Brown, R.P. - Butler, T. - Hawley, S.W. - Ageing of Rubber - Accelerated Weathering and Ozone Test Results-Ismithers Rapra Publishing (2010!11!28)

O3 Ageing of Rubber
Accelerated Weathering and

Ozone Test Results
R.P. Brown, T. Butler

and S.W. Hawley
Europe’s 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 government’s Department of Trade and Industry’s Degradation of
Materials in Aggressive Environments Programme.

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

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 over-
looked.
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
2
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
© Copyright 2001 Rapra Technology Limited i

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
Participant’s 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
ii 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 1999–2000 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.
© Copyright 2001 Rapra Technology Limited 1

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 P1–P10 are materials submitted by industry participants:
Compound P1 ethylene propylene copolymer
Compound P2 siloxane material
Compound P3 medium nitrile, carbon black filled with EV sulphur cure
Compound P4 nitrile, NF standard 0115/2
Compound P5 EPDM, NF standard 0115/1
Compound P6 Vamac G material, black filled with a Diak/DOTG cure system
Compound P7 W type polychloroprene with small amount of SBR, carbon black filled,
sulphur/metal oxide cure
Compound P8 natural rubber
Compound P9 thermoplastic rubber—Santoprene 101 55 V185 from AES
Compound P10 nitrile
Compound P2 was not tested for weathering and ozone resistance because it was a special
purpose cellular material.
2 Ageing of Rubber - Accelerated Weathering and Ozone Test Results

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 [2–3]. 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:
10 1
C⋅ ⋅
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 5–7.
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 modulus–time 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.

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 A–D 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.

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 A–D and the SBR compounds E–H. 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 Rubber—Changes in Physical Properties over
40 Years, Rapra Technology Limited, 2000.
2. ISO 37 1994 Rubber, vulcanised or thermoplastic—Determination of tensile stress-

strain properties.
3. ISO 48 1994 Rubber, vulcanised or thermoplastic—Determination of hardness (Hardness

between 10 IRHD and 1000 IRHD).
4. ISO 4665 1998 Rubber, vulcanised—Resistance to weathering.
5. ISO 1431-1 1989 Rubber, vulcanised or thermoplastic—Resistance to ozone cracking –

Static strain test.

APPENDIX 1
COMPOUND DETAILS

Appendix 1

Natural Rubber
Natural Rubber
Amount
Ingredient
(pphr)
Compound A – Standard Smoked sheet 100
Curing conditions: 35' @ 141 °C HAF black 50
Stearic acid 2.5
Pine tar 4.5
Zinc oxide 5
CBS 0.5
PBN 1.0
Sulphur 2.5
Compound B - Good Ageing Smoked sheet 100
Stearic acid 0.5
Pine tar 4.5
Zinc oxide 5
TMTD 2.5
PBN 1.0
MBT 1.0
Compound C - Mineral Filler Loaded Smoked sheet 100
Curing conditions: 20' @ 141 °C Stearic acid 1.5
Petroleum-based softener 5
Zinc oxide 5
CBS 0.5
PBN 1.0
Sulphur 2.5
Precipitated calcium carbonate 80
Compound D - Mineral Filler Smoked sheet 100
(Heavy Loaded) Stearic acid 1.5
Curing conditions: 20' @ 141 °C Petroleum-based softener 25
Zinc oxide 5
CBS 0.6
PBN 1.0
Sulphur 3.2

Appendix 1
Styrene Butadiene Rubber

Amount
Ingredient
(pphr)
Compound E - General Purpose SBR 1500 100
Stearic acid 2
Petroleum-based softener 4.5
Zinc oxide 3
CBS 1.0
PBN 1.0
Sulphur 1.75
Compound F - Good Ageing SBR 1500 100
Stearic acid 2
Zinc oxide 3
TMTD 3
PBN 1.0
MBTS 1.0
Compound G - General Purpose SBR 1710 100
Stearic acid 2
Zinc oxide 3
CBS 1.0
PBN 1.0
Sulphur 1.75
Compound H - Good Ageing SBR 1710 100
Stearic acid 2
Zinc oxide 3
TMTD 3
PBN 1.0
MBTS 1.0

Butyl Rubber
Butyl Rubber
Amount
Ingredient
(pphr)
Compound J - General Purpose Polysar 301 (high unsaturation) 100
Curing conditions: 40' @ 153 °C FEF black 50
Zinc oxide 5
Stearic acid 2
MBT 0.5
TMT 1.0
Sulphur 2
Compound K - Good Ageing Polysar 100 butyl (low unsaturation) 100
Zinc oxide 25
Sulphur 2
MBTS 4
GMF 2

Appendix 1
Polychloroprene
Amount
Ingredient
(pphr)
Compound L - General Purpose Neoprene type WRT 100
Curing conditions: 60' @ 153 °C Light calcined magnesia 4
PBN 2
Stearic acid 0.5
SRF black 40
Robac 22 0.75
Zinc oxide 5
Compound M - Natural Ageing Neoprene type WRT 100
Akroflex CD 2
Stearic acid 0.5
SRF black 50
DOTG 0.75
TMT-MS 0.75
Sulphur 0.75
Zinc oxide 5
Compound N - Heat Ageing Neoprene type WRT 100
Aranox 0.5
Akroflex CD 2
Octamine 3.5
Stearic acid 0.5
SRF black 30
Low volatile process oil 8
Robac 22 1
Zinc oxide 25

Nitrile Rubber
Nitrile Rubber
Amount
Ingredient
(pphr)
Compound P - General Purpose Nitrile rubber 100
Curing conditions: 40' @ 153 °C ca. 32-34% acrylonitrile)
SRF black 50
DOP 20
Zinc oxide 5
Stearic acid 1
PBN 1
MBTS 1.5
Sulphur 1.5
Compound R - Good Ageing Nitrile rubber 100
Curing conditions: 30' @ 153 °C (ca. 35% acrylonitrile)
SRF black 50
DOP 10
Polypropylene adipate 10
Zinc oxide 5
Stearic acid 1
Flectol H 2
TMTD 3
CBS 3

Appendix 1
Miscellaneous
Amount
Ingredient
(pphr)
Compound S - Acrylate Rubber Hycar 4021 100
Curing conditions: 90' @ 153 °C SRF black 50
Stearic acid 1
Triethylene tetramine 2
TMTM 1
Sulphur 3
Compound T - Hypalon 20 100
Chlorosulphonated polyethylene Precipitated calcium carbonate 45
Curing conditions: 30' @ 153 °C Hydrogenated wood rosin 5
Litharge 20
MBTS 0.5
Flectol H 2
Process oil 10
Robac P25 0.75
Light calcined magnesia 10
Compound W - Polysulphide Rubber Thiokol St 100
Curing conditions: 30' @ 141 °C SRF black 60
Stearic acid 3
GMF 1.5
Zinc oxide 0.5
Compound X - Silicone Rubber Dimethyl silicone gum (slightly 100
Curing conditions: 10' @ 135 °C unsaturated)
Post cure 1 h @ 150 °C, 24 h @ 250 °C Diatomaceous silica 45
in air Fine silica 36
Ferric oxide 1
2,4-dichlorobenzoyl peroxide in 2
silicone fluid

