Ageing of Rubber

Ageing of Rubber
Accelerated Heat Ageing

Test Results
R.P. Brown, T. Butler

and S.W. Hawley
Europes leading independent

plastics and rubber specialists
Ageing of Rubber
Accelerated Heat Ageing
Test Results
R.P. Brown, T. Butler and S.W. Hawley

Rapra Technology Limited
Acknowledgements
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.
The authors are indebted to all those who contributed financially, with provision of
materials, and by giving advice and support. We are particularly grateful to the members of
the Industry Advisory Committee for all their help and guidance throughout the project:
Alfa Laval Saunders Ltd., AWE, British Energy Generation Ltd., British Nuclear Fuels plc,
Enichem UK Ltd., Hiflex Hose, Schlumberger Gas Metflex, Silvertown UK Ltd., Tun Abdul
Razak Research Centre, and Wavin Building Products Ltd.

Shawbury, Shrewsbury, Shropshire SY4 NNR, United Kingdom
Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.rapra.net
First Published 2001 by

Shawbury, Shropshire SY4 4NR, United Kingdom
Copyright 2001 Rapra Technology Limited
ISBN: 1-85957-274-X
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 retrieval system, without prior permission in
writing 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.
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 ..................................................................................................... 4
6. Results .............................................................................................................................. 4
6.1 Presentation ............................................................................................................... 4
6.2 Uncertainty ................................................................................................................ 5
6.3 Prediction of Natural Ageing ..................................................................................... 5
7. Discussion ......................................................................................................................... 8
7.1 Change with Time ...................................................................................................... 8
7.1.1 General ............................................................................................................. 8
7.1.2 Hardness .......................................................................................................... 9
7.1.3 Modulus ........................................................................................................... 9
7.1.4 Tensile Strength .............................................................................................. 10
7.1.5 Elongation at Break ........................................................................................ 10
7.1.6 DMTA ............................................................................................................ 10
7.1.7 Compression Set ............................................................................................. 11
7.2 Predictions ............................................................................................................... 12
7.2.1 General ........................................................................................................... 12
7.2.2 Hardness ........................................................................................................ 15
7.2.3 Modulus ......................................................................................................... 16
7.2.4 Tensile Strength .............................................................................................. 16
7.2.5 Elongation at Break ........................................................................................ 17
7.2.6 DMTA ............................................................................................................ 18
7.2.7 Compression Set ............................................................................................. 18
7.2.8 Choice of Analysis Method ............................................................................ 19
7.2.9 Effectiveness of the Predictions ....................................................................... 20
8. Conclusions .................................................................................................................... 21
References ........................................................................................................................... 22
Appendix 1 - Compound Details ......................................................................................... 23

Appendix 2 - Accelerated Heat Ageing Results .................................................................... 35
Compound A - Natural Rubber - Standard .................................................................... 37
Compound B - Natural Rubber - Good Ageing .............................................................. 41
Compound C - Natural Rubber - Mineral Filler Loaded ................................................ 45
Compound D - Natural Rubber - Mineral Filler (Heavy Loaded) .................................. 49
Compound E - Styrene Butadiene Rubber - General Purpose ......................................... 53
Compound F - Styrene Butadiene Rubber - Good Ageing ............................................... 57
Compound G - Styrene Butadiene Rubber - General Purpose ......................................... 61
Compound H - Styrene Butadiene Rubber - Good Ageing .............................................. 65
Compound J - Butyl Rubber - General Purpose .............................................................. 69
Compound K - Butyl Rubber - Good Ageing .................................................................. 73
Compound L - Polychloroprene - General Purpose ........................................................ 77
Compound M - Polychloroprene - Natural Ageing ......................................................... 81
Compound N - Polychloroprene - Heat Ageing .............................................................. 85
Compound P - Nitrile Rubber - General Purpose ........................................................... 89
Compound R - Polychloroprene - Good Ageing ............................................................. 93
Compound S - Miscellaneous - Acrylate Rubber ............................................................ 97
Compound T - Miscellaneous - Chlorosulphonated Polyethylene ................................ 101
Compound W - Miscellaneous - Polysulphide Rubber .................................................. 105
Compound X - Miscellaneous - Silicone Rubber .......................................................... 109
New Compounds
Compound N1 - FVMQ ............................................................................................... 113
Compound N2 - HNBR ............................................................................................... 117
Compound N3 - Epoxidised Natural ............................................................................ 121
Compound N4 - Chlorinated Polyethylene ................................................................... 125
Compound N5 - Fluorocarbon ..................................................................................... 129
Compound N6 - Exxpro ............................................................................................... 133
Compound N7 - Epichlorohydrin ................................................................................. 137
Compound N8 - EPDM ................................................................................................ 141
Compound N9 - EVA ................................................................................................... 145
Compound N10 - PU .................................................................................................... 149
Participants Compounds
Compound P1 ............................................................................................................... 153
Compound P2 ............................................................................................................... 157
Compound P3 ............................................................................................................... 161
ii
Ageing of Rubber - Accelerated Heat Ageing Test Results
Compound P4 ............................................................................................................... 165

Compound P5 ............................................................................................................... 169
Compound P6 ............................................................................................................... 173
Compound P7 ............................................................................................................... 177
Compound P8 ............................................................................................................... 181
Compound P9 ............................................................................................................... 185
Compound P10 ............................................................................................................. 189
Appendix 3 - Compression Set Results .............................................................................. 193
Appendix 4 - Example Graphs .......................................................................................... 201
iii
iv
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 accelerated
heat ageing tests and their analysis for the prediction of changes after long-term natural ageing.
The accelerated weathering and ozone test results have been published separately [2].
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

Natural rubber 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. The third natural rubber compound (C)
represents a fairly high rubber content non-black filled material. The last 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.
It is important to remember when considering the results obtained for these materials that the
re-mixes will not be identical with the original compounds produced in 1958 and this can be
expected to have significant effect on the correlation between natural and accelerated results.
As well as unavoidable differences in the polymers and compounding ingredients there was no
way of ensuring that the states of cure achieved were identical.
2.2 New Materials

Compound N1 is a fluorosilicone based on LS 2380U. The hydrogenated nitrile material,
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 diene terpolymer (EPDM), compound N8, is a
formulation typically used for radiator hose applications. Compound N9 is an ethylene vinyl
acetate (EVA) 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 cellular 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, carbon 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
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 thick sheets and type A compression set buttons 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:
tensile strength,
elongation at break,
stress at 100% elongation,
stress at 300% elongation,
microhardness,
compression set, and
dynamic mechanical thermal analysis (DMTA).
The first 6 properties listed correspond to properties monitored in the natural ageing
programme. DMTA allows a large amount of dynamic property data to be generated very
efficiently using small test pieces including tan (to relate to resilience), glass transition
temperature Tg, and T2 and T10 to compare with the Gehman low temperature test results.
Tests were carried out in general accordance with the current ISO methods [3-6]. For tensile
properties, type 2 dumbbells were used, with 3 dumbbells being tested for each measurement
point. For compression set, type A buttons were used with 2 buttons tested at each
measurement point. Hardness measurements were made by taking 5 readings on one test
piece. The dynamic measurements were made on a Polymer Laboratories DMTA apparatus
using clamped single cantilever geometry (strip test pieces 10 mm wide, 25 mm long and 2
mm thick) under the following conditions: displacement amplitude 64 x 10-6 m peak to
peak, frequency 1 Hz, temperature 80 C to 80 C, temperature ramp rate 3 C/min. One
test piece was used at each measurement point and 2 additional test pieces were available
to check on repeatability.
5 EXPOSURE OF TEST PIECES

Test pieces were exposed in air exchange ovens complying with ISO 188 [7] for a series of times
and temperatures. The temperatures used for a given material were selected bearing in mind
the known heat resistance of the material and the limitation that the longest exposure (lowest
temperature) would be 6 months. The temperatures are shown on the individual graphs of
property change with time.
For all properties except compression set, 5 batches of test pieces were prepared for each compound
which allowed a maximum of five temperatures to be used. The plan was to aim for a minimum
of 4 temperatures per material. Each batch consisted of 8 sets of 3 dumbbells, a piece of sheet for
hardness measurements and 8 strips (10 mm wide and 150 mm long) for DMTA tests.
Initially, 5 of the 8 sets were exposed at each selected temperature and the first set tested after
3 days. Further exposure times were then selected, adding sets of test pieces if necessary, with
the aim of obtaining useful results at a minimum of 5 exposure times with the longest time
yielding approximately a 50% change in properties. Test pieces were conditioned for a minimum
of 16 hours at 23 C prior to test.
For compression set, 6 sets of 3 buttons were prepared for each compound, which would allow
tests at 3 temperatures with two times at each temperature. (The original plan was for only 2
temperatures.) The times were somewhat arbitrarily chosen as 1 and 5 weeks. All compounds
were tested at 23 C and at 100 C or 150 C depending on the known heat resistance. The
third temperature was selected after consideration of the results at the first two temperatures.
6 RESULTS
6.1 Presentation
For properties other than compression set, the results for each property after artificial ageing
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.
Initially, a line was constructed for each graph that passed through the points. For analysis of
the data, the form of the curve drawn is not important as the Williams Landel Ferry (WLF)
transform uses the data points and the parameters for the Arrhenius plot are extracted from
the graphs manually, when the best fit can be estimated by eye.
There are too many graphs to be reproduced in total but those for hardness, tensile strength,
elongation at break and 100% modulus are given in Appendix 2 by material (there is no 100%
modulus graph for material P2) with all temperatures for a given material/property on one
graph. These are presented as the experimental points without any lines fitted. Predictions
derived from Arrhenius and WLF analysis other than compression set have also been tabulated.
The compression set results are tabulated in Appendix 3, Table 1 and two examples of the
results displayed graphically are given for compounds N1 and N2 in Figures 1 and 2. Predictions
were made from the compression set results by fitting a dose rate equation and these are tabulated
in Appendix 3, Table 2 for 1 and 40 years at 23 C.
The results for natural ageing after 40 years for the original 19 compounds are included in the
prediction tables for comparison.
The results derived from the DMTA measurements were in many cases erratic and/or the
changes were quite small and it was not considered useful to tabulate or show graphically
the full results. However, Tg for compound A and tan for compounds M and A are shown
in Appendix 4, Figures 1, 2 and 3.
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.
The uncertainties in estimates made by extrapolation of the results are inevitably very large.
Comment is made below on the validity and significance of predictions but no attempt at
quantification of the uncertainties has been made.
6.3 Prediction of Natural Ageing

Extrapolation of the accelerated results to longer times at lower temperatures was attempted
by two approachesthe Arrhenius relation and the WLF equationand compression set results
analysed using a dose rate equation. These techniques are outlined below and are discussed in
more detail in a guide to the assessment of the useful life of rubbers [8].
In this report, the predictions are made for change at 23 C and 40 C to equate to long-term
natural ageing under temperate and hot dry conditions. For some applications, particularly
with the more heat resistant polymers, it may be of greater interest to extrapolate to more
elevated temperatures that are representative of service conditions.
The reaction rate/temperature relationship can often be represented by the Arrhenius equation:
E
K(T) = Ae RT
or
E
Log(K(T)) = B
RT
where K(T) is the reaction rate, A and B are constants, E is the activation energy, R is the gas
constant, and T is the absolute temperature.
To enable Arrhenius plots to be constructed, a single measure to represent change with time at
each temperature is derived from the graphs. Ideally, the single measure would describe the
shape of the graph, most simply the slope of a straight line, but this is often not possible. The
most common practice is to take the time for the property to change by a given amount, for
example 50%, but in this work it would be more convenient if the change in a given time
could be used to make comparison with the natural results easier. Unfortunately, this is not
always feasible because of the differing timescales for property change at different
temperatures.
For the first 19 compounds, the measure used was the time to reach the change found in
natural ageing after 40 years under hot dry conditions. The hot dry condition was selected as
the higher temperature is nearer to accelerated ageing than temperate conditions and generally
gives a larger change than temperate conditions. Hot wet conditions are least relevant to
oven ageing.
For the remaining compounds, the times to reach a convenient, but arbitrary, percentage
change were used, which varied from compound to compound and from property to property.
The log of the measure of change of property with time (reaction rate) was plotted against
reciprocal of absolute temperature. Where this sensibly yielded a straight line, the best fit
line was constructed by computer.
The straight lines were extrapolated to give measures of the reaction rates at 23 C and
40 C. For the first 19 compounds these are expressed as the time to reach the level of change
found after 40 years natural ageing under temperate and hot dry conditions. For the remaining
compounds, they are expressed as the time to reach the end point chosen. These predictions
are tabulated, with the activation energies, for each material in Appendix 2. The natural
ageing results (where relevant) are included for comparison. Examples of the Arrhenius plots
are given in Figures 4-7 in Appendix 4.
It is important to appreciate that for the original materials only one end point was taken
the change after 40 years in hot dry conditions. This means that the Arrhenius predictions in
both the 23 C and 40 C columns are for the time to reach that end point. When comparing
the 23 C predictions with natural ageing in temperate conditions, to a first approximation
the predictions should be adjusted by the ratio of the change under temperate conditions to
that under hot dry conditions.
Similarly, when comparing the 40 C predictions with natural ageing in hot dry conditions
consideration should be given to the fact that the hot dry conditions averaged rather less than
40 C and hence all the predictions should be on the low side in terms of number of years.
An alternative to constructing the Arrhenius plot of log (K) against 1/T is to shift the plots of
property against time along the time axis to construct a master curve. It is based on the
principle of time and temperature superpositiona change in temperature being equivalent
to a change in rate. Essentially, the method consists of gradually shifting plots of property
against time determined at different temperatures to the plot at a selected reference temperature
until the curves partially overlap.
Hence, by successive shifts, a master curve at the reference temperature is obtained, for
which the origin of the timescale is fixed by the origin of the isotherm actually determined at
the reference temperature. Based on the same series of isotherms, the master curve naturally
shifts towards the shortest times when the reference temperature is higher.
This procedure has the important advantage that no particular measure of the reaction rate has
to be chosen nor any form assumed for the change of property with time. However, the model
can only be used if the curves have essentially the same form at different temperatures.
Use was made of the WLF equation to perform time temperature superpositions:
a(T T0 )
log(aT ) =
b + (T T0 )
In this expression, aT is the shift factor of an isotherm determined at temperature T, in relation

