1.0 0.0 0 30 60 90 Weathering Period (Days) 120 150 180
94
Miscellaneous - Polysulphide Rubber
Compound W (miscellaneous - polysulphide rubber)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 5.69 310 2.01 5.32 24 7 2.43 -0.37 -63 0.42 -7 -20 21 63 Weathering Period After 6 months' exposure 70 Difference 7.3 % Change 12
Compound W (miscellaneous - polysulphide rubber)

-6.5 -20.3 20.9 -
-1.6 -12.9 19.9 -
-5 -7 1 -
-7 -1 1 1 -
95
Compound W
Hardness Compound W
76
74
72
70
68
66
64
62
Tensile Strength Compound W

8.0
7.0
6.0
5.0
4.0
96
Miscellaneous - Polysulphide Rubber
Elongation at Break Compound W

340
320
300
280
260
240
220
Modulus at 100% Compound W

4.00
3.00
2.00
1.00
97
Compound W
98
Miscellaneous - Silicone Rubber
Compound X (miscellaneous - silicone rubber)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 7.03 219 2.89 7.16 239 2.65 0.13 20 -0.24 2 9 -8 54 Weathering Period After 6 months' exposure 55 Difference 1.2 % Change 2
Compound X (miscellaneous - silicone rubber)

1.8 9.1 -8.3 -
-0.1 -8.2 -1.4 -
2 17 -7 -
3 25 -1 0 -
99
Compound X
Hardness Compound X
60
58
56
54
52
Tensile Strength Compound X

9.0
8.0
7.0
6.0
100
Miscellaneous - Silicone Rubber
Elongation at Break Compound X

300
280
260
240
220
200
180
160
Modulus at 100% Compound X

5.00
4.00
3.00
2.00
1.00
101
Compound X
102
New Compound - FVMQ
Compound N1 (FVMQ)
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 7.5 168 4.29 7. 1 17 6 4.03 -0.4 8 -0.26 -5 5 -6 72 Weathering Period After 6 months' exposure 72 Difference 0.0 % Change 0
Compound N1 (FVMQ)
-5.2 4.9 -6.1 -
-2.7 1.2 48.7 -
-3 4 -55 -
-4 5 -7 8 -
103
Compound N1
Hardness Compound N1
76
75
74
73
72
71
70
69
Tensile Strength Compound N1

10.00
9.00
8.00
7.00
6.00
104
New Compound - FVMQ
Elongation at Break Compound N1

220
200
180
160
140
Modulus at 100% Compound N1

6.00
5.00
4.00
105
Compound N1
106
New Compound - HNBR
Compound N2 (HNBR)
Compound N2 (HNBR)
-1.0 -4.3 7.1 11.6
23.5 3.2 941.0 -2.1
-24 -7 -934 14
-3 5 -1 1 -133 4 20
107
Compound N2
75
73
71
69
67

24.0
22.0
20.0
108
New Compound - HNBR

650
600
550
500
450

5.00
4.00
3.00
2.00
109
Compound N2

20.0
18.0
16.0
14.0
12.0
110
New Compound - Epoxidised Natural
Compound N3 (epoxidised natural)

Compound N3 (epoxidised natural)

-13.2 -15.8 5.9 33.8
-83.8 -76.3 27.3 44.6
71 61 -21 -11
10 1 86 -3 1 -1 5
111
Compound N3
64
62
60
58
56
54

30.0
25.0
20.0
112
New Compound - Epoxidised Natural

700
650
600
550
500
450

3.00
2.50
2.00
1.50
113
Compound N3

12.00
10.00
8.00
6.00
114
New Compound - Chlorinated Polyethylene
Compound N4 (chlorinated polyethylene)

Compound N4 (chlorinated polyethylene)

-10.2 -7.7 3.7 -
-0.7 5.1 14.1 -
-10 -13 -10 -
-1 4 -1 8 -1 5 -
115
Compound N4
92
90
88
86
84

20.0
18.0
16.0
14.0
12.0
116
New Compound - Chlorinated Polyethylene

300
250
200
150

12.00
10.00
8.00
6.00
117
Compound N4
118
New Compound - Fluorocarbon
Compound N5 (fluorocarbon)
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 12.9 218 5.22 12.6 242 5.08 -0.3 24 -0.14 -2 11 -3 71 Weathering Period After 6 months' exposure 74 Difference 3.4 % Change 5
Compound N5 (fluorocarbon)
-2.3 10.9 -2.7 -
-0.8 0.0 -0.2 -
-2 11 -2 -
-2 16 -4 -
119
Compound N5
80
78
76
74
72
70
68