New Compounds
New Compounds
Amount
Ingredient
(pphr)
Compound N1 - FVMQ Silastic LS 238 OU 100
Curing conditions: 10' @ 171 °C, Slastic HT-1 1
Post cure 4 h @ 200 °C in air DHBP (50% silicone oil) 0.9
Compound N2 - HNBR Zetpol 2000L 100
Curing conditions: 30' @ 180 °C Spheron 4000 60
Naugard 445 1.5
Rhenogran ZMMBI 50 3
Zinc Oxide Active 3
Peroximon F40 8
Compound N3 - Epoxidised natural Based on Epoxyprene 50, low
Curing conditions: 23.5' @ 141 °C black loading, sulphur, TMTD,
CBS and stabilised.
Details confidential.
Compound N4 - Chlorinated polyethylene Tyrin CM 3630 100
Curing conditions: 30' @ 180 °C Flectol pastilles 0.2
Maglite DE 10
SRF N772 black 60
FEF N550 black 50
Britomya BSH 20
Bisoflex TOT 35
Drapex 39 4
Perkadox 14/40 6.25
Rhenogran TAC 50 5.6
Compound N5 - Fluorocarbon Viton A-202C 100
Curing conditions: 20' @ 170 °C, MT N990 Black 20
Post cure 24 h @ 225 °C in air Sturge VE 6
Maglite DE 3
Compound N6 - Exxpro Exxpro MDX90-10 100
Curing conditions: 45' @ 150 °C HAF N330 Black 50
Stearic Acid 2
Zinc oxide 0.5
Tetrone A 1

Appendix 1
New Compounds (continued)

Amount
Ingredient
(pphr)
Compound N7 - Epichlorohydrin Hydrin C65 100
Curing conditions: 37' @ 165 °C SRF N772 black 70
Winnofil S 5
Paraplex G50 5
DOP 5
Vulkanox MB 1
Stearic acid 1
Span 60 1
Zisnet F 1
DPG 0.3
Maglite DE 5
Compound N8 - EPDM Vistalon 7000 100
Curing conditions: 17.5' @ 165 °C Zinc Oxide 10
Stearic Acid 2
SRF N772 Black 45
FEF N550 Black 60
Strukpar 2280 59
Sulphur 1
TMTD 2.5
ZDMC 2.67
NDBC 2
Sulfasan R 1.7
Compound N9 - EVA Levapren 400 100
Curing conditions: 30' @ 165 °C Staboxal PCD 3
Post cure 2 h @ 165 °C in steam Zinc stearate 2
Vulkanox DDA 1
FEF N550 Black 30
Mistron Vapour 50
Perkadox 14/40 6
TAC 4
Compound N10 - PU Adiprene FM 100
Curing conditions: 7.5' @ 165 °C FEF N550 Black 40
DBP 5
Stearic Acid 1
Dicup 40C 3
Rhenogran TAC50 2

Participant’s 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.
Compound P2 Silicone gum blended to give a methylvinylsiloxane content of
0.31%
Silicone processing aid
Precipitated silica
Fumed silica
Vinyl specific peroxide
Urea
Compound P8 Natural rubber 100 (pphr)
Activators 7
Fillers 105
Process aids 50
6PPD 3
TMQ 2
Antiozonant wax 4
Sulphenamide 0.75
TMTM 0.1
Sulphur 1.5
Compound P10 NBR (28% ACN) 100 (pphr)
Mineral fillers 100
Silica 25
Zinc oxide 10
Stearic acid 1
Antioxidants
Sulphur cure system

APPENDIX 2
WEATHERING RESULTS

Natural Rubber - Standard
Compound A (natural rubber - standard)

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

Table 2. Estimated changes after 6 months at 45 °C
Property % Change % Change % Change % Change
after 6 after 6 due to due to 10
months of months at weathering years in UK
weathering 45 °C effects alone
Hardness (IRHD) 7.7 10.7 -3 -4
Tensile Properties
Tensile Strength (MPa) -25.9 -15.7 -10 -1 5
Elongation at Break (%) -36.6 -42.4 6 8
Modulus at 100% (MPa) 48.8 11.2 38 54
Modulus at 300% (MPa) 28.7 10.8 18 26

Compound A
Hardness
Compound A
86
84
82
Hardness (Micro-IRHD)
80
78
76
74
72
70
0 30 60 90 120 150 180
Weathering Period (Days)
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 90 120 150 180

Natural Rubber - Standard
Elongation at Break
Compound A
650
600
550
Elongation at Break (%)
500
450
400
350
300
250
0 30 60 90 120 150 180
Modulus at 100%
Compound A
10.00
8.00
Modulus at 100% (MPa)
6.00
4.00
2.00
0.00
0 30 60 90 120 150 180

Compound A
Modulus at 300%
Compound A
30.0
25.0
20.0
15.0
10.0
5.0
0.0
0 30 60 90 120 150 180

Natural Rubber - Good Ageing
Compound B (natural rubber - good ageing)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 1.92 2.08 0.16 8
Modulus at 300% (MPa) 10.9 11.9 1.0 9
Compound B (natural rubber - good ageing)

Hardness (IRHD) 6.2 5. 9 0 0
Tensile Properties
Tensile Strength (MPa) -20.9 0.4 -21 -3 0
Modulus at 100% (MPa) 8.3 67.2 -59 -8 4
Modulus at 300% (MPa) 8.9 17.4 -8 -1 2

Compound B
Hardness
Compound B
76
74
72
70
68
66
64
62
60
0 30 60 90 120 150 180
Tensile Strength
Compound B
30.0
28.0
26.0
24.0
22.0
20.0
18.0
0 30 60 90 120 150 180

Natural Rubber - Good Ageing
Elongation at Break
Compound B
750
700
650
600
550
500
450
400
350
0 30 60 90 120 150 180
Modulus at 100%
Compound B
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound B
Modulus at 300%
Compound B
20.0
15.0
10.0
5.0
0.0
0 30 60 90 120 150 180

Natural Rubber - Mineral Filler Loaded
Compound C (natural rubber - mineral filler loaded)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 1.41 1.30 -0.11 -8
Modulus at 300% (MPa) 4.63 3.82 -0.81 -17
Compound C (natural rubber - mineral filler loaded)

Tensile Properties
Elongation at Break (%) -16.1 -3.0 -13 -1 9
Modulus at 100% (MPa) -7.8 15.6 -23 -3 3
Modulus at 300% (MPa) -17.5 -0.2 -1 7 -2 5

Compound C
Hardness
Compound C
66
64
62
60
58
56
54
52
50
48
0 30 60 90 120 150 180
Tensile Strength
Compound C
30.0
25.0
20.0
15.0
10.0
5.0
0 30 60 90 120 150 180