to the isotherm at the reference temperature T0, and a and b are two adjustable coefficients
dependent upon the material. By definition, when T=T0 there is no shift to apply.
The shifts were made using software developed for the purpose and the values of log(aT) plotted
against the corresponding temperature values. Standard curve fitting techniques were used to
determine the best fit for the WLF equation to give values of the constants a and b.
There is a problem because of the inherent discontinuity in the WLF equation. The form of the
equation is such that if, in the denominator, the best fit estimate for b is equal to T T0 at a
particular value of T, the expression for the shift factor reaches a discontinuity. The effect of
this is that for certain compounds the extrapolated temperature, e.g., 23 C, is in the critical
region. This leads either to abnormally long times (millions of years or more) if the temperature
was just above critical or abnormally short times (fractions of a second) if the temperature was
just below the critical point.
This was encountered in a few cases and in these circumstances a modified approach to the
shift factor was used and the formal WLF equation abandoned. The shift factor concept was
still used but for these situations an Arrhenius equation was fitted to the shift factor (not to
log(aT)):
aT = P exp(Q/RT)
where P and Q are coefficients found by best fit calculation, R is the gas constant and T the
absolute temperature in the normal Arrhenius fashion. This has the advantage that it has no
discontinuities and so a smooth temperature transition is assured.
Using the WLF equation, the master curve was shifted to 23 C and 40 C and predictions for
the changes after 40 years made. In some cases, this required extrapolation of the master curve
in time. These predictions are tabulated for each material with the natural ageing results (where
relevant) in Appendix 2. Note that these results are expressed as change in property after 40
years rather than the time to reach a given change used for the Arrhenius predictions. Examples
of the master curves are given in Figures 8-11 in Appendix 4.
As for the Arrhenius predictions, when comparing the 40 C predictions with natural ageing
in hot dry conditions consideration should be given to the fact that the hot dry conditions
averaged rather less than 40 C and hence all the predictions should be on the high side in
terms of percentage change. The predictions at 23 C can be directly compared to the temperate
natural results.
The predicted changes in tan have been converted to change in resilience to allow better
comparison with the natural ageing results. The relation used was:
Resilience = exp( tan ) x 100
The compression set (CS) results were analysed by fitting a dose rate relation:
CS =
100
t
1+
a
where t is time and a and b are coefficients for a particular material. This relation is self
limiting between 0 and 100 over the whole time range of 0 to infinity. With two values of
compression set and two times, the best fit values for the coefficients can be found.
Predictions were derived for the set after 1 and 40 years at 23 C using the results obtained at
23 C. These are given in Appendix 3, Table 2 with the natural ageing results under temperate
conditions (where relevant).
7 DISCUSSION
7.1 Change with Time
7.1.1 General
It is clear from the graphs in Appendix 2 that the directions and rates of change with time vary
considerably depending on material and property. The shape of the change of property with
time graph is not always consistent at all temperatures for a given material and property. It can
also be seen that in a number of cases the form of change with time is relatively complex.
Whilst apparent complex behaviour can sometimes be attributed to scatter of experimental
points, in many of these cases there appears to be real changes of rate of change and even
change of direction.
Considering the original 19 compounds, this is in contrast to the naturally aged results where,
although in many cases scatter was considerable, the form of change with time was generally
thought to be relatively simple. It is highly probable that many instances of change of rate and
direction in accelerated tests are due to different reactions occurring at different temperatures
and to the severity of degradation produced at higher temperatures and longer times.
This immediately confirms the generally held view that changes seen under high levels of
acceleration are not necessarily representative of changes at normal ambient conditions. Further,
such differences in behaviour are likely to be seen at the degree of acceleration needed to
produce results in what would be generally considered to be a reasonable timescale. The
implication for making predictions by extrapolation from accelerated tests is that the validity
of the results may be very dependent on the measure of change taken to fit the predictive
model, particularly its position along the time axis. It also indicates that longer exposures at
lower temperatures than was possible in the timescale of this work are desirable.
The actual rates of change of property with time in the accelerated tests are not sensibly contrasted
to those from natural ageing from simple observation of the curves. This is simply because it is
the rate at which the rates of change with time change with temperature (activation energy)
that will largely determine predictions made to lower temperatures.
When studying the graphs, note should be taken of the scale used so that the degree of scatter
is put in perspective. Despite the care taken in the preparation of test pieces and the testing, it
is apparent that the scatter is significant and it would have been advantageous if more data
points and more test pieces could have been afforded.
7.1.2 Hardness
Most of the hardness results showed a relatively simple form of change with hardness increasing
with time, but there were notable exceptions. After natural ageing all materials had either
increased or changed very little so overall there is a general correlation between natural and
accelerated results.
The natural rubber compounds AD are examples of where the curves are more complicated.
For compound B it is clear that hardness rises gently until at the two higher temperatures there
is a drop followed by a sharp rise. This report will not generally attempt to relate the changes
seen to reactions taking place but here it could reasonably be argued that reversion followed by
embrittlement occurred at the higher temperatures. With the other 3 materials, a drop in hardness
occurred very quickly except at the lowest temperature. Interestingly, the other natural rubber
compound P8 showed simply a gentle rise in hardness.
The butyl compounds J and K were the only ones consistently to show a decline in hardness
(they changed very little on natural ageing). Acrylate S, ethylene propylene P1 and the
thermoplastic elastomer P9 showed the tendency for a maximum and/or minimum followed by
a steep rise, similar to the behaviour of compounds AD. More complicated behaviour was
also seen in the polysulphide W, the fluorocarbon N5, polyurethane N10 and the cellular
material P2. Compound W is unusual in showing a sharp fall in hardness after an initial rise,
although the rise becomes very small at the lowest temperature. It is likely that the behaviour
of fluorocarbon N5 is due to experimental scatter. Materials N10 and P2 seem to have a
change of the direction of change depending on temperature. Both compounds S and W changed
little on natural ageing and the sharp fall found in accelerated tests for W must be due to a
different mechanism.
7.1.3 Modulus
Superficially at least, the 100% modulus curves are not dissimilar to those for hardness.
Again there is some cyclic behaviour with the natural rubbers AD, acrylate S, ethylene
propylene P1 and the thermoplastic elastomer P9, and compounds W and N10 show
complications. In some cases, the experimental scatter seems more evident than with hardness.
Where the modulus results are missing for longer times it is simply because elongation had
fallen below 100% (it did not reach 100% in the case of P2). There were no notable new
phenomena in the 300% modulus results and there are rather fewer results because of materials
breaking at lower elongations.
7.1.4 Tensile Strength

The scatter of results appears greater for tensile strength than for hardness making it more
difficult in a number of cases to be certain of the trend. However, for the great majority of
materials strength tended to fall. Only for Hypalon T, epichlorohydrin N7, and nitrile rubber
P3 was the trend fairly clearly for a rise in strength. In the natural ageing results compounds S,
T, W and X tended to rise but all the others either fell or changed little. In accelerated tests
compound S did show an initial rise, compound X actually changed very little but compound
W definitely fell. Hence, apart from compound W there was a general correlation between
accelerated and natural results.
Both polychloroprenes, M and N, and hydrogenated nitrile rubber N2 showed an upturn in
strength at the highest temperature only, indicating the onset of a different mechanism. The
nitrile P showed this at 90 C and 100 C but it was followed by a downturn in strength at
100 C. The nitrile R had a somewhat curious scatter of results at 70 C.
There was indication of cyclic behaviour for the hydrogenated nitrile rubber N2, chlorinated
polyethylene N4, nitrile rubber P4 and Vamac material P6. Compounds N2 and P6 appeared
to have maxima, followed by a minimum in the case of compound P6. Compounds N4 and P4
possibly had minima. The tensile strength of compound N5 apparently changes direction falling
slightly in strength at 150 C then rising at 210 C.
7.1.5 Elongation at Break

The change in elongation curves, with very few exceptions, showed a downward trend with
time. This was also the case for natural ageing. Hence, the pattern of change was quite consistent.
However, there were many instances where the curves at different temperatures crossed so that
there was inconsistency in terms of the trend with temperature.
The butyl rubber J exhibited some odd behaviour but this was probably only at the higher
temperatures. Elongation of polychloroprene L deteriorated very rapidly at longer times at the
highest temperature. Acrylate S was a rare case where elongation tended to rise, although it
appeared to go through a minimum first. There was possibly another change of direction at
long times. Hypalon T fell in elongation initially but at longer times there was considerable
scatter and the trend was a little uncertain. Rather curiously, the amount of initial fall seemed
to be inversely related to temperature. The polysulphide W exhibits particularly complex
behaviour and it is probable that the higher temperatures used were too severe. Significant
change only appears at the highest temperature for the fluorocarbon N5.
7.1.6 DMTA
The results from DMTA appeared to be subject to considerable scatter of experimental points
giving rise to particularly large uncertainty.
The general trend was for glass transition temperature to change little or rise with time of
ageing. Silicone X was an exception in that the glass transition temperature tended to fall.
Where the rise was considerable it occurred at longer times and at the higher temperatures.
10
The results for compound A (Appendix 4, Figure 1) illustrate this and reference to the tensile
strength and hardness graphs suggests that large rises in Tg occur after the material is quite
severely degraded.
The same general trend, as expected, was seen for T2 and T10 temperatures with most
materials showing little change or a rise with time for these properties. T2 decreased at
longer times for compound P6 and there were unexplained drops in T2 for materials N4 and
P9 at the longest time at particular temperatures. These three materials showed similar
behaviour for T10 temperature. No sensible results were obtained for P2.
The natural ageing results for T2 and T10 values were also subject to large scatter and it was
concluded that in many cases the changes were not significant. Cases of falling T2 or T10
values in natural ageing were not reflected in the accelerated results. Interestingly, the
correlation between T2 and T10 was probably better for the accelerated results than for the
natural ageing.
Considering the scatter of results, for most materials tan could be said to show little
change. An example is shown for compound M (Appendix 4, Figure 2). Where there was
significant change there were some cases of a rise and some, but less, cases of a fall. Changes
in resilience for the natural ageing were also found to be generally fairly modest. Where
appreciable rise or fall was recorded on natural ageing there was an inverse general
correlation with the direction of change found in the accelerated tests. This should be
expected as tan decreases as resilience increases, and at the tan = 0.2 level a change of
0.01 is equivalent to about 6% resilience. The absolute values of tan and resilience are
unlikely to correlate well as they are obtained at two different frequencies. The results for
compound A (Appendix 4, Figure 3) show that a large increase in tan probably occurs
only after quite severe degradation and at the lowest temperature there is some evidence
that there is first a decrease in tan .
7.1.7 Compression Set