15.0
14.0
13.0
12.0
11.0
120
New Compound - Fluorocarbon

280
260
240
220
200

7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
121
Compound N5
122
New Compound - Exxpro
Compound N6 (Exxpro)
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 18.1 215 6.70 17.2 237 5.22 -0.9 22 -1.48 -5 10 -22 67 Weathering Period After 6 months' exposure 71 Difference 3.5 % Change 5
Compound N6 (Exxpro)
-5.0 10.2 -22.1 -
-22.7 -25.6 0.0 -
18 36 -22 -
25 51 -3 2 -
123
Compound N6
76
74
72
70
68
66
64
62

20.0
19.0
18.0
17.0
16.0
124
New Compound - Exxpro

280
260
240
220
200

9.00
8.00
7.00
6.00
5.00
4.00
125
Compound N6
126
New Compound - Epichlorohydrin
Compound N7 (epichlorohydrin)
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 9.6 299 4.47 9. 6 211 5.04 0 -87 0.57 0 -29 13 79 Weathering Period After 6 months' exposure 84 Difference 5.3 % Change 7
Compound N7 (epichlorohydrin)
0.0 -29.2 12.8 -
1.6 -43.1 3. 6 -
-2 14 9 -
-2 20 13 -
127
Compound N7
90 88 86 84

12.00
11.00
10.00
9.00
8.00
128
New Compound - Epichlorohydrin

400
350
300
250
200
150

6.50
6.00
5.50
5.00
4.50
4.00
3.50
129
Compound N7
130
New Compound - EPDM
Compound N8 (EPDM)
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 16.3 365 4.38 14.0 15.9 35 3 4.24 14.1 -0.5 -12 -0.14 0.1 -3 -3 -3 1 79 Weathering Period After 6 months' exposure 79 Difference 0.0 % Change 0
Compound N8 (EPDM)
-2.9 -3.3 -3.2 1.0
0.6 -27.1 34.5 25.7
-3 24 -38 -25
-5 34 -5 4 -3 5
131
Compound N8
84
82
80
78
76

20.0
18.0
16.0
14.0
132
New Compound - EPDM

500
450
400
350
300
250

6.00
5.50
5.00
4.50
4.00
3.50
133
Compound N8

20.0
18.0
16.0
14.0
12.0
134
New Compound - EVA
Compound N9 (EVA)
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 11.7 173 7.93 12.1 187 8.91 0.4 14 0.98 4 8 12 79 Weathering Period After 6 months' exposure 82 Difference 3.2 % Change 4
Compound N9 (EVA)
3.8 8.0 12.4 -
-0.9 -6.4 -1.3 -
5 14 14 -
7 21 20 -
135
Compound N9
85
83
81
79
77

14.0
13.0
12.0
11.0
10.0
136
New Compound - EVA

250
200
150

11.00
10.00
9.00
8.00
7.00
137
Compound N9
138
New Compound - PU
Compound N10 (PU)

Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 14.7 195 6.24 17.2 174 8.51 2.5 -21 2.27 17 -11 36 74 Weathering Period After 6 months' exposure 79 Difference 4.6 % Change 6
Compound N10 (PU)

17.0 -10.8 36.4 -
-50.7 -50.8 -84.0 -
68 40 120 -
97 57 17 2 -
139
Compound N10

86
84
82
80
78
76
74
72

20.0
18.0
16.0
14.0
140
New Compound - PU

250
200
150

11.00
10.00
9.00
8.00
7.00
6.00
5.00
141
Compound N10
142
Participant Compound - EPR
Compound P1
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 13.2 504 2.15 8.47 12.0 556 2.10 7.32 -1.1 51 -0.05 -1.15 -9 10 -2 -14 71 Weathering Period After 6 months' exposure 71 Difference -0.3 % Change -0.4
Compound P1
Property % Change after 6 months of weathering -0.4 % Change after 6 months at 45 C -1.4 % Change due to weathering effects alone 1 % Change due to 10 years in UK 1
-8.7 10.2 -2.3 -13.6
0.8 0.0 291.6 -
-9 10 -294 -
-1 4 15 -42 0 -
143
Compound P1
Hardness Compound P1
76 75 74 73
Tensile Strength Compound P1