Natural Rubber - Mineral Filler Loaded
Elongation at Break
Compound C
750
700
650
600
550
500
450
400
0 30 60 90 120 150 180
Modulus at 100%
Compound C
3.00
2.50
2.00
1.50
1.00
0.50
0.00
0 30 60 90 120 150 180

Compound C
Modulus at 300%
Compound C
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Natural Rubber - Mineral Filler (Heavy Loaded)
Compound D (natural rubber - mineral filler (heavy loaded))

After 6 months'
exposure
Hardness (IRHD) 62 82 21 33
Tensile Properties
Modulus at 100% (MPa) 1.57 1.45 -0.12 -8
Modulus at 300% (MPa) 4.50 3.95 -0.55 -12
Compound D (natural rubber - mineral filler (heavy loaded))

Hardness (IRHD) 33.4 -0.3 34 48
Tensile Properties
Modulus at 100% (MPa) -7.6 29.3 -37 -5 3
Modulus at 300% (MPa) -12.2 12.2 -24 -3 5

Compound D
Hardness
Compound D
100
95
90
85
80
75
70
65
60
0 30 60 90 120 150 180
Tensile Strength
Compound D
14.0
12.0
10.0
8.0
6.0
4.0
2.0
0 30 60 90 120 150 180

Natural Rubber - Mineral Filler (Heavy Loaded)
Elongation at Break
Compound D
700
650
600
550
500
450
400
350
300
250
0 30 60 90 120 150 180
Modulus at 100%
Compound D
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound D
Modulus at 300%
Compound D
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Styrene Butadiene Rubber - General Purpose
Compound E (styrene butadiene rubber - general purpose)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 2.66 3.47 0.81 30
Modulus at 300% (MPa) 14.8 18.4 3.6 24
Compound E (styrene butadiene rubber - general purpose)

months of months at 4 weathering years in UK
Tensile Properties
Modulus at 100% (MPa) 30.5 60.9 -30 -4 3
Modulus at 300% (MPa) 24.3 43.9 -20 -2 8

Compound E
Hardness
Compound E
80
78
76
74
72
70
68
66
64
62
60
0 30 60 90 120 150 180
Tensile Strength
Compound E
32.0
30.0
28.0
26.0
24.0
22.0
20.0
0 30 60 90 120 150 180

Elongation at Break
Compound E
600
550
500
450
400
350
300
0 30 60 90 120 150 180
Modulus at 100%
Compound E
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound E
Modulus at 300%
Compound E
30.0
25.0
20.0
15.0
10.0
5.0
0.0
0 30 60 90 120 150 180

Styrene Butadiene Rubber - Good Ageing
Compound F (styrene butadiene rubber - good ageing)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 1.93 2.00 0.07 4
Modulus at 300% (MPa) 11.3 11.2 -0.10 -0.9
Compound F (styrene butadiene rubber - good ageing)

Hardness (IRHD) 3.0 5. 8 -3 -4
Tensile Properties
Modulus at 100% (MPa) 3.6 37.8 -34 -4 9
Modulus at 300% (MPa) -0.9 22.1 -23 -3 3

Compound F
Hardness
Compound F
70
69
68
67
66
65
64
63
62
61
60
0 30 60 90 120 150 180
Tensile Strength
Compound F
30.0
28.0
26.0
24.0
22.0
20.0
18.0
0 30 60 90 120 150 180

Elongation at Break
Compound F
700
650
600
550
500
450
400
0 30 60 90 120 150 180
Modulus at 100%
Compound F
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound F
Modulus at 300%
Compound F
20.0
15.0
10.0
5.0
0.0
0 30 60 90 120 150 180

Compound G (styrene butadiene rubber - general purpose)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 1.84 2.31 0.47 26
Modulus at 300% (MPa) 9.64 12.3 2.66 28
Compound G (styrene butadiene rubber - general purpose)

Tensile Properties
Tensile Strength (MPa) -12.4 -12.4 0 0
Modulus at 100% (MPa) 25.5 53.3 -28 -4 0
Modulus at 300% (MPa) 27.6 41.1 -14 -1 9

Compound G
Hardness
Compound G
74
72
70
68
66
64
62
60
0 30 60 90 120 150 180
Tensile Strength
Compound G
24.0
22.0
20.0
18.0
16.0
0 30 60 90 120 150 180

Elongation at Break
Compound G
700
650
600
550
500
450
400
350
0 30 60 90 120 150 180
Modulus at 100%
Compound G
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound G
Modulus at 300%
Compound G
20.00
15.00
10.00
5.00
0.00
0 30 60 90 120 150 180

Compound H (styrene butadiene rubber - good ageing)

Table 1. Property changes after six months' exposure
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 1.44 1.37 -0.07 -5
Modulus at 300% (MPa) 8.34 7.64 -0.70 -8
Compound H (styrene butadiene rubber - good ageing)

Tensile Properties
Modulus at 100% (MPa) -4.9 49.3 -54 -7 7
Modulus at 300% (MPa) -8.4 81.1 -89 -12 8

Compound H
Hardness
Compound H
65
64
63
62
61
60
59
58
57
56
55
0 30 60 90 120 150 180
Tensile Strength
Compound H
24.0
22.0
20.0
18.0
16.0
14.0
12.0
0 30 60 90 120 150 180

Elongation at Break
Compound H
750
700
650
600
550
500
450
400
350
0 30 60 90 120 150 180
Modulus at 100%
Compound H
3.00
2.50
2.00
1.50
1.00
0.50
0.00
0 30 60 90 120 150 180

Compound H
Modulus at 300%
Compound H
14.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0 30 60 90 120 150 180

Butyl Rubber - General Purpose
Compound J (butyl rubber - general purpose)

After 6 months'
exposure
Hardness (IRHD) 67 67 0.4 0.6
Tensile Properties
Modulus at 100% (MPa) 2.62 2.56 -0.06 -2
Modulus at 300% (MPa) 9.64 9.52 -0.12 -1
Compound J (butyl rubber - general purpose)

Hardness (IRHD) 0.6 -1.5 2 3
Tensile Properties
Modulus at 100% (MPa) -2.3 11.1 -13 -1 9
Modulus at 300% (MPa) -1.2 0.0 -1 -2

Compound J
Hardness
Compound J
72
71
70
69
68
67
66
65
64
63
62
0 30 60 90 120 150 180
Tensile Strength
Compound J
15.0
14.0
13.0
12.0
11.0
10.0
0 30 60 90 120 150 180

Butyl Rubber - General Purpose
Elongation at Break
Compound J
500
450
400
350
300
0 30 60 90 120 150 180
Modulus at 100%
Compound J
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound J
Modulus at 300%
Compound J
16.00
14.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0 30 60 90 120 150 180

Butyl Rubber - Good Ageing
Compound K (butyl rubber - good ageing)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 2.12 2.16 0.04 2
Modulus at 300% (MPa) 6.72 6.95 0.23 3
Compound K (butyl rubber - good ageing)