Not surprisingly, in all cases compression set increased with time of exposure and with
increasing temperature. Hence, the direction of change shows complete correlation between
natural and accelerated exposure. Some of the rates of increase with time at 23 C are small
and there was no change with the polysulphide W at the highest temperature as it reached
100% set in the shorter time. The test pieces of fluorocarbon N5 crumbled on removal from
the jigs at 140 C and 200 C (the highest temperatures used). The most plausible explanation
is that local breaking strains at the elevated temperature were exceeded, possibly in
combination with incomplete knitting of a rolled blank.
The two examples of the compression set results presented graphically in Figures 1 and 2,
Appendix 3 (for compounds N1 and N2, respectively) illustrate how the rate of change
with time will vary for different materials and for different temperatures. As set approaches
100% the rate of change with time will become smaller because of the asymptotic nature
of set curves.
11
7.2 Predictions
7.2.1 General
The predictions obtained by WLF and Arrhenius analysis are presented by material in Appendix
2, blank cells indicating where it was not possible to obtain a prediction or, in the case of 300%
modulus, where there were no (or insufficient) results.
The quality of the WLF master curves and the Arrhenius plots varied considerably. A good
WLF master curve is where the transforms fit smoothly and for Arrhenius plots, the best appear
as a perfect straight line. By way of illustration, the Arrhenius plot for elongation at break of
compound G is given in Appendix 4, Figure 4, which is a good example and, in Appendix 4,
Figure 5, the Arrhenius plot for elongation at break of compound N9 which is rather less good.
The very respectable WLF master curve for elongation at break of compound M at 40 C is
given in Appendix 4, Figure 8, and the unsatisfactory WLF master curve for elongation at
break of compound K at 23 C in Appendix 4, Figure 9.
Where the WLF master curve was particularly bad and essentially a scatter diagram or the
Arrhenius plot was far from a straight line no prediction could be made. However, there was
apparently not good correlation between relatively poor WLF or Arrhenius plots and wrong
or unreasonable predictions, nor between particularly good plots and good predictions. This
is probably because poor predictions are more related to the shapes and direction of the
property-time curves at elevated temperatures.
Considering first the original 19 materials and the results for hardness and tensile properties,
predictions were obtained using the WLF equation for about 95% of the cases (property and
material) but using the Arrhenius relation a prediction was only obtained in about 75% of the
cases. Where no prediction was obtained by WLF theory it was because the data did not yield
a sensible fit to the transform. No prediction was obtained using the Arrhenius relation when
either there was no sensible change in the property with time at the various temperatures or the
heat ageing results showed a change in the opposite direction to natural ageing. It is largely
because of the latter point that there are fewer predictions using the Arrhenius relation than
when using WLF theory.
In over 85% of the predictions made using WLF theory, the change predicted was in the same
direction as that seen in natural ageing. Because of the end point chosen, all the predictions
obtained using the Arrhenius relation were in the same direction as seen in natural ageing.
Hence, ignoring magnitude, predictions from the accelerated tests are apparently showing the
same trend as natural ageing in over 80% of cases using WLF theory and over 75% using the
Arrhenius relation. In about 60% of the cases where the WLF prediction was in the wrong
direction a prediction was not obtained using the Arrhenius relation. Hence, there is a relatively
small but significant number of cases where there is disagreement between the two approaches.
This can doubtless be related to the choice of end point with the Arrhenius approach (where a
different end point could result in the prediction changing direction) and the use of all the data
with WLF theory. This in turn is related to cases where the change of property with time
changes direction.
A prediction being in the right direction is perhaps more significant than how near it is in
magnitude to the change seen in natural ageing. If the correct trend is predicted it gives some
12
confidence that accelerated tests were a valid approach. The degree of extrapolation being
applied to these results is so large that the uncertainty in magnitude of the predictions is such
that a result within 50% of that realised in natural ageing would be considered good.
The magnitude, and in some cases the direction, of change predicted by the Arrhenius relation
can be changed by choosing a different end point. The magnitude can also be changed by
ignoring results at one or more of the test temperatures. The magnitude of change predicted by
WLF theory is subject to the interpretation of the master curve and can also be changed by
ignoring a temperature.
It will be appreciated that to make numerous analyses of all the data in this study would
constitute a prohibitive volume of work for one report. However, in many cases there is scope
for more detailed study of particular material/property combinations using different criteria
from the ageing curves as input.
As a simple illustration of possible alternatives, further analysis of the hardness changes of two
compounds by the Arrhenius and WLF relations has been made.
As can be seen from the plots of the hardness results for compounds B and R (given in
Appendix 2), compound B showed relatively complicated behaviour with the shape of the
hardnesstime plot changing with temperature, whilst compound R showed relatively consistent
increase of hardness with time.
This is reflected in the WLF master curves (Appendix 4, Figures 10 and 11) where compound
R gives a much smoother fit than compound B. The best predictions from these for change in
hardness after 40 years at 40 C are 49% for compound B and 82% for compound R. After
long-term exposure in a hot dry climate (not averaging as high as 40 C) these materials actually
changed by 24% and 55%, respectively.
Arrhenius plots were constructed with the end point taken as 24% and 55% (which required
judicious extrapolation for some curves) and are shown in Appendix 4, Figures 7 and 8,
respectively. These yielded predictions of 7 years and 6 years at 40 C for compounds B and R,
respectively, and 24 years and 16 years at 23 C. Considering the shapes of the hardnesstime
curves for compound B, this end point would be difficult to justify and it is perhaps remarkable
that sensible predictions were obtained.
The Arrhenius plot for compound B in particular is clearly not a perfect straight line. If the
70 C point is ignored the prediction becomes 21 years at 40 C and 124 years at 23 C, whilst
if the 100 C point is ignored these figures are 3.5 years and 9 years, respectively. This is not the
direction one would expect and is probably an artifact of the end point used.
The effect of ignoring points for compound R is less drastic, reflecting the better straight line
seen in the Arrhenius plot. The corresponding figures are 6 years and 17 years ignoring the
70 C point and 4.5 years and 11 years ignoring the 100 C point.
Had it not been for an interest in making direct comparisons with long-term exposures, it
would be sensible to have chosen rather lower end points. If an end point of 10% is taken for
compound B the scatter on the Arrhenius plot is increased and the predictions are 1.5 years at
40 C and 4 years at 23 C for a 10% change. However, if the 100 C point is ignored these
become 5 years at 40 C and 35 years at 23 C. With linear extrapolation this is equivalent to
12 years and 84 years to reach 24% change at 40 C and 23 C, respectively.
13
Taking an end point of 20% for compound R also increases the scatter on the Arrhenius plot
and yields predictions of 2 years at 40 C and 9 years at 23 C. Ignoring the 100 C point yields
3.5 years at 40 C and 20 years at 23 C. With linear extrapolation this is equivalent to 10
years and 55 years to reach 55% change at 40 C and 23 C, respectively.
Where the Arrhenius plot is not linear there is justification in ignoring the highest temperature
as not being representative of reactions at lower temperatures. With this selective use of the
data very reasonable predictions in comparison to natural exposure could be obtained.
All the predictions in these examples showed the same trend as in natural exposure but tended
to overestimate the rate of change. Considering the uncertainty in actual temperature on natural
exposure, the WLF predictions could be said to be good for both compounds, in spite of the
shapes of the property-time curves for compound B. With selective use of the data, good
predictions were obtained for both compounds by the Arrhenius approach.
In considering any of the predictions obtained for the original 19 materials it should be
remembered that the accelerated tests were carried out on re-mixes which will not be identical
with the original compounds mixed 40 years previously.
Considering hardness and tensile properties for the new compounds, predictions could not be
obtained in about 6% of cases. This is rather less than for the original materials but, remembering
that there were no restrictions on the choice of end point for Arrhenius, is probably not
significant.
There are of course no natural ageing results for these materials so taking these predictions to
be valid is an act of faith. Judging from the results for the original 19 materials it might be
postulated that the odds would be on less than 15% being totally wrong, but that is pure
conjecture. Of course, the same situation applies to these results as to those for the original
materials and by making alternative analyses, for example with different end points, different
predictions could be obtained. The choice of end points for the predictions given were somewhat
arbitrary and not restricted by needing comparison with natural ageing.
Taking a broad view of the comparison between the Arrhenius and WLF approaches there is
complete conflict in the direction of the predictions in about 5% of cases.
As noted in sections 6.1 and 7.1.6, the results derived from the DMTA measurements were
rather less satisfactory than for hardness and tensile properties. In consequence, the predictions
made are subject to even more uncertainty. Predictions were obtained in only 32% of cases and
a number of these would appear highly suspect. The problem is a combination of the degree of
change being relatively small in the majority of cases and the degree of scatter in the results.
The magnitude of the predicted changes in comparison to natural ageing is considered property
by property below. For the original 19 compounds the WLF predictions are directly comparable
with natural ageing as they are given in percentage change after 40 years. A direct comparison
of the magnitude of change predicted by Arrhenius with natural ageing is not possible because
of the restrictions of the analysis. Hence it is necessary to compare the changes that occurred in
40 years with predictions of the number of years to produce the same change.
As pointed out in section 6.3, it is important to note that the Arrhenius predictions in years
are the times to reach the degree of change that were found after 40 years natural ageing in
14
the hot dry climate. Hence, taking the hardness of compound A in Appendix 2, as an example,
the Arrhenius predictions are for a change of 7.6% (i.e., the change found for natural ageing
after 40 years under hot dry conditions). It is also important to remember when comparing
the 40 C predictions from both the Arrhenius and WLF approaches with natural exposure
under hot dry conditions that the average temperature in the natural exposures was rather
less than 40 C.
The Arrhenius analysis yields figures for the activation energy which is a measure of the rate of
change of the reaction rate (or end point) with temperature. The activation energies obtained
vary over a very large range and it is highly probable that they reflect the uncertainty of the
data. In a few cases (in addition to those where no Arrhenius predictions were obtained) no
activation energy is tabulated because it was clear that the calculated value was largely a product
of noise in the data. Figures found in the literature generally range between 70 kJ and 120 kJ so
the lower energies predicted in some cases could be considered unrealistic. However, it is
interesting that low predicted activation energies did not correlate with particularly poor
estimates of change of properties.
7.2.2 Hardness
Considering the original 19 materials, predictions were obtained in all cases using WLF theory.
There were 3 instances where no prediction was obtained using the Arrhenius relation:
compounds J, K and T. For compound J there could not be a prediction as there was no change
on natural ageing, for compound K change was too little at two of the temperatures, and for
compound T there was very little change on natural ageing.
For compounds C, D, K and W there were WLF predictions in the wrong direction. It is obvious
that for compounds C and D the drop followed by a rise in hardness accounts for the difference
between the 23 C and 40 C predictions. For compound K there was little change at 3
temperatures and an excessive drop in hardness at the highest temperature and a prediction is
not really sensible. For compound W the rates of change at the highest 3 temperatures were
clearly excessive.
In the great majority of cases WLF theory overpredicts the degree of change by a factor of 2 or
more. For materials J, N and S the predictions can be considered remarkably accurate. In just
two cases, compounds L and X, does the prediction underestimate the change although the
difference is certainly within the uncertainty band.
The Arrhenius approach also overestimates the degree of change, or rather underestimates the
time for the change, in most cases. For materials C, D and P the predictions overestimate the
time for change at 23 C. For compound E the predicted time at 23 C is remarkably accurate.
For compounds S and X the times for change are overestimated for both 23 C and 40 C.
It is interesting that the Arrhenius approach has in a few cases underpredicted the time at 40 C
but overpredicted the time at 23 C. In this context, it should be noted that for both the WLF and
Arrhenius approach the hot dry climate of the natural exposures has been approximated as 40 C
whereas in fact it was probably less than this. The temperate climate was very close to 23 C.
For the new compounds predictions were obtained using both the WLF and Arrhenius
approaches in all cases except one; no prediction was obtained for compound P2 using the
15
Arrhenius approach. For two compounds, N10 and P1, there is conflict as to the direction of
change predicted by the 2 approaches. This can be attributed to the change in hardness changing
direction with time and in the case of N10 to the WLF fit being very poor. There are several
cases where the WLF and Arrhenius predictions are in the same direction but differ in magnitude
by a very large margin, the more obvious being N2, N4, P5, P6, and P9 where the times
predicted by the Arrhenius relation are very long.
7.2.3 Modulus
For the original 19 materials predictions were obtained using WLF theory in all possible cases
except for compounds A and X at 100% and compound T at 300%. Arrhenius predictions
were not obtained for compounds J, K, S, T, W and X at 100%. At 300%, predictions were
only obtained for materials B, C, F and H. For compounds A and X the changes in 100%
modulus were very small. For compound T there were few results for 300%. The lack of
Arrhenius predictions is largely because of the conflicting direction of change in natural and
accelerated tests and changes in direction for accelerated ageing, but scatter of results is also a
factor. It is interesting that modulus appears to be a far less reliable property for obtaining
predictions than hardness.
The WLF predictions were in the wrong direction for 100% modulus of compounds K and W
at 40 C, probably because of the accelerated results changing direction with time. The same
applies to compound D at 300%. The 300% modulus predictions were also in the wrong
direction for compounds A, C, G and N. For compounds A and C changing direction in
accelerated tests was again apparent but for compounds G and N the natural and accelerated
results are simply different.
As for hardness, WLF theory overestimates the degree of change in the great majority of cases
but there are several underestimates for one of the two temperatures and several cases where
the predictions match the natural results quite well.
With the exceptions of compounds C and X, the Arrhenius predictions underestimate the
time for change and the predictions for compounds M and N at 23 C are very near to the
natural results.
For the new compounds, predictions were obtained in all possible cases except from WLF
theory for 100% modulus of compounds N5 and P5 and 300% modulus of P1, and from the
Arrhenius relation for 100% modulus of compounds N5, N6 and P9 and for 300% modulus
of compounds P1 and P9. There are no conflicts between the two approaches, and although
WLF theory predicts no change for compound P6, the Arrhenius prediction is for a very long
time to see appreciable change. However, there are again cases of WLF and Arrhenius predictions
differing in magnitude by a large margin.
7.2.4 Tensile Strength

For the 19 original materials, tensile strength predictions were not obtained by WLF theory for
compounds K, M and R and by the Arrhenius relation for compounds J, K, L, P, S, T, W and X.
These cases are associated with either a small change on natural ageing, small changes from accelerated
ageing, anomalous behaviour or too great an extrapolation needed from the WLF master curve.
16
WLF predictions were in the wrong direction for compounds J, N, S and W although for
compound J the differences were fairly small. The changes on natural ageing for compound X
were also quite small and the prediction was for no change.
Again, WLF theory overestimated the change in almost all cases although the predictions for
compounds L and P were very near to the natural results and the prediction for compound C
was an underestimate.
Underestimates of the time for change were again obtained from the Arrhenius predictions in
most cases but overestimates were given for compounds C and E whilst the estimates for
compounds A, B and G at 23 C were very near to the natural ageing results.
For the new compounds, predictions were obtained by WLF theory in all cases except materials
N5, P2 and P6 and by the Arrhenius relation in all cases except compounds N5, N8, N9, P2
and P6. The trend with time for compound N5 changed with temperature and there was also
evidence of this with compounds P2 and N9. Compounds P6 and N8 showed a large degree of
scatter. There is conflict as to the direction of change with compounds P1, P4 and P10 at 40 C,
which is probably associated with change in strength changing direction with time. With
compounds N1, N7 and P5, WLF theory predicts no change whilst the Arrhenius approach
predicts a fairly modest increase in strength. In these cases there are also changes in direction of
change in strength. Once again there are cases of WLF and Arrhenius predictions differing in
magnitude by a very large margin.
7.2.5 Elongation at Break

Considering the original 19 compounds, predictions were obtained in all cases using WLF
theory except for material R, whilst no predictions were obtained using the Arrhenius relation
for compounds K, L, S, T and W. The change of elongation for compound R was very rapid at
all except the lowest temperature. The changes on natural ageing were small for compounds K,
L and S. The accelerated results for compound K were somewhat scattered, compound L changed
very little, there were changes of direction with temperature for compound S, changes of direction
with time for compound T and changes with both temperature and time for compound W.
The two approaches did not agree on the direction of change for compounds W, J and K at
40 C. For compound X, WLF theory predicted no change at 23 C but on natural ageing
compound X showed a small rise in elongation. The Arrhenius relation predicted that compound
X would have a large drop in elongation. The disagreement for compound W can probably be
attributed to the change of direction with time and temperature and for compounds J and K to
scatter and change of direction with time. The disagreement for compound X illustrates the
effect of a relatively modest swing from a positive to a negative change of direction.
Yet again, WLF theory overestimated the change in the great majority of cases with only
compounds C and N resulting in underestimates. The predictions for compounds S, E and M at
23 C were close to the natural results.
The Arrhenius predictions are almost all underestimates of the time for the change but the
prediction for compound G is an overestimate at 23 C. The predictions that best match the
natural results at 23 C are for compounds R, N, E and C.
17
The only cases where no predictions were obtained for the new compounds were for P9 using
WLF theory and for compounds N5 and P2 using the Arrhenius relation. The WLF master
curve for compound P9 resembles a scatter diagram. There was some change of direction with
time and temperature for compound N5 and little change in elongation for compound P2.
There were no disagreements of direction of change between the 2 approaches. For material
P6, WLF theory predicted no change but the Arrhenius relation predicted thousands of years
for a 25% change. The same situation applied to elongation as to the other properties in that
there were some large differences in magnitude between WLF and Arrhenius predictions.
7.2.6 DMTA
Predictions for the DMTA parameters were generally only obtained in 2550% of the cases
although almost 75% were obtained for T2 using the Arrhenius relation. Although only of the
order of 15% of the cases where WLF predictions were obtained were in the wrong direction
compared to natural ageing, there were very few where the prediction was reasonable. This
could said to be the case for T2 of compounds C and W at 23 C, T10 of compounds E at 23
C, T10 of K, and resilience of G and F. There were a similar number of reasonable predictions
using the Arrhenius approach. It is concluded that the reproducibility of these DMTA parameters
is too poor for them to be effective for this type of long-term prediction and the situation is not
helped by the changes in natural ageing being small for most of the parameters.
Some of the Arrhenius plots obtained were clearly unsatisfactory but many of them appeared
to be quite reasonable and did not immediately indicate that predictions would be poor. It was
clear that almost all of the WLF master curves showed far from perfect fit of the transforms
which would indicate that predictions were likely to be unreliable. However, the best fits did
not correlate with the cases where reasonable predictions were obtained.
7.2.7 Compression Set