18.0
17.0
16.0
15.0
14.0
13.0
12.0
11.0
144
Participant Compound - EPR
Elongation at Break Compound P1

600
550
500
450
Modulus at 100% Compound P1

4.00
3.00
2.00
1.00
145
Compound P1

14.00
12.00
10.00
8.00
6.00
146
Participant Compound - Medium Nitrile Rubber
Compound P3
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 15.7 242 10.6 14.7 22 8 9.9 -1.0 -14 -0.8 -7 -6 -7 83 Weathering Period After 6 months' exposure 85 Difference 2.0 % Change 2
Compound P3
-6.6 -5.7 -7.2 -
-1.9 -35.1 18.9 -
-5 29 -26 -
-7 42 -3 7 -
147
Compound P3
90
88
86
84
82
80
78

18.0
17.0
16.0
15.0
14.0
13.0
148
Participant Compound - Medium Nitrile Rubber

280
270
260
250
240
230
220
210

15.00 14.00 13.00 12.00
11.00 10.00 9.00 8.00 7.00 6.00 5.00 0 30 60 90 Weathering Period (Days) 120 150 180
149
Compound P3
150
Participant Compound - Nitrile Rubber
Compound P4
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 23.7 514 3.02 13.1 20.0 44 3 3.22 13.6 -3.7 -71 0.2 0.5 -15 -14 7 4 67 Weathering Period After 6 months' exposure 67 Difference 0.2 % Change 0.3
Compound P4
-15.5 -13.9 6.6 4.0
-42.2 -69.5 39.4 61.8
27 56 -33 -58
38 79 -4 7 -8 3
151
Compound P4
74
72
70
68
66
64
62

26.0
24.0
22.0
20.0
18.0
152

600
550
500
450
400

5.00
4.50
4.00
3.50
3.00
2.50
153
Compound P4

18.0
16.0
14.0
12.0
154
Participant Compound - EPDM
Compound P5
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 12.1 139 6.62 13.3 150 6.09 1.2 11 -0.53 10 8 -8 71 Weathering Period After 6 months' exposure 71 Difference 0.0 % Change 0.0
Compound P5
9.7 7.8 -8.0 -
3. 3 -23.0 -
6 31 -
9 44 -
155
Compound P5
75
74
73
72
71
70
69
68

17.0
16.0
15.0
14.0
13.0
12.0
11.0
10.0
156
Participant Compound - EPDM

200
180
160
140
120

9.00
8.00
7.00
6.00
5.00
157
Compound P5
158
Participant Compound - Vamac G
Compound P6
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 11.6 233 7.37 12.1 22 7 8.25 0.5 -6 0.88 4 -2 12 78 Weathering Period After 6 months' exposure 83 Difference 4.9 % Change 6
Compound P6
3.9 -2.4 11.9 -
0. 0 4.7 42.5 -
4 -7 -31 -
6 -1 0 -4 4 -
159
Compound P6
89
87
85
83
81
79
77

14.0
13.0
12.0
11.0
160
Participant Compound - Vamac G

300
250
200

10.00
9.00
8.00
7.00
6.00
161
Compound P6
162
Participant Compound - W Type Polychloroprene
Compound P7
Compound P7
-20.1 -17.6 20.2 -
-6.6 -18.6 25.9 -
-14 1 -6 -
-1 9 1 -8 -
163
Compound P7
77
75
73
71
69
67
65

17.0
16.0
15.0
14.0
13.0
12.0
11.0
164
Participant Compound - W Type Polychloroprene

350
300
250

5.00
4.50
4.00
3.50
3.00
2.50
165
Compound P7
166
Participant Compound - Natural Rubber
Compound P8
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 12.0 542 1.00 5.63 9. 4 38 5 1.81 7.16 -2.6 -157 0.81 1.53 -22 -29 81 27 58 Weathering Period After 6 months' exposure 69 Difference 10.9 % Change 19
Compound P8
-21.8 -28.9 81.0 27.2
0.8 -13.1 145.0 -2.3
-23 -16 -64 29
-3 2 -2 3 -9 1 42
167
Compound P8