Tensile Properties
Modulus at 100% (MPa) 1.9 16.0 -14 -2 0
Modulus at 300% (MPa) 3.4 0.0 3 5

Compound K
Hardness
Compound K
85
84
83
82
81
80
79
78
77
76
75
0 30 60 90 120 150 180
Tensile Strength
Compound K
17.0
16.0
15.0
14.0
13.0
12.0
11.0
10.0
0 30 60 90 120 150 180

Butyl Rubber - Good Ageing
Elongation at Break
Compound K
750
700
650
600
550
500
450
0 30 60 90 120 150 180
Modulus at 100%
Compound K
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound K
Modulus at 300%
Compound K
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0 30 60 90 120 150 180

Polychloroprene - General Purpose
Compound L (polychloroprene - general purpose)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 3.91 4.32 0.41 10
Modulus at 300% (MPa) 21.0 20.9 -0.10 -0.5
Compound L (polychloroprene - general purpose)

Tensile Properties
Modulus at 100% (MPa) 10.5 -4.1 15 21
Modulus at 300% (MPa) -0.5 0.5 -1 -1

Compound L
Hardness
Compound L
80
78
76
74
72
70
68
66
64
0 30 60 90 120 150 180
Tensile Strength
Compound L
26.0
24.0
22.0
20.0
18.0
16.0
14.0
0 30 60 90 120 150 180

Polychloroprene - General Purpose
Elongation at Break
Compound L
400
350
300
250
200
0 30 60 90 120 150 180
Modulus at 100%
Compound L
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound L
Modulus at 300%
Compound L
30.0
25.0
20.0
15.0
10.0
5.0
0.0
0 30 60 90 120 150 180

Polychloroprene - Natural Ageing
Compound M (polychloroprene - natural ageing)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 4.00 4.49 0.49 12
Modulus at 300% (MPa) 18.7 19.7 1.0 5
Compound M (polychloroprene - natural ageing)

Tensile Properties
Tensile Strength (MPa) -6.8 -4.8 -2 -3
Elongation at Break (%) -10.8 -8.1 -3 -4
Modulus at 100% (MPa) 12.3 7. 0 5 8
Modulus at 300% (MPa) 5.3 5.9 -1 -1

Compound M
Hardness
Compound M
80
78
76
74
72
70
68
66
64
0 30 60 90 120 150 180
Tensile Strength
Compound M
26.0
24.0
22.0
20.0
18.0
16.0
14.0
0 30 60 90 120 150 180

Polychloroprene - Natural Ageing
Elongation at Break
Compound M
400
350
300
250
200
0 30 60 90 120 150 180
Modulus at 100%
Compound M
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound M
Modulus at 300%
Compound M
30.0
25.0
20.0
15.0
10.0
5.0
0.0
0 30 60 90 120 150 180

Polychloroprene - Heat Ageing
Compound N (polychloroprene - heat ageing)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 2.89 4.19 1.3 45
Modulus at 300% (MPa) 8.28 8.54 0.26 3
Compound N (polychloroprene - heat ageing)

Hardness (IRHD) 13.6 3.5 10 14
Tensile Properties
Modulus at 100% (MPa) 45.0 27.0 18 26
Modulus at 300% (MPa) 3.1 4. 6 -1 -2

Compound N
Hardness
Compound N
96
94
92
90
88
86
84
82
80
78
76
0 30 60 90 120 150 180
Tensile Strength
Compound N
12.0
11.0
10.0
9.0
8.0
7.0
6.0
0 30 60 90 120 150 180

Polychloroprene - Heat Ageing
Elongation at Break
Compound N
450
400
350
300
250
200
0 30 60 90 120 150 180
Modulus at 100%
Compound N
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound N
Modulus at 300%
Compound N
14.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0 30 60 90 120 150 180

Nitrile Rubber - General Purpose
Compound P (nitrile rubber - general purpose)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 1.86 2.01 0.15 8
Modulus at 300% (MPa) 8.8 10.7 1.9 22
Compound P (nitrile rubber - general purpose)

Tensile Properties
Modulus at 100% (MPa) 8.1 29.6 -22 -3 1
Modulus at 300% (MPa) 21.6 54.5 -33 -4 7

Compound P
Hardness
Compound P
64
62
60
58
56
54
52
50
0 30 60 90 120 150 180
Tensile Strength
Compound P
24.0
22.0
20.0
18.0
16.0
14.0
12.0
10.0
0 30 60 90 120 150 180

Nitrile Rubber - General Purpose
Elongation at Break
Compound P
650
600
550
500
450
400
350
300
0 30 60 90 120 150 180
Modulus at 100%
Compound P
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound P
Modulus at 300%
Compound P
16.00
14.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0 30 60 90 120 150 180

Polychloroprene - Good Ageing
Compound R (polychloroprene - good ageing)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 1.67 1.85 0.18 11
Modulus at 300% (MPa) 7.37 8.86 1.5 20
Compound R (polychloroprene - good ageing)

Hardness (IRHD) 9.3 17.6 -8 -1 2
Tensile Properties
Tensile Strength (MPa) -25.5 - - -
Modulus at 100% (MPa) 10.8 63.5 -53 -7 5
Modulus at 300% (MPa) 20.2 34.2 -14 -2 0

Compound R
Hardness
Compound R
66
64
62
60
58
56
54
52
0 30 60 90 120 150 180
Tensile Strength
Compound R
26.0
24.0
22.0
20.0
18.0
16.0
14.0
0 30 60 90 120 150 180

Nitrile Rubber - Good Ageing
Elongation at Break
Compound R
750
700
650
600
550
500
450
400
0 30 60 90 120 150 180
Modulus at 100%
Compound R
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound R
Modulus at 300%
Compound R
14.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0 30 60 90 120 150 180

Miscellaneous - Acrylate Rubber
Compound S (miscellaneous - acrylate rubber)

After 6 months'
exposure
Tensile Properties
Tensile Strength (MPa) 11.3 11.6 0.3 3
Elongation at Break (%) 223 241 18 8
Modulus at 100% (MPa) 3.47 3.18 -0.29 -8
Modulus at 300% (MPa) - - - -
Compound S (miscellaneous - acrylate rubber)

Tensile Properties
Tensile Strength (MPa) 2.7 -19.7 22 32
Elongation at Break (%) 8.1 -13.5 22 31
Modulus at 100% (MPa) -8.4 -0.9 -7 -1 1

Compound S
Hardness
Compound S
60
58
56
54
52
50
48
46
0 30 60 90 120 150 180
Tensile Strength
Compound S
14.0
13.0
12.0
11.0
10.0
9.0
0 30 60 90 120 150 180

Miscellaneous - Acrylate Rubber
Elongation at Break
Compound S
300
280
260
240
220
200
180
160
0 30 60 90 120 150 180
Modulus at 100%
Compound S
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound S