The predictions for compression set are always in the right direction. As can be seen from Appendix
3, Table 2 the magnitude of predictions for set after 40 years is always smaller than was found in
natural ageing under temperate conditions. The predictions for set after 1 year are also lower
than natural ageing for most compounds but in 3 cases, compounds F, H and N, the predictions
are larger. The two values are similar for compound K. There is little correlation in terms of
ranking of materials between the predictions and natural ageing after 40 years but, with the
exception of compounds F, H, N and K, there is quite reasonable correlation after 1 year.
As only two times of exposure were used, perhaps it would be surprising if the results had been
any better. If measurements were made at several times and for up to 6 months as for the other
properties it is likely that much better extrapolations could be obtained for set behaviour.
However, it is curious that all the predictions at 40 years and the great majority at 1 year are
low, which cannot reasonably be attributed to differences between the original materials and
the re-mixes. Three possibilities are suggested. Chemical ageing could play a significant part
after 40 years, although this does not explain the bias to low results after 1 year. It would,
however, affect the correlation between predictions and natural ageing. The rate of recovery
may be proportional to exposure time and hence higher set would be recorded at longer times
using the standard 30 minute recovery period. It is also possible that the difference in test piece
18
dimensions between the natural and accelerated ageing samples is significant (a special annulus
test piece was used in the natural exposures).
The predictions in this table were obtained using the results at 23 C only. Including the data at
elevated temperatures gave a worse fit to the dose rate relation. If there had been more time
points it might be that using all temperatures would be advantageous.
It can also be noted that the results do not support the idea that single point compression set
data obtained at elevated temperature will correlate with longer term performance at ambient
temperature. For example, the data obtained for 1 week at 70 C is roughly split 50% either
side of the natural results after one year.
7.2.8 Choice of Analysis Method

Since there are the two techniques available for estimating the change in property that will
result at a time or temperature other than those experimentally chosen, the question arises as
to which is the better. Both techniques have certain advantages and drawbacks.
The WLF approach relies on the validity of the time-temperature superposition principle whilst
the Arrhenius approach is dependent on the validity of the assumption that increasing
temperature merely increases the rates of change and does not introduce new types of change.
Neither of these is likely to be completely true in all cases, primarily because there will be
different reactions taking place at different temperatures.
The WLF approach provides a master curve that encapsulates the whole of the accumulated
data and therefore potentially provides the greatest information. The Arrhenius approach on
the other hand usually disregards the bulk of the data gathered being limited to a specific end
point, which may have been arbitrarily chosen. If it is possible to use all the data at each
temperature to obtain a reaction rate then this disadvantage of the Arrhenius approach would
disappear.
Although the Arrhenius approach is mathematically simpler, with computer help the WLF
approach is practically easier to use because of there being no need to specify a measure of
reaction rate nor to make any assumptions when interpolating between points.
The WLF approach is also more versatile in that it is relatively easy to produce predictions in
terms of time to reach an end point and as change in a given time. With the Arrhenius approach
this necessitates re-doing the calculation completely with a different measure of reaction rate.
It does not appear that one of the methods consistently gives better correlation with natural
ageing results. Where the change of property with time is uncomplicated and consistent, very
similar results can be expected from the two approaches.
The problems arrive when the change of property with time is complex, for example if it first
falls and then rises. It was seen several times in this work that the WLF approach in taking all
the data may produce a prediction which is dominated by one part of the ageing curves.
Sometimes intuition suggests that this is giving an invalid prediction. With the Arrhenius
approach it is necessary to make a choice of which part of the curve will be used and the
validity of the prediction will then be dependent on whether that choice was correct.
19
When a WLF master curve is generated the timescale it spans depends on the timescale of the
ageing tests and on the activation energy. In some cases it is necessary to extrapolate the master
curve to the time of interest which increases uncertainty. If the extrapolation needed is unreasonably
large no prediction can be obtained from what appears to be perfectly good raw data.
Both methods will indicate if results at one temperature are out of line with the others (for
example because of a different reaction taking place). With Arrhenius the plot will be curved
for the Arrhenius approach and using the WLF approach the poor fit to the master curve will
be obvious.
One conclusion is that more time should be spent than was possible for this report on studying
the data in each case and that several analyses should be made, using all and parts of the data.
Alternatively, if you are certain that all the data is relevant and valid then the WLF approach is
usually the better choice, whereas if it is believed that part of the data is more valid than the
rest then the Arrhenius approach is more appropriate.
7.2.9 Effectiveness of the Predictions

Without restrictions on the end point used, predictions for hardness and tensile stress-strain
properties were obtainable in over 90% of exposure trials. There was some variation between
the different parameters with hardness being most successful and 300% modulus least successful.
For DMTA parameters there was a much lower success rate for obtaining predictions. The
differences between the properties being considered is largely attributable to differences in
their repeatability and reproducibility but is also affected by the magnitude of the changes seen
and the shapes of the plots of change of property with time. There are obviously least problems
with relatively large changes in property and low degrees of scatter.
The ease of obtaining a prediction also varies with material where, apart from differences in
variability, the main factor is the shapes of the plots of change of property with time.
It is one thing to obtain a prediction but quite another to obtain a valid or reliable prediction.
In this work, the success rate in terms of predicting the same direction of change as seen in
natural ageing was good for the hardness and tensile properties. In most of the cases where the
direction was wrongly predicted it was possible to see how this could arise because of some
complexity in the property-time curves. The predictions for the DMTA parameters were far
less good but it was possible in most cases to see the probable causes of difficulty associated
with scatter of results, magnitude of the changes and the shapes of the property-time curves.
Compression set was shown to be a special case in that the direction of change and the general
form of the compression set-time curve are always correctly predicted. Relatively few
compression set results were obtained in this work and the predictions made from them always
underestimated the long-term set found in natural ageing. However, the results raised optimism
that if a quantity of results comparable with that obtained for the other properties were to be
obtained good predictions could result.
For the hardness and tensile properties, where the direction of change was correctly predicted,
the majority of predictions overestimated the degree of change. The reasons for this are not
entirely clear but are doubtless connected with changes in reaction rate and shape of the propertytime curve with temperature.
20
In all cases where the property-time curve changes in shape or direction, either with time or
with temperature, the choice of ageing temperature and the measure of change used will be
critical. The analysis in this report only scratched at the surface of what could be done with the
mass of data collected by taking different measures of change and rejecting parts of the data.
With different analysis it is likely that some predictions could be improved.
It was also very evident that, despite the size of the programme and the care taken, it really
needed more temperatures, more time points and more test pieces to be used to reduce
uncertainty. In particular, there were many cases when testing at lower temperatures and for
longer times was highly desirable, confirming the view that successful accelerated testing will
inevitably be very costly in time and effort.
The main conclusion from the work is that accelerated ageing to predict performance at longer
times is certainly not all good but is by no means all bad. The results obtained here may be
disappointing in some respects but are also encouraging in that with sufficient time and effort
it seems likely that very useful predictions could be obtained in most cases. Conversely, the
results show that if the times and temperatures used are inadequate and/or the experimental
uncertainty is too high then there is a high chance of obtaining poor predictions.
8 CONCLUSIONS
An accelerated heat ageing programme involving a total of 39 rubber compounds has been
successfully completed.
The results showed that in many cases the curve of property change with time was complex
indicating that reactions occurred which were not present in natural ageing.
For hardness and tensile stress-strain properties, predictions (sensible or otherwise) of change
at ambient temperatures could be made in 90% of the cases using WLF and Arrhenius relations,
but the use of DMTA parameters was far less successful.
A significant number of predictions were in conflict with the results of natural ageing. Where
the direction of change was correctly predicted the predictions overestimated the degree of
change in most cases.
For compression set, the direction and general form of the change with time could always be
correctly predicted but with the limited results obtained in this programme the set after long
times was underestimated.
There is considerable scope for more extensive analysis of the data generated by taking different
measures of change and rejecting parts of the data.
To reliably obtain useful predictions from accelerated test requires the use of more temperatures
and data points than were possible in this work, in particular testing for longer times at lower
temperatures.
21
REFERENCES
1. R.P. Brown and T. Butler, Natural Ageing of RubberChanges in Physical Properties over
40 Years, Rapra Technology Limited, 2000.
2. R.P. Brown, T. Butler and S.W. Hawley, Ageing of RubberAccelerated Weathering and
Ozone Test Results, Rapra Technology Limited, 2001.
3. ISO 37 1994 Rubber, vulcanised or thermoplasticDetermination of tensile stress-strain
properties.
4. ISO 48 1994 Rubber, vulcanised or thermoplasticDetermination of hardness.
5. ISO 815 1991 Rubber, vulcanised or thermoplasticDetermination of compression set at
ambient, elevated or low temperatures
6. ISO 4664 1998 RubberDetermination of dynamic properties of vulcanisates for
classification purposes (by forced sinusoidal shear strain).
7. ISO 188 1998 Rubber, vulcanisedAccelerated ageing or heat resistance tests.
8. R.P. Brown, Practical Guide to the Assessment of the Useful Life of Rubbers, Rapra
Technology Limited, 2001.
22
APPENDIX 1
COMPOUND DETAILS
23
Appendix 1
24
Natural Rubber
Natural Rubber
Ingredient
Amount
(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
CBS
0.5
PBN
1.0
Sulphur
2.5
Compound B - Good Ageing
Smoked sheet
100
HAF black
50
Stearic acid
0.5
Pine tar
4.5
Zinc oxide
TMTD
2.5
PBN
1.0
MBT
1.0
Compound C - Mineral Filler Loaded
Smoked sheet
100
Stearic acid
1.5
Petroleum-based softener
Zinc oxide
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
25
Zinc oxide
CBS
0.6
PBN
1.0
Sulphur
3.2
200
25
Appendix 1
Styrene Butadiene Rubber

Ingredient
Amount
(pphr)
Compound E - General Purpose
SBR 1500
100
HAF black
50
Stearic acid
4.5
Zinc oxide
CBS
1.0
PBN
1.0
Sulphur
1.75
Compound F - Good Ageing
SBR 1500
100
HAF black
50
Stearic acid
4.5
Zinc oxide
TMTD
PBN
1.0
MBTS
1.0
Compound G - General Purpose
SBR 1710
100
HAF black
50
Stearic acid
4.5
Zinc oxide
CBS
1.0
PBN
1.0
Sulphur
1.75
Compound H - Good Ageing
SBR 1710
100
HAF black
50
Stearic acid
4.5
Zinc oxide
TMTD
PBN
1.0
MBTS
1.0
26
Butyl Rubber
Butyl Rubber
Ingredient
Amount
(pphr)
Compound J - General Purpose
Polysar 301 (high unsaturation)
100
FEF black
50
Zinc oxide
Stearic acid
MBT
0.5
TMT
1.0
Sulphur
Compound K - Good Ageing
Polysar 100 butyl (low unsaturation) 100
HAF black
50
Zinc oxide
25
Sulphur
MBTS
GMF
27
Appendix 1
Polychloroprene
Ingredient
Amount
(pphr)
Compound L - General Purpose
Neoprene type WRT
100
Light calcined magnesia
PBN
Stearic acid
0.5
SRF black
40
Robac 22
0.75
Zinc oxide
Compound M - Natural Ageing
Neoprene type WRT
100
Akroflex CD
Stearic acid
0.5
SRF black
50
DOTG
0.75
TMT-MS
0.75
Sulphur
0.75
Zinc oxide
Compound N - Heat Ageing
Neoprene type WRT
100
Aranox
0.5
Akroflex CD
Octamine
3.5
Stearic acid
0.5
SRF black
30
90
Low volatile process oil
Robac 22
Zinc oxide
25
28
Nitrile Rubber
Nitrile Rubber
Compound P - General Purpose
Ingredient
Amount
(pphr)
Nitrile rubber
100
Compound R - Good Ageing
(ca. 32-34% acrylonitrile)

SRF black
50
DOP
20
Zinc oxide
Stearic acid
PBN
MBTS
1.5
Sulphur
1.5
Nitrile rubber
100
(ca. 35% acrylonitrile)

SRF black
50
DOP
10
Polypropylene adipate
10
Zinc oxide
Stearic acid
Flectol H
TMTD
CBS
29
Appendix 1
Miscellaneous
Ingredient
Amount
(pphr)
Compound S - Acrylate Rubber
Hycar 4021
100
SRF black
50
Stearic acid
Triethylene tetramine
TMTM
Sulphur
Compound T -
Hypalon 20
100
Chlorosulphonated polyethylene
45
Hydrogenated wood rosin
Litharge
20
MBTS
0.5
Flectol H
Process oil
10
Robac P25
0.75
10
Compound W - Polysulphide Rubber
Thiokol St
100
SRF black
60
Stearic acid
GMF
1.5
Zinc oxide
0.5
Dimethyl silicone gum (slightly

unsaturated)
100
Diatomaceous silica
45
Fine silica
36
Ferric oxide
2,4-dichlorobenzoyl peroxide in
silicone fluid
Compound X - Silicone Rubber

Post cure 1 h @ 150 C, 24 h @ 250 C
in air
30
New Compounds
New Compounds
Ingredient
Amount
(pphr)
Compound N1 - FVMQ
Silastic LS 238 OU
100
Curing conditions: 10' @ 171 C,
Silastic HT-1
Post cure 4 h @ 200 C in air
DHBP (50% silicone oil)
0.9
Compound N2 - HNBR
Zetpol 2000L
100
Spheron 4000
60
Naugard 445
1.5
Rhenogran ZMMBI 50
Zinc Oxide Active
Peroximon F40
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
Flectol pastilles
0.2
Maglite DE
10
SRF N772 black
60
FEF N550 black
50
Britomya BSH
20
Bisoflex TOT
35
Drapex 39
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
Maglite DE
Compound N6 - Exxpro
Exxpro MDX90-10
100
HAF N330 Black
50
Stearic Acid
Zinc oxide
0.5
Tetrone A
31
Appendix 1
New Compounds (continued)

Ingredient
Amount
(pphr)
Compound N7 - Epichlorohydrin
Hydrin C65
100
SRF N772 black
70
Winnofil S
Paraplex G50
DOP
Vulkanox MB
Stearic acid
Span 60
Zisnet F
DPG
0.3
Maglite DE
Compound N8 - EPDM
Vistalon 7000
100
Zinc Oxide
10
Stearic Acid
SRF N772 Black
45
FEF N550 Black
60
Strukpar 2280
59
Sulphur
TMTD
2.5
ZDMC
2.67
NDBC
Sulfasan R
1.7
Compound N9 - EVA
Levapren 400
100
Staboxal PCD
Post cure 2 h @ 165 C in steam
Zinc stearate
Vulkanox DDA
FEF N550 Black
30
Mistron Vapour
50
Perkadox 14/40
TAC
Compound N10 - PU
Adiprene FM
100
FEF N550 Black
40
DBP
Stearic Acid
Dicup 40C
Rhenogran TAC50
32
Participants Compounds
Participants' 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
Activators
Fillers
Process aids
6PPD
TMQ
Antiozonant wax
Sulphenamide
TMTM
Sulphur
100
7
105
50
3
2
4
0.75
0.1
1.5
(pphr)
Compound P10
NBR (28% ACN)