14.0
13.0
12.0
11.0
10.0
9.0
168
Participant Compound - Natural Rubber

600
550
500
450
400
350

3.00
2.50
2.00
1.50
1.00
0.50
169
Compound P8

10.00
9.00
8.00
7.00
6.00
5.00
170
Participant Compound - Santoprene 101 55 V185
Compound P9
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 5.8 460 1.98 4.10 4.4 397 1.75 3.55 -1.4 -63 -0.23 -0.55 -24 -14 -12 -13 68 Weathering Period After 6 months' exposure 68 Difference -0.1 % Change -0.1
Compound P9
Property % Change after 6 months of weathering -0.1 % Change after 6 months at 45 C 0.0 % Change due to weathering effects alone 0 % Change due to 10 years in UK 0
-23.8 -13.7 -11.6 -13.4
2.9 -2.0 -1.2
-27 -10 -12
-3 8 -1 4 -1 7
171
Compound P9
72
71
70
69
68
67
66

7.00
6.00
5.00
4.00
172
Participant Compound - Santoprene 101 55 V185

500
450
400
350

3.00
2.50
2.00
1.50
1.00
173
Compound P9

6.00
5.00
4.00
3.00
174
Compound P10
Property Initial Hardness (IRHD) Tensile Properties Tensile Strength (MPa) Elongation at Break (%) Modulus at 100% (MPa) Modulus at 300% (MPa) 11.8 524 3.19 5.80 6. 7 41 9 3.47 5.43 -5.1 -104 0.28 -0.37 -43 -20 9 -6 83 Weathering Period After 6 months' exposure 91 Difference 7.5 % Change 9
Compound P10
-43.0 -19.9 8.8 -6.4
-2.5 -29.2 22.9 33.1
-40 9 -14 -39
-5 8 13 -2 0 -5 6
175
Compound P10

94
92
90
88
86
84
82

14.0 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 0 30 60 90 Weathering Period (Days) 120 150 180
176

600
550
500
450
400
350

5.00
4.50
4.00
3.50
3.00
2.50
177
Compound P10

9.00
8.00
7.00
6.00
5.00
178
Figure 1 Surface cracking of natural rubber Compound C
Figure 2 Surface cracking of natural rubber Compound D
179
180
Ozone Results
APPENDIX 3 OZONE RESULTS
181
Appendix 3
182
Ozone Results
Table 1. Time to Grade 1 cracking (first cracking) at 50 pphm, h

Compound reference A B C D E F G H J K P R W N3 N7 P3 P4 P8 P10 Strain level, % 5 4 360 2 8 24 2 4 72 # # 48 240 # 8 # 24 360 # # 10 4 4 2 8 2 2 4 8 # # 2 456 # 2 # 8 48 # 408 15 4 4 2 2 2 2 4 4 # 38 4 2 48 240 2 # 2 24 # 72 20 4 4 2 2 2 2 4 4 # 288 2 4 19 2 2 576 2 16 # 72 30 4 4 2 2 2 2 4 4 57 6 28 8 2 4 96 2 57 6 2 8 264 24
# Cracking was never observed
183
Time to first cracking (hours)
184
Ozone Resistance Results at 50 pphm
Appendix 3
700
600
500
400
300
5% Strain 10% Strain 15% Strain 20% Strain 30% Strain
200
100
0 E F G H J K P R W N3 N7 P3 P4 P8 P10 Compound References
Figure 1
Ozone Results
Table 2. Time to Grade 3 cracking at 50 pphm, h

Compound reference A B C D E F G H P R N3 P3 P4 P8 P10 Strain level, % 5 360 # 432 360 48 24 72 72 216 # 48 72 384 # # 10 # # 216 360 8 8 16 48 192 45 6 24 24 120 # # 15 552 600 72 72 24 24 8 16 192 96 24 16 72 # 72 20 36 0 432 72 72 24 24 8 16 192 24 16 16 72 # 72 30 21 6 36 0 72 48 24 48 8 16 12 0 24 48 16 72 264 72
# Cracking was either never recorded or did not reach Grade 3 level
185
Time to Grade 3 cracking (hours)
186
Appendix 3
700
600
500
400
300
200
100
0 D E F G H P R N3 P3 P4 P8 P10 Compound References
Figure 2
Ozone Results
Table 3. Time to Grade 1 cracking (first cracking) at 200 pphm, h