Miscellaneous - Chlorosulphonated Polyethylene
Compound T (miscellaneous - chlorosulphonated polyethylene)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 2.88 3.99 1.1 39
Modulus at 300% (MPa) 6.27 5.23 -1.0 -17
Compound T (miscellaneous - chlorosulphonated polyethylene)

Hardness (IRHD) 26.6 11.7 15 21
Tensile Properties
Elongation at Break (%) -40.0 -37.4 -3 -4
Modulus at 100% (MPa) 38.5 -2.1 41 58
Modulus at 300% (MPa) -16.6 - - -

Compound T
Hardness
Compound T
75
70
65
60
55
50
0 30 60 90 120 150 180
Tensile Strength
Compound T
10.0
9.0
8.0
7.0
6.0
5.0
4.0
0 30 60 90 120 150 180

Miscellaneous - Chlorosulphonated Polyethylene
Elongation at Break
Compound T
500
450
400
350
300
250
200
0 30 60 90 120 150 180
Modulus at 100%
Compound T
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

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 90 120 150 180

Miscellaneous - Polysulphide Rubber
Compound W (miscellaneous - polysulphide rubber)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 2.01 2.43 0.42 21
Compound W (miscellaneous - polysulphide rubber)

Tensile Properties
Modulus at 100% (MPa) 20.9 19.9 1 1

Compound W
Hardness
Compound W
76
74
72
70
68
66
64
62
60
0 30 60 90 120 150 180
Tensile Strength
Compound W
8.0
7.0
6.0
5.0
4.0
3.0
0 30 60 90 120 150 180

Miscellaneous - Polysulphide Rubber
Elongation at Break
Compound W
340
320
300
280
260
240
220
200
0 30 60 90 120 150 180
Modulus at 100%
Compound W
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound W

Miscellaneous - Silicone Rubber
Compound X (miscellaneous - silicone rubber)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 2.89 2.65 -0.24 -8
Compound X (miscellaneous - silicone rubber)

Tensile Properties
Modulus at 100% (MPa) -8.3 -1.4 -7 -1 0

Compound X
Hardness
Compound X
60
58
56
54
52
50
0 30 60 90 120 150 180
Tensile Strength
Compound X
9.0
8.0
7.0
6.0
5.0
0 30 60 90 120 150 180

Miscellaneous - Silicone Rubber
Elongation at Break
Compound X
300
280
260
240
220
200
180
160
140
0 30 60 90 120 150 180
Modulus at 100%
Compound X
5.00
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound X

New Compound - FVMQ
Compound N1 (FVMQ)
After 6 months'
exposure
Tensile Properties
Tensile Strength (MPa) 7.5 7. 1 -0.4 -5
Elongation at Break (%) 168 17 6 8 5
Modulus at 100% (MPa) 4.29 4.03 -0.26 -6
Compound N1 (FVMQ)
Tensile Properties
Elongation at Break (%) 4.9 1.2 4 5
Modulus at 100% (MPa) -6.1 48.7 -55 -7 8

Compound N1
Hardness
Compound N1
76
75
74
73
72
71
70
69
68
0 30 60 90 120 150 180
Tensile Strength
Compound N1
10.00
9.00
8.00
7.00
6.00
5.00
0 30 60 90 120 150 180

New Compound - FVMQ
Elongation at Break
Compound N1
220
200
180
160
140
120
0 30 60 90 120 150 180
Modulus at 100%
Compound N1
6.00
5.00
4.00
3.00
0 30 60 90 120 150 180

Compound N1

New Compound - HNBR
Compound N2 (HNBR)
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 2.68 2.87 0.19 7
Modulus at 300% (MPa) 14.3 15.9 1.7 12
Compound N2 (HNBR)
Hardness (IRHD) 4.7 30.9 -26 -3 7
Tensile Properties
Elongation at Break (%) -4.3 3.2 -7 -1 1
Modulus at 100% (MPa) 7.1 941.0 -934 -133 4
Modulus at 300% (MPa) 11.6 -2.1 14 20

Compound N2
Hardness
Compound N2
75
73
71
69
67
65
0 30 60 90 120 150 180
Tensile Strength
Compound N2
24.0
22.0
20.0
18.0
0 30 60 90 120 150 180

New Compound - HNBR
Elongation at Break
Compound N2
650
600
550
500
450
400
0 30 60 90 120 150 180
Modulus at 100%
Compound N2
5.00
4.00
3.00
2.00
1.00
0 30 60 90 120 150 180

Compound N2
Modulus at 300%
Compound N2
20.0
18.0
16.0
14.0
12.0
10.0
0 30 60 90 120 150 180

New Compound - Epoxidised Natural
Compound N3 (epoxidised natural)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 1.87 1.98 0.11 6
Modulus at 300% (MPa) 6.71 8.98 2.27 34
Compound N3 (epoxidised natural)

Tensile Properties
Tensile Strength (MPa) -13.2 -83.8 71 10 1
Modulus at 100% (MPa) 5.9 27.3 -21 -3 1
Modulus at 300% (MPa) 33.8 44.6 -11 -1 5

Compound N3
Hardness
Compound N3
64
62
60
58
56
54
52
0 30 60 90 120 150 180
Tensile Strength
Compound N3
30.0
25.0
20.0
15.0
0 30 60 90 120 150 180

New Compound - Epoxidised Natural
Elongation at Break
Compound N3
700
650
600
550
500
450
400
0 30 60 90 120 150 180
Modulus at 100%
Compound N3
3.00
2.50
2.00
1.50
1.00
0 30 60 90 120 150 180

Compound N3
Modulus at 300%
Compound N3
12.00
10.00
8.00
6.00
4.00
0 30 60 90 120 150 180

New Compound - Chlorinated Polyethylene
Compound N4 (chlorinated polyethylene)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 8.07 8.37 0.30 4
Compound N4 (chlorinated polyethylene)

Tensile Properties
Modulus at 100% (MPa) 3.7 14.1 -10 -1 5

Compound N4
Hardness
Compound N4
92
90
88
86
84
82
0 30 60 90 120 150 180
Tensile Strength
Compound N4
20.0
18.0
16.0
14.0
12.0
10.0
0 30 60 90 120 150 180

New Compound - Chlorinated Polyethylene
Elongation at Break
Compound N4
300
250
200
150
100
0 30 60 90 120 150 180
Modulus at 100%
Compound N4
12.00
10.00
8.00
6.00
4.00
0 30 60 90 120 150 180

Compound N4

New Compound - Fluorocarbon
Compound N5 (fluorocarbon)
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 5.22 5.08 -0.14 -3
Compound N5 (fluorocarbon)
Tensile Properties
Modulus at 100% (MPa) -2.7 -0.2 -2 -4

Compound N5
Hardness
Compound N5
80
78
76
74
72
70
68
66
0 30 60 90 120 150 180
Tensile Strength
Compound N5
15.0
14.0
13.0
12.0
11.0
10.0
0 30 60 90 120 150 180