Mineral fillers
Silica
Zinc oxide
Stearic acid
Antioxidants
Sulphur cure system
100
100
25
10
1
(pphr)
33
34
APPENDIX 2
ACCELERATED HEAT AGEING RESULTS
35
36
Natural Rubber - Standard
Hardness
Compound A
100C
70C
80C
90C
100
Hardness (Micro-IRHD)
90
80
70
60
0
30
60
90
120
150
180
50
60
Heat Ageing Period (Days)
Tensile Strength
Compound A
100C
70C
80C
90C
40.0
Tensile Strength (Mpa)
30.0
20.0
10.0
0.0
0
10
20
30
40
37
Compound A
Elongation at Break
Compound A
100C
70C
80C
90C
600
Elongation at Break (%)
500
400
300
200
100
0
0
10
20
30
40
50
60
40
50
60
Modulus at 100%
Compound A
100C
70C
80C
90C
10.0
Modulus at 100% (Mpa)
8.0
6.0
4.0
2.0
0.0
0
10
20
30
38
4.3
-0.2
T2
T10
-21
1.9
6.7
45
44
-10
-0.2
24
36
-71
-83.5
-155.3
0.0
-100
-64.0
-91.7
36
300% Modulus
-5.3
44
100% Modulus
-81
-71
33.3
40 years at
23 C
Rebound Resilience
-48
Elongation at Break
-77
6.7
Hot Wet
-48.7
-35
Tensile Strength
7.6
Hot Dry
-100
-87
-18
-100
-82.7
33.3
40 years at
40 C
WLF Predictions (%)
Tg
12
Temperate
40 Year Natural Ageing Change (%)
Hardness
Property
Compound A (natural rubber - standard)
62.3 years
16.7 years
43.1 years
61.9 years
633.4 days
17.5 years
80.8 years
11.5 years
23 C
(time)
5.6 years
2.5 years
4.3 years
4.1 years
156.9 days
2.7 years
7.1 years
2.1 years
40 C
(time)
Arrhenius Predictions
109.2
87.0
104.8
122.8
63.3
85.2
110.6
77.0
Activation
Energy
(kJ)
Natural Rubber - Standard
39
Compound A
40
Natural Rubber - Good Ageing
Hardness
Compound B
100C
70C
80C
90C
100
90
80
70
60
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound B
100C
70C
80C
90C
30.0
20.0
10.0
0.0
0
30
60
90
120
41
Compound B
Elongation at Break
Compound B
100C
70C
80C
90C
700
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound B
100C
70C
80C
90C
8.0
6.0
4.0
2.0
0.0
0
30
60
90
120
42
-13
75
27
3.1
-0.9
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
12
-11
Tensile Strength
Tg
10
Temperate
18
-1.6
1.5
14
121
-38
-24
24
Hot Dry
15
-2.4
-2.4
30
95
-40
-34
21
Hot Wet
Hardness
Property
Compound B (natural rubber - good ageing)
-7.3
-50.6
-48.4
67.0
172.9
-86.1
-15.2
49.3
40 years at
23 C
-28.5
-74.1
-194.3
24.3
154.8
-100.0
-70.8
49.3
40 years at
40 C
WLF Predictions (%)
394.9 days
21.8 years
153.6 days
9.6 years
30.2 years
101.8 years
24.4 years
23 C
(time)
226 days
5.3 years
49 days
2.4 years
5.1 years
13 years
6.6 years
40 C
(time)
25.3
64.4
51.9
62.1
81.0
93.4
59.5
Activation
Energy
(kJ)
Natural Rubber - Good Ageing
43
Compound B
44
Natural Rubber - Mineral Filler Loaded
Hardness
Compound C
100C
70C
80C
90C
100
80
60
40
20
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound C
100C
70C
80C
90C
30.0
20.0
10.0
0.0
0
30
60
90
120
45
Compound C
Elongation at Break
Compound C
100C
70C
80C
90C
800
700
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound C
100C
70C
80C
90C
5.0
4.0
3.0
2.0
1.0
0.0
0
30
60
90
120
46
-2
-1.7
T2
T10
-6.7
-0.9
0.5
5.6
54
-3.3
-2.7
-3.7
-1.4
31
-24
-34.4
-3.3
-1.3
10.6
-5.0
-7.0
-39.6
46
300% Modulus
1.7
73
100% Modulus
-18
-49
0.0
40 years at
23 C
Rebound Resilience
-11
Elongation at Break
-43
7.9
Hot Wet
-20.3
-24
Tensile Strength
Hot Dry
-41.8
-39.8
-73.6
-54.6
-28.3
85.4
-92.2
-82.8
-29.6
40 years at
40 C
WLF Predictions (%)
Tg
10
Temperate
Hardness
Property
Compound C (natural rubber - mineral filler loaded)
3.8 years
265.2 years
291.6 years
648.2 years
100.5 days
607.8 years
41.2 years
127.8 years
89 years
23 C
(time)
250.5 days
21.5 years
20.1 years
29.3 years
34.8 days
45.4 years
4.8 years
9 years
12 years
40 C
(time)
78.1
113.9
121.4
140.5
48.1
117.7
97.6
120.5
91.0
Activation
Energy
(kJ)
Natural Rubber - Mineral Filler Loaded
47
Compound C
48
Natural Rubber - Mineral Filler (Heavy Loaded)
Hardness
Compound D
100C
70C
80C
90C
100
90
80
70
60
50
40
0
30
60
90
120
150
180
100
120
Tensile Strength
Compound D
100C
70C
80C
90C
15.0
10.0
5.0
0.0
0
20
40
60
80
49
Compound D
Elongation at Break
Compound D
100C
70C
80C
90C
700
600
500
400
300
200
100
0
0
20
40
60
80
100
120
80
100
120
Modulus at 100%
Compound D
100C
70C
80C
90C
3.5
3.0
2.5
2.0
1.5
1.0
0
20
40
60
50
-73
83
92
-0.9
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
5.3
-19
Tensile Strength
Tg
8.9
Temperate
-8.2
1.3
2.4
49
72
-86
-31
7.6
Hot Dry
-3.5
-0.9
-0.6
30
11 5
-85
-14
16
Hot Wet
Hardness
Property
5.3
-38.0
-104.9
21.8
96.8
0.0
-41.7
-12.3
40 years at
23 C
-5.8
-64.9
-198.0
-62.8
177.7
-91.5
-82.3
63.9
40 years at
40 C
WLF Predictions (%)
Compound D (natural rubber - mineral filler (heavy loaded))
175.8 years
26.2 years
11.5 years
22.7 years
13.3 years
68.1 years
23 C
(time)
15.2 years
3.0 years
2.5 years
4.3 years
520.7 days
9.6 years
40 C
(time)
111.1
98.3
68.8
75.1
101.2
88.8
Activation
Energy
(kJ)
Natural Rubber - Mineral Filler (Heavy Loaded)
51
Compound D
52
Styrene Butadiene Rubber - General Purpose
Hardness
Compound E
100C
70C
80C
90C
100
90
80
70
60
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound E
100C
70C
80C
90C
35.0
30.0
25.0
20.0
15.0
10.0
0
30
60
90
120
53
Compound E
Elongation at Break
Compound E
100C
70C
80C
90C
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound E
100C
70C
80C
90C
20.0
15.0
10.0
5.0
0.0
0
30
60
90
120
54
-1.6
-1.1
T2
T10
11
0.7
-3.5
79
172
8.2
1.5
-3
73
133
-63
-10.7
-87.9
>53.4
554.1
-83.0
-26.8
17.9
28
300% Modulus
12
108
100% Modulus
-66
-31
19.7
40 years at
23 C
Rebound Resilience
-47
Elongation at Break
-30
15
Hot Wet
-28.6
- 20
Tensile Strength
18
Hot Dry
16.1
-58.8
-52.3
-161.3
>53.4
839.8
-100.0
-57.6
37.4
40 years at
40 C
WLF Predictions (%)
Tg
12
Temperate
Hardness
Property
Compound E (styrene butadiene rubber - general purpose)
5.9 years
322.3 years
4.3 years
11.2 years
20.8 years
40.4 years
176 years
50.1 years
23 C
(time)
461.3 days
23.1 years
434.1 days
3.4 years
4.2 years
7.9 years
18 years
8 years
40 C
(time)
69.9
119.5
58.1
54.5
72.6
74.1
104.4
83.5
Activation
Energy
(kJ)
55
Compound E
56
Styrene Butadiene Rubber - Good Ageing
Hardness
Compound F
100C
70C
80C
90C
100
90
80
70
60
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound F
100C
70C
80C
90C
35.0
30.0
25.0
20.0
15.0
10.0
0
30
60
90
120
57
Compound F
Elongation at Break
Compound F
100C
70C
80C
90C
700
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound F
100C
70C
80C
90C
15.00
10.00
5.00
0.00
0
30
60
90
120
58
-23
57
34
1.3
-0.7
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
7.4
-3.5
Tensile Strength
Tg
11
Temperate
11
-0.3
-2
53
13 3
-46
-17
17
Hot Dry
10
0.3
-1.2
75
126
-53
-26
15
Hot Wet
Hardness
Property
17.6
80.4
322.4
-34.3
-24.4
27.5
40 years at
23 C
17.6
174.8
553.1
-56.4
-31.9
56.3
40 years at
40 C
WLF Predictions (%)
Compound F (styrene butadiene rubber - good ageing)
241 days
659.7 days
16.7 years
13.4 years
19.2 years
13.3 years
18 years
11 years
23 C
(time)
72.3 days
429.5 days
2.5 years
2.2 years
4.4 years
3.1 years
3.8 years
3.3 years
40 C
(time)
54.6
19.5
81.6
66.6
66.8
70.0
54.2
Activation
Energy
(kJ)
59
Compound F
60
Hardness
Compound G
100C
70C
80C
90C
100
90
80
70
60
50
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound G
100C
70C
80C
90C
25.0
20.0
15.0
10.0
5.0
0
30
60
90
120
61
Compound G
Elongation at Break
Compound G
100C
70C
80C
90C
600
500
400
300
200
100
0
0
30
60
90
120
150
180
Modulus at 100%
Compound G
100C
70C
80C
90C
15.00
10.00
5.00
0.00
0
30
60
90
120
150
180
62
-48
107
-31
-0.1
0.4
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
4.3
-17
Tensile Strength
Tg
18
Temperate
1.9
0.3
-0.4
-90
200
-66
-27
25
Hot Dry
0.53
2.1
0.3
-93
51
-72
-46
24
Hot Wet
Hardness
Property
-0.4
-6.0
-406.4
95.2
550.3
-69.8
-38.8
45.0
40 years at
23 C
-30.3
-37.9
80.7
1091.3
-100.0
-54.3
61.3
40 years at
40 C
WLF Predictions (%)
Compound G (styrene butadiene rubber - general purpose)
12.9 years
23.1 years
76.1 years
27.1 years
89.5 years
41 years
34.3 years
23 C
(time)
3.1 years
5.4 years
13.2 years
4.9 years
12.2 years
5.8 years
6.5 years
40 C
(time)
64.7
65.8
79.3
77.8
90.3
88.6
75.3
Activation
Energy
(kJ)
63
Compound G
64
Hardness
Compound H
100C
70C
80C
90C
100
90
80
70
60
50
0
30
60
90
120
150
180
120
150
180
Tensile Strength
Compound H
100C
70C
80C
90C
25.0
20.0
15.0
10.0
5.0
0
30
60
90
65
Compound H
Elongation at Break
Compound H
100C
70C
80C
90C
700
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound H
100C
70C
80C
90C
15.00
10.00
5.00
0.00
0
30
60
90
120
66
-24
94
26
-0.6
-1.1
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
14
-11
Tensile Strength
Tg
14
Temperate
16
-1
0.3
64
205
-48
-25
21
Hot Dry
16
1.2
65
96
-53
-26
18
Hot Wet
Hardness
Property
-92.8
-34.6
-373.2
>100.8
373.8
-100.0
-45.9
45.1
40 years at
23 C
-64.1
-442.9
>100.8
1162.1
-100.0