Compound reference A B C D J K L M N P R W P4 P8 P10 Strain level, % 5 4 4 2 4 # # 144 # # 2 48 # 48 # # 10 2 2 2 2 # # 144 # 14 4 2 16 96 16 # 16 15 2 2 2 2 # # 96 # # 2 2 72 8 19 2 2 20 2 2 2 2 552 168 72 192 96 2 2 48 4 48 2 30 2 2 2 2 36 0 12 0 48 14 4 96 2 2 48 2 16 2
# Cracking was never observed
187
Time to first cracking (hours)
188
Appendix 3
600
500
400
300
200
100
0 D J K L M N P R W P4 P8 P10 Compound References
Figure 3
Ozone Results
Table 4. Time to Grade 3 cracking at 200 pphm, h

Compound reference A B C D L M N P R W P4 P8 P10 Strain level, % 5 48 24 8 # 168 # # 2 48 # 72 # # 10 72 48 48 # 168 # 14 4 8 24 # 24 # 24 15 48 24 48 16 144 # # 8 8 432 24 192 8 20 24 16 48 16 96 192 96 8 4 432 24 48 8 30 48 16 48 16 96 14 4 96 8 4 38 4 16 16 8
# Cracking was either never recorded or did not reach Grade 3 level
189
Time to Grade 3 cracking (hours)
190
Appendix 3
500
450
400
350
300
250
200
150
100
50
0 D L M N P R W P4 P8 P10 Compound References
Figure 4
Ozone Results
Compound P4 Grade 1 & 3 Cracking at 50 pphm

predicted for grade 3 predicted for grade 1 40.0 35.0 30.0 25.0
Strain (%)
observed for grade 3 observed for grade 1
20.0 15.0 10.0 5.0 0.0 0 100 200 300 Time (hours) 400 500 600 700
Figure 5
Compound W Grade of Cracking at 200 pphm

predicted for grade 1 40.0 35.0 30.0 25.0 observed for grade 1
Strain (%)
20.0 15.0 10.0 5.0 0.0 0 20 40 60 80 100 Time (hours) 120 140 160 180 200
Figure 6
191
Appendix 3
Compound P10 Grade 1 Cracking at 50 pphm

predicted for grade 1 40.0 35.0 30.0 25.0 observed for grade 1
Strain (%)
20.0 15.0 10.0 5.0 0.0 0 100 200 300 Time (hours) 400 500 600 700
Figure 7
192

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Accelerated Weathering and Ozone Test Results

R.P. Brown, T. Butler and S.W. Hawley

Europes leading independent plastics and rubber specialists

R.P. Brown, T. Butler and S.W. Hawley Rapra Technology Limited

Rapra Technology Limited

Practical Guide to Polyethylene

First Published in 2001 by

Rapra Technology Limited

Copyright 2001 Rapra Technology Limited

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

2.1 Original Materials

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2.2 New Materials

Compound P8 Compound P9 Compound P10

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

3 PREPARATION OF TEST PIECES

5 EXPOSURE OF TEST PIECES

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5.2 Ozone Exposure

6 WEATHERING RESULTS (APPENDIX 2)

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

6.3 Interpretation of results

Copyright 2001 Rapra Technology Limited

7 OZONE RESULTS (APPENDIX 3)

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Copyright 2001 Rapra Technology Limited

8.1.4 Tensile Strength

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

8.1.5 Elongation at Break

8.1.6 Effect of Temperature

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

APPENDIX 1 COMPOUND DETAILS

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Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Copyright 2001 Rapra Technology Limited

Styrene Butadiene Rubber

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Copyright 2001 Rapra Technology Limited

New Compounds (continued)

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

APPENDIX 2 WEATHERING RESULTS

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Natural Rubber - Standard

Compound A (natural rubber - standard)

Compound A (natural rubber - standard)

-25.9 -36.6 48.8 28.7

-15.7 -42.4 11.2 10.8

Copyright 2001 Rapra Technology Limited

70 0 30 60 90 Weathering Period (Days) 120 150 180

Tensile Strength Compound A

18.0 0 30 60 90 Weathering Period (Days) 120 150 180

Ageing of Rubber - Accelerated Weathering and Ozone Test Results