New Compound - Fluorocarbon
Elongation at Break
Compound N5
280
260
240
220
200
180
0 30 60 90 120 150 180
Modulus at 100%
Compound N5
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
0 30 60 90 120 150 180

Compound N5

New Compound - Exxpro
Compound N6 (Exxpro)
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 6.70 5.22 -1.48 -22
Modulus at 300% (MPa) - - -
Compound N6 (Exxpro)
Tensile Properties
Modulus at 100% (MPa) -22.1 0.0 -22 -3 2

Compound N6
Hardness
Compound N6
76
74
72
70
68
66
64
62
60
0 30 60 90 120 150 180
Tensile Strength
Compound N6
20.0
19.0
18.0
17.0
16.0
15.0
0 30 60 90 120 150 180

New Compound - Exxpro
Elongation at Break
Compound N6
280
260
240
220
200
180
0 30 60 90 120 150 180
Modulus at 100%
Compound N6
9.00
8.00
7.00
6.00
5.00
4.00
3.00
0 30 60 90 120 150 180

Compound N6

New Compound - Epichlorohydrin
Compound N7 (epichlorohydrin)
After 6 months'
exposure
Tensile Properties
Tensile Strength (MPa) 9.6 9. 6 0 0
Elongation at Break (%) 299 211 -87 -29
Modulus at 100% (MPa) 4.47 5.04 0.57 13
Compound N7 (epichlorohydrin)
Tensile Properties
Tensile Strength (MPa) 0.0 1.6 -2 -2
Modulus at 100% (MPa) 12.8 3. 6 9 13

Compound N7
Hardness
Compound N7
90
88
86
84
82
80
78
76
74
72
70
0 30 60 90 120 150 180
Tensile Strength
Compound N7
12.00
11.00
10.00
9.00
8.00
7.00
0 30 60 90 120 150 180

New Compound - Epichlorohydrin
Elongation at Break
Compound N7
400
350
300
250
200
150
100
0 30 60 90 120 150 180
Modulus at 100%
Compound N7
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
0 30 60 90 120 150 180

Compound N7

New Compound - EPDM
Compound N8 (EPDM)
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 4.38 4.24 -0.14 -3
Modulus at 300% (MPa) 14.0 14.1 0.1 1
Compound N8 (EPDM)
Tensile Properties
Tensile Strength (MPa) -2.9 0.6 -3 -5
Modulus at 100% (MPa) -3.2 34.5 -38 -5 4
Modulus at 300% (MPa) 1.0 25.7 -25 -3 5

Compound N8
Hardness
Compound N8
84
82
80
78
76
74
0 30 60 90 120 150 180
Tensile Strength
Compound N8
20.0
18.0
16.0
14.0
12.0
0 30 60 90 120 150 180

New Compound - EPDM
Elongation at Break
Compound N8
500
450
400
350
300
250
200
0 30 60 90 120 150 180
Modulus at 100%
Compound N8
6.00
5.50
5.00
4.50
4.00
3.50
3.00
0 30 60 90 120 150 180

Compound N8
Modulus at 300%
Compound N8
20.0
18.0
16.0
14.0
12.0
10.0
0 30 60 90 120 150 180

New Compound - EVA
Compound N9 (EVA)
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 7.93 8.91 0.98 12
Compound N9 (EVA)
Tensile Properties
Modulus at 100% (MPa) 12.4 -1.3 14 20

Compound N9
Hardness
Compound N9
85
83
81
79
77
75
0 30 60 90 120 150 180
Tensile Strength
Compound N9
14.0
13.0
12.0
11.0
10.0
9.0
0 30 60 90 120 150 180

New Compound - EVA
Elongation at Break
Compound N9
250
200
150
100
0 30 60 90 120 150 180
Modulus at 100%
Compound N9
11.00
10.00
9.00
8.00
7.00
6.00
0 30 60 90 120 150 180

Compound N9

New Compound - PU
Compound N10 (PU)

After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 6.24 8.51 2.27 36
Compound N10 (PU)

Hardness (IRHD) 6.2 -39.2 45 65
Tensile Properties
Modulus at 100% (MPa) 36.4 -84.0 120 17 2

Compound N10
Hardness
Compound N10
86
84
82
80
78
76
74
72
70
0 30 60 90 120 150 180
Tensile Strength
Compound N10
20.0
18.0
16.0
14.0
12.0
0 30 60 90 120 150 180

New Compound - PU
Elongation at Break
Compound N10
250
200
150
100
0 30 60 90 120 150 180
Modulus at 100%
Compound N10
11.00
10.00
9.00
8.00
7.00
6.00
5.00
4.00
0 30 60 90 120 150 180

Compound N10

Participant Compound - EPR
Compound P1
After 6 months'
exposure
Hardness (IRHD) 71 71 -0.3 -0.4
Tensile Properties
Modulus at 100% (MPa) 2.15 2.10 -0.05 -2
Modulus at 300% (MPa) 8.47 7.32 -1.15 -14
Compound P1
Hardness (IRHD) -0.4 -1.4 1 1
Tensile Properties
Modulus at 100% (MPa) -2.3 291.6 -294 -42 0
Modulus at 300% (MPa) -13.6 - - -

Compound P1
Hardness
Compound P1
76
75
74
73
72
71
70
69
68
67
66
0 30 60 90 120 150 180
Tensile Strength
Compound P1
18.0
17.0
16.0
15.0
14.0
13.0
12.0
11.0
10.0
0 30 60 90 120 150 180

Participant Compound - EPR
Elongation at Break
Compound P1
600
550
500
450
400
0 30 60 90 120 150 180
Modulus at 100%
Compound P1
4.00
3.00
2.00
1.00
0.00
0 30 60 90 120 150 180

Compound P1
Modulus at 300%
Compound P1
14.00
12.00
10.00
8.00
6.00
4.00
0 30 60 90 120 150 180

Participant Compound - Medium Nitrile Rubber
Compound P3
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 10.6 9.9 -0.8 -7
Compound P3
Tensile Properties
Modulus at 100% (MPa) -7.2 18.9 -26 -3 7

Compound P3
Hardness
Compound P3
90
88
86
84
82
80
78
76
0 30 60 90 120 150 180
Tensile Strength
Compound P3
18.0
17.0
16.0
15.0
14.0
13.0
12.0
0 30 60 90 120 150 180

Participant Compound - Medium Nitrile Rubber
Elongation at Break
Compound P3
280
270
260
250
240
230
220
210
200
0 30 60 90 120 150 180
Modulus at 100%
Compound P3
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 90 120 150 180

Compound P3

Participant Compound - Nitrile Rubber
Compound P4
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 3.02 3.22 0.2 7
Modulus at 300% (MPa) 13.1 13.6 0.5 4
Compound P4
Hardness (IRHD) 0.3 10.4 -10 -1 4
Tensile Properties
Modulus at 100% (MPa) 6.6 39.4 -33 -4 7
Modulus at 300% (MPa) 4.0 61.8 -58 -8 3