-65.2
68.6
40 years at
40 C
WLF Predictions (%)
Compound H (styrene butadiene rubber - good ageing)
34.2 years
14.2 years
84.7 years
672.8 days
15.3 years
4.3 years
13.4 years
10.2 years
23 C
(time)
8.5 years
5 years
19 years
231.1 days
4.4 years
512 days
3.4 years
3.2 years
40 C
(time)
63.0
47.1
67.8
48.5
56.4
50.4
62.5
51.9
Activation
Energy
(kJ)
67
Compound H
68
Butyl Rubber - General Purpose
Hardness
Compound J
70C
100C
80C
90C
120C
80
70
60
50
40
30
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound J
80C
90C
100C
70C
120C
15.0
10.0
5.0
0.0
0
30
60
90
120
69
Compound J
Elongation at Break
Compound J
80C
90C
100C
70C
120C
800
700
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound J
80C
90C
100C
70C
120C
5.0
4.0
3.0
2.0
1.0
0.0
0
30
60
90
120
70
8.3
-4.4
-3
300% Modulus
T2
T10
Rebound Resilience
18
14
100% Modulus
Tg
-9.4
Tensile Strength
Elongation at Break
Temperate
27
-1.8
-3.1
25
30
-19
0.8
Hot Dry
19
-2
-1
13
14
-8.8
7. 3
Hot Wet
Hardness
Property
Compound J (butyl rubber - general purpose)
-1.9
-35.7
11.0
22.2
-22.9
-3.2
0.0
40 years at
23 C
-16.7
-75.0
5.8
2.6
54.7
-20.6
-3.3
40 years at
40 C
WLF Predictions (%)
27.9 years
1026.1 years
609 days
23 C
(time)
5.1 years
109.9 years
244 days
40 C
(time)
76.7
101.4
41.5
Activation
Energy
(kJ)
Butyl Rubber - General Purpose
71
Compound J
72
Butyl Rubber - Good Ageing
Hardness
Compound K
100C
70C
80C
90C
120C
90
80
70
60
50
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound K
80C
90C
100C
70C
120C
20.0
15.0
10.0
5.0
0.0
0
30
60
90
120
73
Compound K
Elongation at Break
Compound K
80C
90C
100C
70C
120C
700
600
500
400
300
200
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound K
80C
90C
100C
70C
120C
4.0
3.0
2.0
1.0
0.0
0
30
60
90
120
74
-14
45
66
-3
-2.2
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
21
-5.1
Tensile Strength
Tg
4.4
Temperate
23
-1.4
-2.2
-20
2.4
0.72
4.3
Hot Dry
6.1
-1.5
-1
8.4
27
-15
6.9
Hot Wet
Hardness
Property
Compound K (butyl rubber - good ageing)
28.9
32.3
-52.8
-10.7
40 years at
23 C
-0.8
48.1
14.6
-56.7
-10.7
40 years at
40 C
WLF Predictions (%)
33.5 years
3.5 years
23 C
(time)
7.7 years
2.0 years
40 C
(time)
66.7
25.0
Activation
Energy
(kJ)
Butyl Rubber - Good Ageing
75
Compound K
76
Polychloroprene - General Purpose
Hardness
Compound L
100C
70C
90C
80C
100
90
80
70
60
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound L
100C
70C
90C
80C
25.0
20.0
15.0
10.0
0
30
60
90
120
77
Compound L
Elongation at Break
Compound L
100C
70C
90C
80C
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound L
100C
70C
90C
80C
20.0
15.0
10.0
5.0
0.0
0
30
60
90
120
78
300% Modulus
Rebound Resilience
Tg
7.8
-0.9
40
100% Modulus
T10
-12
Elongation at Break
-1.7
-1.2
Tensile Strength
T2
5.6
Temperate
4.4
-0.08
-1.4
53
-11
-5.3
10
Hot Dry
0.5
-1.5
89
-13
-18
13
Hot Wet
Hardness
Property
0.5
28.1
-39.3
0.0
1.4
40 years at
23 C
0.5
79.0
-62.9
0.0
4.1
40 years at
40 C
WLF Predictions (%)
Compound L (polychloroprene - general purpose)
26 years
8.3 years
23 C
(time)
6.3 years
2.9 years
40 C
(time)
64.1
47.1
Activation
Energy
(kJ)
Polychloroprene - General Purpose
79
Compound L
80
Polychloroprene - Natural Ageing
Hardness
Compound M
100C
70C
80C
90C
100
90
80
70
60
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound M
100C
70C
80C
90C
30.0
25.0
20.0
15.0
0
30
60
90
120
81
Compound M
Elongation at Break
Compound M
100C
70C
80C
90C
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound M
100C
70C
80C
90C
25.0
20.0
15.0
10.0
5.0
0.0
0
30
60
90
120
82
-31
74
12
-3.3
-0.5
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
13
-12
Tensile Strength
Tg
16
Temperate
2.1
0.3
-1.6
66
100
-42
-15
21
Hot Dry
2.2
0.8
0.2
24
72
-42
-17
23
Hot Wet
Hardness
Property
18.7
104.1
-36.1
32.4
40 years at
23 C
39.0
412.3
-100.0
42.9
40 years at
40 C
WLF Predictions (%)
Compound M (polychloroprene - natural ageing)
43.3 years
59.6 years
24 years
16.1 years
15.1 years
23 C
(time)
12.4 years
9.1 years
5.6 years
4.7 years
4.5 years
40 C
(time)
56.6
85.2
66.1
55.4
54.7
Activation
Energy
(kJ)
Polychloroprene - Natural Ageing
83
Compound M
84
Polychloroprene - Heat Ageing
Hardness
Compound N
100C
70C
80C
90C
100
95
90
85
80
75
0
30
60
90
120
150
120
150
180
Tensile Strength
Compound N
100C
70C
80C
90C
18.0
16.0
14.0
12.0
10.0
8.0
0
30
60
90
180
85
Compound N
Elongation at Break
Compound N
100C
70C
80C
90C
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound N
100C
70C
80C
90C
15.0
10.0
5.0
0.0
0
30
60
90
120
86
-29
96
-10
-6.2
-1.1
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
25
-16
Tensile Strength
Tg
11
Temperate
25
-0.7
-6.3
-48
135
-57
-13
11
Hot Dry
18
0.3
-3.4
-34
11 7
-65
-20
14
Hot Wet
Hardness
Property
Compound N (polychloroprene - heat ageing)
18.4
185.1
-8.4
103.9
14.1
40 years at
23 C
42.5
332.5
-62.2
147.6
25.0
40 years at
40 C
WLF Predictions (%)
629.3 days
66.6 years
72.3 years
13.8 years
11.4 years
23 C
(time)
454.7 days
11.2 years
14.5 years
4.1 years
3.7 years
40 C
(time)
14.7
81.0
72.9
55.3
51.3
Activation
Energy
(kJ)
Polychloroprene - Heat Ageing
87
Compound N
88
Nitrile Rubber - General Purpose
Hardness
Compound P
100C
80C
90C
100
90
80
70
60
50
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound P
100C
80C
90C
70C
25.0
20.0
15.0
10.0
0
30
60
90
120
89
Compound P
Elongation at Break
Compound P
100C
80C
90C
70C
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound P
100C
80C
90C
70C
25.0
20.0
15.0
10.0
5.0
0.0
0
30
60
90
120
90
-34
75
62
-3.6
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
14
-4.8
Tensile Strength
Tg
21
Temperate
15
-0.2
-2.4
175
16 4
-52
28
Hot Dry
10
1.1
-2.5
17 5
12 7
-48
5.8
23
Hot Wet
Hardness
Property
Compound P (nitrile rubber - general purpose)
-28.6
-57.3
158.4
130.4
-100.0
0.0
39.5
40 years at
23 C
-170.9
-90.1
205.4
1148.6
-100.0
0.0
81.8
40 years at
40 C
WLF Predictions (%)
30 years
30.3 years
9.6 years
43.2 years
24.3 years
138.9 years
23 C
(time)
4.4 years
6.6 years
2.8 years
8 years
5.5 years
19.8 years
40 C
(time)
87.0
69.0
55.9
76.5
67.7
88.3
Activation
Energy
(kJ)
Nitrile Rubber - General Purpose
91
Compound P
92
Nitrile Rubber - Good Ageing
Hardness
Compound R
100C
70C
80C
90C
100
90
80
70
60
50
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound R
100C
70C
80C
90C
25.0
20.0
15.0
10.0
5.0
0.0
0
30
60
90
120
93
Compound R
Elongation at Break
Compound R
100C
70C
80C
90C
700
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound R
100C
70C
80C
90C
20.00
15.00
10.00
5.00
0.00
0
30
60
90
120
94
-28
126
62
-1.3
-0.1
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
16
-8.3
Tensile Strength
Tg
34
Temperate
4.4
-1.3
10
176
-42
-11
55
Hot Dry
-11
0.4
-0.5
92
129
-37
-13
54
Hot Wet
Hardness
Property
Compound R (nitrile rubber - good ageing)
41.1
123.4
72.5
40 years at
23 C
179.5
259.3
81.8
40 years at
40 C
WLF Predictions (%)
31.7 years
69.5 years
32 days
15.8 years
23 C
(time)
6.7 years
5.8 years
13 days
5.8 years
40 C
(time)
70.8
113.0
39.8
45.2
Activation
Energy
(kJ)
Nitrile Rubber - Good Ageing
95
Compound R
96
Miscellaneous - Acrylate Rubber
Hardness
Compound S
150C
170C
160C
140C
100
90
80
70
60
50
40
30
0
30
60
90
120
150
180
Tensile Strength
Compound S
150C
170C
160C
140C
15.0
10.0
5.0
0.0
0
30
60
90
120
97
Compound S
Elongation at Break
Compound S
150C
170C
160C
140C
600
500
400
300
200
100
0
0
30
60
90
120
90
120
Modulus at 100%
Compound S
150C
170C
160C
140C
8.0
6.0
4.0
2.0
0.0
0
30
60
98
Rebound Resilience
Tg
-14
0.7
T10
300% Modulus
0.4
-1.3
100% Modulus
T2
-5.5
-4.8
Temperate
-10
0. 6
0. 7
9.4
-3.2
8.4
-4.1
Hot Dry
-48
1.2
1.1
5.9
-2.9
10
-5.5
Hot Wet
Elongation at Break
Tensile Strength
Hardness
Property
Compound S (acrylate rubber)
-74.3
>-76.1
40 years at
23 C
-83.4
>-76.1
40 years at
40 C
WLF Predictions (%)
3863 years
23 C
(time)
646 years
40 C
(time)
81.2
Activation
Energy
(kJ)
Miscellaneous - Acrylate Rubber
99
Compound S
100
Miscellaneous - Chlorosulphonated Polyethylene
Hardness
Compound T
100C
80C
90C
70C
70
65
60
55
50
45
0
30
60
90
120
150
180
Tensile Strength
Compound T
100C
80C
90C
70C
14.0
12.0
10.0
8.0
6.0
0
30
60
90
120
150
180
101
Compound T
Elongation at Break
Compound T
100C
80C
90C
70C
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound T
100C
80C
90C
70C
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0
30
60
90
120
102
-34
55
41
-0.4
-0.9
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Rebound Resilience
14
14
Tensile Strength
Tg
3.3
Temperate
34
-0.3
-0.2
38
62
-32
18
Hot Dry
45
-0.9
-0.6
49
63
-38
7.3
Hot Wet
Hardness
Property
67.0
-43.5
30.5
96.1
68.8
-57.8
36.7
96.1
40 years at
40 C
WLF Predictions (%)