Compound P4
Hardness
Compound P4
74
72
70
68
66
64
62
60
0 30 60 90 120 150 180
Tensile Strength
Compound P4
26.0
24.0
22.0
20.0
18.0
16.0
0 30 60 90 120 150 180

Elongation at Break
Compound P4
600
550
500
450
400
350
0 30 60 90 120 150 180
Modulus at 100%
Compound P4
5.00
4.50
4.00
3.50
3.00
2.50
2.00
0 30 60 90 120 150 180

Compound P4
Modulus at 300%
Compound P4
18.0
16.0
14.0
12.0
10.0
0 30 60 90 120 150 180

Participant Compound - EPDM
Compound P5
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 6.62 6.09 -0.53 -8
Compound P5
Tensile Properties
Modulus at 100% (MPa) -8.0 - - -

Compound P5
Hardness
Compound P5
75
74
73
72
71
70
69
68
67
0 30 60 90 120 150 180
Tensile Strength
Compound P5
17.0
16.0
15.0
14.0
13.0
12.0
11.0
10.0
9.0
0 30 60 90 120 150 180

Participant Compound - EPDM
Elongation at Break
Compound P5
200
180
160
140
120
100
0 30 60 90 120 150 180
Modulus at 100%
Compound P5
9.00
8.00
7.00
6.00
5.00
4.00
0 30 60 90 120 150 180

Compound P5

Participant Compound - Vamac G
Compound P6
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 7.37 8.25 0.88 12
Compound P6
Hardness (IRHD) 6.3 23.1 -17 -2 4
Tensile Properties
Modulus at 100% (MPa) 11.9 42.5 -31 -4 4

Compound P6
Hardness
Compound P6
89
87
85
83
81
79
77
75
0 30 60 90 120 150 180
Tensile Strength
Compound P6
14.0
13.0
12.0
11.0
10.0
0 30 60 90 120 150 180

Participant Compound - Vamac G
Elongation at Break
Compound P6
300
250
200
150
0 30 60 90 120 150 180
Modulus at 100%
Compound P6
10.00
9.00
8.00
7.00
6.00
5.00
0 30 60 90 120 150 180

Compound P6

Participant Compound - W Type Polychloroprene
Compound P7
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 3.36 4.04 0.68 20
Compound P7
Tensile Properties
Modulus at 100% (MPa) 20.2 25.9 -6 -8

Compound P7
Hardness
Compound P7
77
75
73
71
69
67
65
63
0 30 60 90 120 150 180
Tensile Strength
Compound P7
17.0
16.0
15.0
14.0
13.0
12.0
11.0
10.0
0 30 60 90 120 150 180

Participant Compound - W Type Polychloroprene
Elongation at Break
Compound P7
350
300
250
200
0 30 60 90 120 150 180
Modulus at 100%
Compound P7
5.00
4.50
4.00
3.50
3.00
2.50
2.00
0 30 60 90 120 150 180

Compound P7

Participant Compound - Natural Rubber
Compound P8
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 1.00 1.81 0.81 81
Modulus at 300% (MPa) 5.63 7.16 1.53 27
Compound P8
Tensile Properties
Modulus at 100% (MPa) 81.0 145.0 -64 -9 1
Modulus at 300% (MPa) 27.2 -2.3 29 42

Compound P8
Hardness
Compound P8
73
71
69
67
65
63
61
59
57
55
0 30 60 90 120 150 180
Tensile Strength
Compound P8
14.0
13.0
12.0
11.0
10.0
9.0
8.0
0 30 60 90 120 150 180

Participant Compound - Natural Rubber
Elongation at Break
Compound P8
600
550
500
450
400
350
300
0 30 60 90 120 150 180
Modulus at 100%
Compound P8
3.00
2.50
2.00
1.50
1.00
0.50
0.00
0 30 60 90 120 150 180

Compound P8
Modulus at 300%
Compound P8
10.00
9.00
8.00
7.00
6.00
5.00
4.00
0 30 60 90 120 150 180

Participant Compound - Santoprene 101 55 V185
Compound P9
After 6 months'
exposure
Hardness (IRHD) 68 68 -0.1 -0.1
Tensile Properties
Modulus at 100% (MPa) 1.98 1.75 -0.23 -12
Modulus at 300% (MPa) 4.10 3.55 -0.55 -13
Compound P9
Hardness (IRHD) -0.1 0.0 0 0
Tensile Properties
Elongation at Break (%) -13.7 - - -
Modulus at 100% (MPa) -11.6 -2.0 -10 -1 4
Modulus at 300% (MPa) -13.4 -1.2 -12 -1 7

Compound P9
Hardness
Compound P9
72
71
70
69
68
67
66
65
0 30 60 90 120 150 180
Tensile Strength
Compound P9
7.00
6.00
5.00
4.00
3.00
0 30 60 90 120 150 180

Participant Compound - Santoprene 101 55 V185
Elongation at Break
Compound P9
500
450
400
350
300
0 30 60 90 120 150 180
Modulus at 100%
Compound P9
3.00
2.50
2.00
1.50
1.00
0.50
0 30 60 90 120 150 180

Compound P9
Modulus at 300%
Compound P9
6.00
5.00
4.00
3.00
2.00
0 30 60 90 120 150 180

Compound P10
After 6 months'
exposure
Tensile Properties
Modulus at 100% (MPa) 3.19 3.47 0.28 9
Modulus at 300% (MPa) 5.80 5.43 -0.37 -6
Compound P10
Tensile Properties
Modulus at 100% (MPa) 8.8 22.9 -14 -2 0
Modulus at 300% (MPa) -6.4 33.1 -39 -5 6

Compound P10
Hardness
Compound P10
94
92
90
88
86
84
82
80
0 30 60 90 120 150 180
Tensile Strength
Compound P10
14.0
13.0
12.0
11.0
10.0
9.0
8.0
7.0
6.0
5.0
0 30 60 90 120 150 180

Elongation at Break
Compound P10
600
550
500
450
400
350
300
0 30 60 90 120 150 180
Modulus at 100%
Compound P10
5.00
4.50
4.00
3.50
3.00
2.50
2.00
0 30 60 90 120 150 180

Compound P10
Modulus at 300%
Compound P10
9.00
8.00
7.00
6.00
5.00
4.00
0 30 60 90 120 150 180

Figure 1
Surface cracking of natural rubber Compound C
Figure 2
Surface cracking of natural rubber Compound D

Ozone Results
APPENDIX 3
OZONE RESULTS

Appendix 3

Ozone Results
Table 1. Time to Grade 1 cracking (first cracking) at 50 pphm, h

Compound Strain level, %
reference
5 10 15 20 30
A 4 4 4 4 4
B 360 4 4 4 4
C 2 2 2 2 2
D 8 8 2 2 2
E 24 2 2 2 2
F 2 2 2 2 2
G 4 4 4 4 4
H 72 8 4 4 4
J # # # # 57 6
K # # 38 4 288 28 8
P 48 2 2 2 2
R 240 456 48 4 4
W # # 240 19 2 96
N3 8 2 2 2 2
N7 # # # 576 57 6
P3 24 8 2 2 2
P4 360 48 24 16 8
P8 # # # # 264
P10 # 408 72 72 24
# Cracking was never observed

Ozone Resistance Results at 50 pphm
184
700
Appendix 3
600
500
400 5% Strain
10% Strain
15% Strain
20% Strain
300 30% Strain
Time to first cracking (hours)

200
100
0
A B C D E F G H J K P R W N3 N7 P3 P4 P8 P10
Compound References
Figure 1
Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Ozone Results
Table 2. Time to Grade 3 cracking at 50 pphm, h

reference
5 10 15 20 30
A 360 # 552 36 0 21 6
B # # 600 432 36 0
C 432 216 72 72 72
D 360 360 72 72 48
E 48 8 24 24 24
F 24 8 24 24 48
G 72 16 8 8 8
H 72 48 16 16 16
P 216 192 192 192 12 0
R # 45 6 96 24 24
N3 48 24 24 16 48
P3 72 24 16 16 16
P4 384 120 72 72 72
P8 # # # # 264
P10 # # 72 72 72
# Cracking was either never recorded or did not reach Grade 3 level

186
700
Appendix 3
600
500
400 5% Strain
10% Strain
15% Strain
20% Strain
300 30% Strain
Time to Grade 3 cracking (hours)

200
100
0
A B C 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

reference
5 10 15 20 30
A 4 2 2 2 2
B 4 2 2 2 2
C 2 2 2 2 2
D 4 2 2 2 2
J # # # 552 36 0
K # # # 168 12 0
L 144 144 96 72 48
M # # # 192 14 4
N # 14 4 # 96 96
P 2 2 2 2 2
R 48 16 2 2 2
W # 96 72 48 48
P4 48 16 8 4 2
P8 # # 19 2 48 16
P10 # 16 2 2 2
# Cracking was never observed

188
600
Appendix 3
500
400
5% Strain
10% Strain
300 15% Strain
20% Strain
30% Strain
200
Time to first cracking (hours)

100
0
A B C 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

reference
5 10 15 20 30
A 48 72 48 24 48
B 24 48 24 16 16
C 8 48 48 48 48
D # # 16 16 16
L 168 168 144 96 96
M # # # 192 14 4
N # 14 4 # 96 96
P 2 8 8 8 8
R 48 24 8 4 4
W # # 432 432 38 4
P4 72 24 24 24 16
P8 # # 192 48 16
P10 # 24 8 8 8
# Cracking was either never recorded or did not reach Grade 3 level

190
500
Appendix 3
450
400
350
300
5% Strain
10% Strain
250 15% Strain
20% Strain
30% Strain
200
150
Time to Grade 3 cracking (hours)

100
50
0
A B C 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 observed for grade 3
40.0
35.0
30.0
25.0
Strain (%)
20.0
15.0
10.0
5.0
0.0
0 100 200 300 400 500 600 700
Time (hours)
Figure 5
Compound W Grade of Cracking at 200 pphm

40.0
35.0
30.0
25.0
Strain (%)
20.0
15.0
10.0
5.0
0.0
0 20 40 60 80 100 120 140 160 180 200
Time (hours)
Figure 6

Appendix 3
Compound P10 Grade 1 Cracking at 50 pphm

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

Brown, R.P. - Butler, T. - Hawley, S.W. - Ageing of Rubber - Accelerated Weathering and Ozone Test Results-Ismithers Rapra Publishing (2010!11!28)

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O3 Ageing of Rubber

Accelerated Weathering and

R.P. Brown, T. Butler

Europe’s leading independent

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

Rapra Technology Limited

First Published in 2001 by

Rapra Technology Limited

©Copyright 2001 Rapra Technology Limited

All rights reserved. Except as permitted under current legislation no part

Typeset by Rapra Technology Limited

3. Preparation of Test Pieces ................................................................................................. 3

4. Physical Tests .................................................................................................................... 3

5. Exposure of Test Pieces ..................................................................................................... 3

6. Weathering Results (Appendix 2) ..................................................................................... 4

7. Ozone Results (Appendix 3) ............................................................................................. 6

Appendix 1 - Compound Details ......................................................................................... 13

Appendix 2 - Weathering Results ........................................................................................ 25

© Copyright 2001 Rapra Technology Limited i

Appendix 3 - Ozone Results .............................................................................................. 181

ii Ageing of Rubber - Accelerated Weathering and Ozone Test Results

2.1 Original Materials

© Copyright 2001 Rapra Technology Limited 1

2.2 New Materials

Compound N1 is a fluorosilicone-based on LS 2380U. The hydrogenated nitrile compound

Compounds P1–P10 are materials submitted by industry participants:

Compound P1 ethylene propylene copolymer

Compound P2 siloxane material

Compound P3 medium nitrile, carbon black filled with EV sulphur cure

Compound P4 nitrile, NF standard 0115/2

Compound P5 EPDM, NF standard 0115/1

Compound P6 Vamac G material, black filled with a Diak/DOTG cure system

Compound P8 natural rubber

Compound P9 thermoplastic rubber—Santoprene 101 55 V185 from AES

Compound P10 nitrile

2 Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Standard 2 mm sheets were produced by compression moulding.

The cure conditions arrived at are given in Appendix 1.

5 EXPOSURE OF TEST PIECES

© Copyright 2001 Rapra Technology Limited 3

5.2 Ozone Exposure

6 WEATHERING RESULTS (APPENDIX 2)

4 Ageing of Rubber - Accelerated Weathering and Ozone Test Results

6.3 Interpretation of results

© Copyright 2001 Rapra Technology Limited 5

where C is the net change due to weathering after 6 months.

7 OZONE RESULTS (APPENDIX 3)

As an indication of performance in relation to service, a material passing a typical specification

6 Ageing of Rubber - Accelerated Weathering and Ozone Test Results

Several overall observations can be made.

© Copyright 2001 Rapra Technology Limited 7

8.1.4 Tensile Strength

8 Ageing of Rubber - Accelerated Weathering and Ozone Test Results

8.1.5 Elongation at Break

8.1.6 Effect of Temperature

The estimates of change due to temperature over 6 months at 45 °C obtained by extrapolation

© Copyright 2001 Rapra Technology Limited 9

It is interesting to note differences between properties in respect of the weathering changes

10 Ageing of Rubber - Accelerated Weathering and Ozone Test Results

© Copyright 2001 Rapra Technology Limited 11

An accelerated weathering and ozone exposure programme involving a total of 38 rubber

2. ISO 37 1994 Rubber, vulcanised or thermoplastic—Determination of tensile stress-

3. ISO 48 1994 Rubber, vulcanised or thermoplastic—Determination of hardness (Hardness