40 years at
23 C
Compound T (chlorosulphonated polyethylene)

23 C
(time)
40 C
(time)
Activation
Energy
(kJ)
Miscellaneous - Chlorosulphonated Polyethylene
103
Compound T
104
Miscellaneous - Polysulphide Rubber
Hardness
Compound W
100C
70C
80C
90C
80
70
60
50
40
30
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound W
100C
70C
80C
90C
8.0
6.0
4.0
2.0
0.0
0
30
60
90
120
105
Compound W
Elongation at Break
Compound W
100C
70C
80C
90C
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound W
100C
70C
80C
90C
4.0
3.0
2.0
1.0
0.0
0
30
60
90
120
106
300% Modulus
Rebound Resilience
Tg
1.9
-1.9
12
100% Modulus
T10
1.7
Elongation at Break
5.4
11
Tensile Strength
T2
5.7
Temperate
-1.5
5.2
4.3
6.7
9.3
5.9
Hot Dry
-2.1
-1.6
2.2
4.3
-4.1
2.1
3.1
Hot Wet
Hardness
Property
Compound W (polysulphide rubber)
-55.8
-67.7
3.0
-63.2
4. 0
-17.1
-13.5
-100.0
40 years at
23 C
-100.0
-100.9
-192.5
-100.0
-100.0
-67.7
-100.0
-100.0
40 years at
40 C
WLF Predictions (%)
413.4 years
9 years
23 C
(time)
29.6 years
679 days
40 C
(time)
103.3
119.6
71.7
Activation
Energy
(kJ)
Miscellaneous - Polysulphide Rubber
107
Compound W
108
Miscellaneous - Silicone Rubber
Hardness
Compound X
150C
170C
210C
70
65
60
55
50
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound X
150C
170C
210C
9.0
8.0
7.0
6.0
5.0
0
30
60
90
120
109
Compound X
Elongation at Break
Compound X
150C
170C
210C
300
250
200
150
100
50
0
0
30
60
90
120
150
180
120
150
180
Modulus at 100%
Compound X
150C
170C
210C
6.0
5.0
4.0
3.0
2.0
1.0
0.0
0
30
60
90
110
16
7.4
-8.3
Tensile Strength
Elongation at Break
100% Modulus
Rebound Resilience
12
1.9
T10
Tg
0.9
T2
300% Modulus
13
Temperate
14
1.6
0.8
-4.1
-20
7.9
12
Hot Dry
9.4
0.5
0.4
-5.5
4.6
22
11
Hot Wet
Hardness
Property
Compound X (silicone rubber)
0. 0
0. 0
0. 0
40 years at
23 C
-11.0
0.0
0.0
40 years at
40 C
WLF Predictions (%)
171.6 years
263.9 years
23 C
(time)
44.1 years
73.3 years
40 C
(time)
103.3
61.6
58.1
Activation
Energy
(kJ)
Miscellaneous - Silicone Rubber
111
Compound X
112
New Compound - FVMQ
Hardness
Compound N1
150C
170C
210C
85
80
75
70
65
0
30
60
90
120
150
180
Tensile Strength
Compound N1
150C
170C
210C
10.00
9.00
8.00
7.00
6.00
5.00
4.00
0
30
60
90
120
150
180
113
Compound N1
Elongation at Break
Compound N1
150C
170C
210C
250
200
150
100
50
0
0
30
60
90
120
150
180
120
150
180
Modulus at 100%
Compound N1
150C
170C
210C
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0
30
60
90
114
0.0
-31.8
29.4
Tensile Strength
Elongation at Break
100% Modulus
Rebound Resilience
Tg
T10
T2
300% Modulus
0.0
40 years at 23 C
41.6
-41.2
0.0
0.0
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound N1 (FVMQ)
25%
-25%
-10%
10%
Measured Change
456.6 days
2.2 years
3.4 years
41.1 years
23 C
(time)
298.9 days
498.3 days
2.0 years
16.6 years
40 C
(time)
19.2
21.1
23.5
41.3
Activation
Energy
(kJ)
New Compound - FVMQ
115
Compound N1
116
New Compound - HNBR
Hardness
Compound N2
150C
170C
160C
140C
100
90
80
70
60
0
30
60
90
120
150
180
Tensile Strength
Compound N2
150C
170C
160C
140C
30.0
28.0
26.0
24.0
22.0
20.0
18.0
16.0
0
30
60
90
120
117
Compound N2
Elongation at Break
Compound N2
150C
170C
160C
140C
700
600
500
400
300
200
100
0
0
30
60
90
120
90
120
Modulus at 100%
Compound N2
150C
170C
160C
140C
25.0
20.0
15.0
10.0
5.0
0.0
0
30
60
118
>28.2
-49.4
>595.2
68.6
Tensile Strength
Elongation at Break
100% Modulus
300% Modulus
Rebound Resilience
Tg
T10
T2
49.3
40 years at 23 C
68.6
>595.2
-57.5
>28.2
49.3
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound N2 (HNBR)
50%
300%
-25%
10%
25%
Measured Change
41.9 days
157.1 years
13.6 years
2.11E+7 years
8408.7 years
23 C
(time)
25.3 days
32.1 years
3.6 years
568837 years
947.2 years
40 C
(time)
23.0
72.0
59.7
163.9
99.1
Activation
Energy
(kJ)
New Compound - HNBR
119
Compound N2
120
New Compound - Epoxidised Natural
Hardness
Compound N3
100C
70C
80C
90C
100
90
80
70
60
50
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound N3
100C
70C
80C
90C
30.0
25.0
20.0
15.0
10.0
5.0
0.0
0
30
60
90
120
121
Compound N3
Elongation at Break
Compound N3
100C
70C
80C
90C
700
600
500
400
300
200
100
0
0
30
60
90
120
150
180
Modulus at 100%
Compound N3
100C
70C
80C
90C
8.00
6.00
4.00
2.00
0.00
0
30
60
90
120
150
122
88.7
>-79.6
-100.0
>251.1
>124.1
728.6
-458.0
-948.6
-100.0
Tensile Strength
Elongation at Break
100% Modulus
300% Modulus
T2
T10
Tg
Rebound Resilience
40 years at 23 C
-100.0
1012.2
>124.1
>251.1
-100.0
>-79.6
88.7
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound N3 (epoxidised natural)
-10%
5C
5C
5C
50%
50%
-25%
-25%
25%
Measured Change
50.1 years
27.4 years
24.9 years
38.0 years
13.6 years
26.4 years
11.9 years
9.0 years
52.8 years
23 C
(time)
5.3 years
4.1 years
3.9 years
4.8 years
624.2 days
3.8 years
581.1 days
557 days
7.4 years
40 C
(time)
102.2
85.8
84.7
94.2
94.2
88.1
91.3
80.7
89.1
Activation
Energy
(kJ)
New Compound - Epoxidised Natural
123
Compound N3
124
New Compound - Chlorinated Polyethylene
Hardness
Compound N4
100C
150C
160C
130C
140C
100
95
90
85
80
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound N4
100C
150C
160C
130C
140C
22.0
20.0
18.0
16.0
14.0
12.0
10.0
8.0
0
30
60
90
120
125
Compound N4
Elongation at Break
Compound N4
100C
150C
160C
130C
140C
250
200
150
100
50
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound N4
100C
150C
160C
130C
140C
15.00
10.00
5.00
0.00
0
30
60
90
120
126
-6.8
>57.7
Elongation at Break
100% Modulus
Rebound Resilience
Tg
T10
T2
0. 0
-4.0
Tensile Strength
300% Modulus
2.4
40 years at 23 C
78.9
>57.7
-24.3
-21.5
4.8
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound N4 (chlorinated polyethylene)
25%
-25%
-15%
10%
Measured Change
135.1 years
396.7 years
1692.4 years
1808.4 years
23 C
(time)
23.4 years
59.8 years
205.6 years
223.2 years
40 C
(time)
79.6
85.8
95.6
94.9
Activation
Energy
(kJ)
New Compound - Chlorinated Polyethylene
127
Compound N4
128
New Compound - Fluorocarbon
Hardness
Compound N5
170C
150C
210C
75
73
71
69
67
65
0
30
60
90
120
150
180
Tensile Strength
Compound N5
150C
210C
170C
18.0
16.0
14.0
12.0
10.0
0
20
40
60
80
100
129
Compound N5
Elongation at Break
Compound N5
150C
170C
210C
300.0
250.0
200.0
150.0
100.0
0
20
40
60
80
100
80
100
Modulus at 100%
Compound N5
150C
170C
210C
10.00
8.00
6.00
4.00
2.00
0.00
0
20
40
60
130
Rebound Resilience
Tg
T10
T2
300% Modulus
100% Modulus
Elongation at Break
Tensile Strength
Hardness
Property
0.0
0.0
40 years at 23 C
0.0
0.0
40 years at 40 C
WLF Predictions (%)
Compound N5 (fluorocarbon)
-15%
Measured Change
2.5 years
23 C
(time)
299.8 days
40 C
(time)
50.6
Activation
Energy
(kJ)
New Compound - Fluorocarbon
131
Compound N5
132
New Compound - Exxpro
Hardness
Compound N6
80C
90C
70C
100C
80
75
70
65
0
30
60
90
120
150
180
120
150
180
Tensile Strength
Compound N6
80C
90C
70C
100C
20.0
18.0
16.0
14.0
12.0
10.0
0
30
60
90
133
Compound N6
Elongation at Break
Compound N6
80C
90C
70C
100C
250
200
150
100
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound N6
80C
90C
70C
100C
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0
30
60
90
120
134
-27.1
-36.7
0.0
Tensile Strength
Elongation at Break
100% Modulus
Rebound Resilience
Tg
T10
T2
300% Modulus
20.9
40 years at 23 C
0.0
-39.5
-42.0
22.4
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound N6 (Exxpro)
-15%
-15%
10%
Measured Change
86.5 days
2.5 years
3.1 years
23 C
(time)
48.7 days
299.8 days
493.1 days
40 C
(time)
26.1
50.6
38.1
Activation
Energy
(kJ)
New Compound - Exxpro
135
Compound N6
136
New Compound - Epichlorohydrin
Hardness
Compound N7
80C
90C
100C
70C
95
90
85
80
75
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound N7
80C
90C
100C
70C
14.00
13.00
12.00
11.00
10.00
9.00
8.00
0
30
60
90
120
137
Compound N7
Elongation at Break
Compound N7
80C
90C
100C
70C
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound N7
80C
90C
100C
70C
15.00
10.00
5.00
0.00
0
30
60
90
120
138
0.0
-77.7
232.6
Tensile Strength
Elongation at Break
100% Modulus
Rebound Resilience
Tg
T10
T2
300% Modulus
16.7
40 years at 23 C
243.4
-82.3
0.0
20.5
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound N7 (epichlorohydrin)
50%
-25%
10%
10%
Measured Change
19.4 years
4.7 years
24.3 years
11.1 years
23 C
(time)
4.3 years
388.2 days
3.2 years
2.8 years
40 C
(time)
68.7
67.1
91.9
61.9
Activation
Energy
(kJ)
New Compound - Epichlorohydrin
139
Compound N7
140
New Compound - EPDM
Hardness
Compound N8
100C
80C
90C
110C
90
85
80
75
70
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound N8
100C
80C
90C
110C
20.0
19.0
18.0
17.0
16.0
15.0
14.0
0
30
60
90
120
141
Compound N8
Elongation at Break
Compound N8
100C
80C
90C
110C
500
400
300
200
100
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound N8
100C
80C
90C
110C
10.00
8.00
6.00
4.00
2.00
0.00
0
30
60
90
120
142
0.6
-47.9
82.6
>83.8
Tensile Strength
Elongation at Break
100% Modulus
300% Modulus
Rebound Resilience
Tg
T10
T2
0.0
40 years at 23 C
>83.8
82.6
>-44.0
0.6
1.3
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound N8 (EPDM)
10%
50%
-25%
5%
Measured Change
36.5 days
188.9 days
214.3 days
20.4 years
23 C
(time)
18.3 days
125 days
104.3 days
6.2 years
40 C
(time)
31.3
18.7
32.6
53.8
Activation
Energy
(kJ)
New Compound - EPDM
143
Compound N8
144
New Compound - EVA
Hardness
Compound N9
100C
150C
170C
160C
140C
100
95
90
85
80
75
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound N9
100C
150C
170C
160C
140C
20.0
18.0
16.0
14.0
12.0
10.0
8.0
0
30
60
90
120
145
Compound N9
Elongation at Break
CompoundN9
100C
150C
170C
160C
140C
250
200
150
100
50
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound N9
100C
150C
170C
160C
140C
20.00
15.00
10.00
5.00
0.00
0
30
60
90
120
146
Rebound Resilience
Tg
T10
T2
0. 0
19.8
100% Modulus
300% Modulus
>-95.9
-1.7
Tensile Strength
Elongation at Break
8.9
40 years at 23 C
0.0
29.9
>-95.9
-2.6
12.7
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound N9 (EVA)
5C
50 %
-25%
10%
Measured Change
24.6 years
228.7 years
506 years
17 years
23 C
(time)
9.3 years
47.2 years
82.5 years
7.1 years
40 C
(time)
44.3
71.6
82.3
39.7
Activation
Energy
(kJ)
New Compound - EVA
147
Compound N9
148
New Compound - PU
Hardness
Compound N10
80C
90C
70C
100C
100
90
80
70
60
50
40
30
0
30
60
90
120
150
180
Tensile Strength
Compound N10
80C
90C
70C
100C
20.0
18.0
16.0
14.0
12.0
10.0
8.0
6.0
4.0
2.0
0.0
0
10
12
14
16
18
20
149
Compound N10
Elongation at Break
Compound N10
80C
90C
70C
100C
250.0
200.0
150.0
100.0
50.0
0.0
0
10
12
14
16
18
20
Modulus at 100%
Compound N10
80C
90C
70C
100C
10.0
8.0
6.0
4.0
2.0
0.0
0
10
12
14
16
18
20
150
>-69.0
-84.0
Elongation at Break
100% Modulus
Rebound Resilience
Tg
-10%
5C
T10
-25%
-25%
-25%
-25%
18.5 days
545.2 days
83.1 days
280.4 days
12 days
9.6 days
59.7 days
23 C
(time)
Measured Change
5C
-100.0
-84.0
>-69.0
>-86.4
14.9
40 years at 40 C
T2
-100.0
-42.9
Tensile Strength
300% Modulus
6.8
40 years at 23 C
WLF Predictions (%)
Hardness
Property
Compound N10 (PU)
8.7 days
103.7 days
30.3 days
75.8 days
6.4 days
5.7 days
25.5 days
40 C
(time)
34.6
75.3
45.8
59.4
28.3
23.8
38.6
Activation
Energy
(kJ)
New Compound - PU
151
Compound N10
152
Participant Compound - EPR
Hardness
Compound P1
150C
170C
160C
140C
100
95
90
85
80
75
70
65
0
10
20
30
40
50
60
70
80
90
100
80
90
Tensile Strength
Compound P1
150C
170C
160C
140C
20.0
15.0
10.0
5.0
0.0
0
10
20
30
40
50
60
70
153
Compound P1
Elongation at Break
Compound P1
150C
170C
160C
140C
600
500
400
300
200
100
0
0
10
20
30
40
50
60
70
80
90
90
100
Modulus at 100%
Compound P1
150C
170C
160C
140C
10.00
8.00
6.00
4.00
2.00
0.00
0
10
20
30
40
50
60
70
80
154
-47.6
>300.5
Elongation at Break
100% Modulus
Rebound Resilience
Tg
T10
T2
0.0
18.2
Tensile Strength
300% Modulus
-1.4
40 years at 23 C
0.0
>300.5
-54.0
10.6
-1.4
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound P1 (EPR)
100%
-25%
-25%
15%
Measured Change
6.0 years
66.2 days
6266360.7 yrs
1760.5 years
23 C
(time)
685.2 days
36 days
234097 years
291.6 years
40 C
(time)
52.8
27.7
149.1
81.6
Activation
Energy
(kJ)
Participant Compound - EPR
155
Compound P1
156
Participant Compound - Siloxane Cellular Material
Hardness
Compound P2
150C
170C
210C
40
Hardness (Shore 00)
35
30
25
20
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound P2
150C
170C
210C
0.500
0.400
0.300
0.200
0.100
0.000
0
30
60
90
120
157
Compound P2
Elongation at Break
Compound P2
150C
170C
210C
140.0
120.0
100.0
80.0
60.0
40.0
20.0
0.0
0
30
60
90
120
150
180
158
Rebound Resilience
Tg
T10
T2
300% Modulus
100% Modulus
Elongation at Break
Tensile Strength
Hardness
Property
0.0
18.5
40 years at 23 C
0.0
22.2
40 years at 40 C
WLF Predictions (%)
Compound P2 (siloxane cellular material)

Measured Change
23 C
(time)
40 C
(time)
Activation
Energy
(kJ)
Participant Compound - Siloxane Cellular Material
159
Compound P2
160
Participant Compound - Medium Nitrile Rubber
Hardness
Compound P3
100C
80C
90C
100
95
90
85
80
75
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound P3
100C
80C
90C
70C
22.0
20.0
18.0
16.0
14.0
12.0
10.0
0
30
60
90
120
161
Compound P3
Elongation at Break
Compound P3
100C
80C
90C
70C
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound P3
100C
80C
90C
70C
25.00
20.00
15.00
10.00
5.00
0.00
0
30
60
90
120
162
26.1
-88.5
>83.0
Tensile Strength
Elongation at Break
100% Modulus
-62.3
-120.5
T10
Tg
Rebound Resilience
3.0
T2
300% Modulus
22.0
40 years at 23 C
-198.9
-111.6
87.9
>83.0
>-41.4
35.0
22.0
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound P3 (medium nitrile rubber)
5C
50%
-25%
10%
15%
Measured Change
11.2 years
8.6 years
53.3 years
4.0 years
117.6 years
23 C
(time)
4.1 years
2.5 years
5.6 years
525.1 days
20.3 years
40 C
(time)
45.2
55.8
102.2
47.0
79.6
Activation
Energy
(kJ)
Participant Compound - Medium Nitrile Rubber
163
Compound P3
164
Participant Compound - Nitrile Rubber
Hardness
Compound P4
100C
80C
90C
70C
100
90
80
70
60
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound P4
100C
80C
90C
70C
30.0
25.0
20.0
15.0
10.0
5.0
0
30
60
90
120
165
Compound P4
Elongation at Break
Compound P4
100C
80C
90C
70C
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound P4
100C
80C
90C
70C
25.00
20.00
15.00
10.00
5.00
0.00
0
30
60
90
120
166
>-72.2
177.9
87.6
Elongation at Break
100% Modulus
300% Modulus
-10%
Rebound Resilience
10%
100%
-25%
-25%
10%
8.8 days
597.4 days
153.1 days
3.0 years
327 days
9.6 years
5.3 years
23 C
(time)
Measured Change
5C
-58.6
78.3
559.9
>-72.2
>7.3
49.3
40 years at 40 C
Tg
T10
-51.4
>7.3
Tensile Strength
T2
49.3
40 years at 23 C
WLF Predictions (%)
Hardness
Property
Compound P4 (nitrile rubber)
7.1 days
421.9 days
47.5 days
495 days
84.4 days
405.6 days
1.9 years
40 C
(time)
9.3
15.8
53.1
36.8
61.5
97.9
45.7
Activation
Energy
(kJ)
167
Compound P4
168
Participant Compound - EPDM
Hardness
Compound P5
150C
170C
160C
140C
100
90
80
70
60
0
30
60
90
120
150
180
50
60
Tensile Strength
Compound P5
150C
170C
160C
140C
20.0
15.0
10.0
5.0
0.0
0
10
20
30
40
169
Compound P5
Elongation at Break
Compound P5
150C
170C
160C
140C
150
100
50
0
0
10
20
30
40
50
60
Modulus at 100%
Compound P5
150C
170C
160C
140C
15.00
10.00
5.00
0.00
0
10
20
30
40
170
Rebound Resilience
Tg
T10
T2
300% Modulus
100% Modulus
>-87.5
0.0
Tensile Strength
Elongation at Break
5.5
40 years at 23 C
>-87.5
0.0
19.3
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound P5 (EPDM)
25%
-25%
-25%
15%
Measured Change
5.9 years
338.5 years
2.9E+06 years
2230.8 years
23 C
(time)
622.7 days
50.5 years
1.0E+05 years
339.3 years
40 C
(time)
56.3
86.3
152.7
85.4
Activation
Energy
(kJ)
Participant Compound - EPDM
171
Compound P5
172
Participant Compound - Vamac G
Hardness
Compound P6
150C
170C
160C
140C
100
95
90
85
80
75
0
30
60
90
120
Tensile Strength
Compound P6
150C
170C
160C
140C
14.0
13.0
12.0
11.0
10.0
0
30
60
90
120
150
180
173
Compound P6
Elongation at Break
Compound P6
150C
170C
160C
140C
300
250
200
150
100
50
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound P6
150C
170C
160C
140C
15.00
13.00
11.00
9.00
7.00
5.00
0
30
60
90
120
174
0.0
100% Modulus
Rebound Resilience
Tg
T10
T2
300% Modulus
0.0
6.4
40 years at 23 C
0.0
0.0
9.0
40 years at 40 C
WLF Predictions (%)
Elongation at Break
Tensile Strength
Hardness
Property
Compound P6 (Vamac G)
50%
-25%
15%
Measured Change
1126406.5 years
2668132.7 years
341864.8 years
23 C
(time)
67897.0 years
111474.2 years
21078.2 years
40 C
(time)
127.4
144.1
126.4
Activation
Energy
(kJ)
Participant Compound - Vamac G
175
Compound P6
176
Participant Compound - W Type Polychloroprene
Hardness
Compound P7
100C
70C
80C
90C
100
90
80
70
60
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound P7
100C
70C
80C
90C
25.0
20.0
15.0
10.0
5.0
0
30
60
90
120
177
Compound P7
Elongation at Break
Compound P7
100C
70C
80C
90C
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound P7
100C
70C
80C
90C
20.00
15.00
10.00
5.00
0.00
0
30
60
90
120
178
-58.6
140.9
Elongation at Break
100% Modulus
Rebound Resilience
-485.2
5C
-54.8
Tg
5C
100%
-25%
-15%
25%
88.5 years
95.3 years
68.6 years
52.8 years
23.3 years
4094.8 years
64.7 years
23 C
(time)
Measured Change
5C
-226.3
>315.2
>-97.4
-9.2
56.3
40 years at 40 C
T10
T2
-63.2
-17.6
Tensile Strength
300% Modulus
45.3
40 years at 23 C
WLF Predictions (%)
Hardness
Property
Compound P7 (W type polychloroprene)
10.6 years
12.3 years
9.1 years
7.1 years
3.4 years
112.5 years
9.3 years
40 C
(time)
96.4
93.0
91.5
90.8
86.7
163.1
87.9
Activation
Energy
(kJ)
Participant Compound - W Type Polychloroprene
179
Compound P7
180
Participant Compound - Natural Rubber
Hardness
Compound P8
100C
70C
80C
90C
100
90
80
70
60
50
40
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound P8
100C
70C
80C
90C
15.0
10.0
5.0
0.0
0
30
60
90
120
181
Compound P8
Elongation at Break
Compound P8
100C
70C
80C
90C
700
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound P8
100C
70C
80C
90C
5.00
4.00
3.00
2.00
1.00
0.00
0
30
60
90
120
182
-31.2
-84.3
>286.7
20.2
Tensile Strength
Elongation at Break
100% Modulus
300% Modulus
Rebound Resilience
Tg
T10
T2
46.3
40 years at 23 C
59.3
>286.7
>-72.4
-73.8
85.2
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound P8 (natural rubber)
5C
25%
100%
-25%
-25%
25%
Measured Change
1558.9 years
33.9 years
3.4 years
18 years
218.8 years
9.4 years
23 C
(time)
63.7 years
2.3 years
321.6 years
2.7 years
17.3 years
2.3 years
40 C
(time)
145.1
122.8
61.8
85.6
115.2
64.2
Activation
Energy
(kJ)
Participant Compound - Natural Rubber
183
Compound P8
184
Participant Compound - Santoprene 101 55 V185
Hardness
Compound P9
100C
140C
170C
150C
160C
100
90
80
70
60
50
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound P9
100C
140C
170C
150C
160C
8.00
6.00
4.00
2.00
0.00
0
30
60
90
120
185
Compound P9
Elongation at Break
Compound P9
100C
140C
170C
150C
160C
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound P9
100C
140C
170C
150C
160C
5.00
4.00
3.00
2.00
1.00
0.00
0
30
60
90
120
186
-25.3
Tensile Strength
0.0
300% Modulus
-4.5
0.0
Tg
Rebound Resilience
T10
T2
0.0
100% Modulus
Elongation at Break
47.1
40 years at 23 C
0.0
-7.0
-0.2
0.0
-41.9
47.1
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound P9 (Santoprene 101 55 V185)
-25%
-25%
10%
Measured Change
201192.6 yrs
688079.1 yrs
119209.9 yrs
23 C
(time)
12722.4 yrs
32237.6 yrs
10874.1 yrs
40 C
(time)
125.3
138.9
108.6
Activation
Energy
(kJ)
Participant Compound - Santoprene 101 55 V185
187
Compound P9
188
Hardness
Compound P10
100C
80C
90C
70C
100
95
90
85
80
75
0
30
60
90
120
150
180
150
180
Tensile Strength
Compound P10
100C
80C
90C
70C
16.0
14.0
12.0
10.0
8.0
6.0
0
30
60
90
120
189
Compound P10
Elongation at Break
Compound P10
100C
80C
90C
70C
600
500
400
300
200
100
0
0
30
60
90
120
150
180
150
180
Modulus at 100%
Compound P10
100C
80C
90C
70C
15.00
10.00
5.00
0.00
0
30
60
90
120
190
>-97.7
80.7
130.0
Elongation at Break
100% Modulus
300% Modulus
Rebound Resilience
Tg
T10
-32.1
-10.7
Tensile Strength
T2
19.5
40 years at 23 C
-42.9
189.6
180.4
>-97.7
24.6
22.0
40 years at 40 C
WLF Predictions (%)
Hardness
Property
Compound P10 (nitrile rubber)
5C
5C
50%
50%
-25%
-10%
10%
Measured Change
7.3 years
7.5 years
7.9 years
22.1 years
29.6 years
37.2 days
11.0 years
23 C
(time)
2.7 years
3.4 years
662.6 days
3.4 years
4.6 years
23.4 days
2.7 years
40 C
(time)
45.6
35.5
66.8
85.2
84.1
21.0
63.7
Activation
Energy
(kJ)
191
Compound P10
192
APPENDIX 3
COMPRESSION SET RESULTS
193
Appendix 3
194
3.3
10.3
11.2
13.0
12.4
13.4
6.5
20.0
5.0
6.3
8.5
7.8
9.9
6.0
55.1
30.5
9.4
12.5
7.7
1
week
11.2
33.8
62.0
7.4
10.4
9.3
15.9
9.1
6.7
25.0
7.3
17.8
16.8
19.2
17.1
21.5
6.8
20.5
13.3
5
weeks
23 C
Compound
Reference
80.6
73.7
23.4
23.8
56.7
39.5
39.3
37.6
85.1
48.9
37.4
56.7
1
week
97.4
86.3
40.6
42.0
67.0
64.1
59.3
57.7
95.3
68.3
57.1
70.9
5
weeks
70 C
16.7
102.2
88.4
67.6
51.7
60.6
48.1
42.6
20.9
84.6
76.8
23.5
57.5
25.1
58.8
96.3
71.6
52.7
71.9
1
week
29.3
102.2
95.3
81.5
62.5
77.9
68.7
60.0
40.9
92.9
86.3
38.7
72.1
41.7
72.3
98.0
78.7
68.5
81.9
5
weeks
100 C
65.1
68.8
49.8
56.7
1
week
91.6
100.0
93.8
92.1
5
weeks
140 C
56.6
94.6
1
week
88.9
104.1
5
weeks
150 C
Table 1. Compression Set Results (%)
60.0
1
week
106.3
5
weeks
160 C
1
week
5
weeks
200 C
Compression Set Results
195
196
21.3
31.7
14.4
22.3
0.1
5.6
13.0
2.1
8.0
10.8
20.7
12.7
18.2
N8
N9
N10
P1
P2
P3
P4
P5
P6
P7
P8
P9
P10
9.4
N5
9.9
19.0
N4
N7
10.4
N3
17.8
24.4
N2
N6
5.9
1
week
27.1
16.2
29.0
18.3
15.6
4.1
19.2
12.8
2.5
34.1
26.8
45.5
32.5
13.0
23.6
10.8
29.9
15.6
33.6
9.1
5
weeks
23 C
N1
Compound
Reference
35.9
72.5
42.4
20.4
48.7
38.7
1
week
49.3
86.3
64.3
38.0
65.6
55.6
5
weeks
70 C
50.5
90.7
72.4
60.4
32.0
30.2
44.3
53.7
34.0
39.8
68.3
63.2
39.3
12.7
1
week
69.2
96.0
85.0
69.3
44.4
44.7
63.2
90.7
58.2
63.3
81.1
97.1
63.7
23.9
5
weeks
100 C
45.6
62.6
63.2
35.1
75.6
9.8
47.7
1
week
63.3
93.5
96.4
47.6
90.2
22.1
84.9
5
weeks
140 C
72.1
9.5
50.9
95.9
33.2
1
week
80.0
16. 7
65.1
102.8
71.8
5
weeks
150 C
Table 1. Compression Set Results (%) Continued
70.4
59.7
64.2
88.4
1
week
77.5
84. 3
75.3
109.4
5
weeks
160 C
16.1
104.3
81.4
42. 3
1
week
27.5
111.6
120.1
72.4
5
weeks
200 C
Appendix 3
Table 2. Predicted Compression Set Results (%)

Compound
Reference
Natural Results
Prediction Results
1 year
40 years
1 year
40 years
46.8
100.0
27.0
45.9
58.2
92.0
37.8
57.9
35.3
71.1
18.1
38.6
72.8
98.2
49.2
76.3
42.2
81.9
29.7
45.4
21.1
60.6
31.8
47.0
42.9
92.9
25.3
35.6
24.0
74.3
26.1
36.0
24.0
75.0
10.1
13.2
38.2
79.5
33.6
43.0
19.4
59.0
10.1
14.8
32.8
78.8
15.2
23.6
32.8
81.1
34.6
58.5
39.2
77.9
12.2
15.6
26.2
81.9
13.3
16.1
15.7
40.8
10.0
13.3
83.9
97.0
71.2
78.5
69.9
85.0
39.1
44.3
45.9
72.4
14.4
18.0
197
Appendix 3
Table 2. Predicted Compression Set Results (%) Continued

Compound Reference
Prediction Results
1 year
40 years
N1
16.6
27.5
N2
49.4
64.5
N3
26.6
40.8
N4
50.5
69.9
N5
12.9
15.4
N6
34.2
45.9
N7
19.0
26.5
N8
52.7
71.1
N9
66.1
81.4
N10
53.2
76.9
P1
54.9
73.3
P2
74.4
99.6
P3
35.3
65.5
P4
31.6
46.5
P5
10.4
23.3
P6
35.5
60.9
P7
35.2
55.8
P8
43.8
59.0
P9
22.5
29.9
P10
43.9
61.3
198
Compression Set
Compound N1
23 C
100 C
150 C
100.0
90.0
80.0
Compression Set (%)
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
5.0
6.0
Weeks
Figure 1
Compression Set
Compound N2
23 C
100 C
150 C
120.0
110.0
100.0
Compression Set (%)
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0.0
0.0
1.0
2.0
3.0
4.0
Weeks
Figure 2
199
Appendix 3
200
APPENDIX 4
EXAMPLE GRAPHS
201
Appendix 4
202
Example Graphs
Glass Transition Temperature

Compound A
100C
70C
80C
90C
-25.00
Glass Transition Temperature (C)
10
20
30
40
50
60
150
180
-30.00
-35.00
-40.00
-45.00
Figure 1
Tan Delta
Compound M
100C
70C
80C
90C
0.300
Tand Delta at 23C
0.200
0.100
0.000
0
30
60
90
120
Figure 2
203
Appendix 4
Tan Delta
Compound A
100C
70C
80C
90C
0.300
Tan Delta at 23C
0.250
0.200
0.150
0.100
0
10
20
30
40
50
60
Figure 3
Arrhenius Plot for Change in Elongation at Break with Time

Compound G
Time (days) to end point
1000.000
100.000
10.000
1.000
0.00265
0.00270
0.00275
0.00280
0.00285
0.00290
0.00295
Reciprocal Temperature (kelvin)
Figure 4
204
Example Graphs
Arrhenius Plot for Change in Elongation at Break with Time

Compound N9
1000.000
100.000
10.000
1.000
0.00220
0.00225
0.00230
0.00235
0.00240
0.00245
0.00250
0.00255
0.00260
0.00265
0.00270
0.00275
Figure 5
Arrhenius Plot for Change in Hardness with Time

Compound B for 10% Change
1000.000
100.000
10.000
1.000
0.002650
0.002700
0.002750
0.002800
0.002850
0.002900
0.002950
Figure 6
205
Appendix 4
Arrhenius Plot for Change in Hardness with Time

Compound R
1000
100
10
1
0.00265
0.00270
0.00275
0.00280
0.00285
0.00290
0.00295
Reciprocal Temperature (Kelvin)
Figure 7
WLF Temperature Shifted Elongation at Break - Compound M

Reference Temperature = 40C
100C
70C
80C
90C
500
Elongation at break (%)
400
300
200
100
0
1
10
100
1,000
Time (Months)
Figure 8
206
Example Graphs
WLF Temperature Shifted Elongation at Break - Compound K

80C
90C
100C
70C
120C
700
600
Elongation at break (%)
500
400
300
200
100
0
0
10
100
1,000
Time (Months)
Figure 9
WLF Temperature Shifted Hardness - Compound B

100C
70C
80C
90C
100
95
90
85
80
75
70
65
60
0
10
100
1,000
Time (Months)
Figure 10
207
Appendix 4
WLF Temperature Shifted Hardness - Compound R

100C
70C
80C
90C
100
95
90
85
80
75
70
65
60
55
50
1
10
100
1,000
Time (Months)
Figure 11
208

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Ageing of Rubber - Accelerated Heat Ageing Test Results

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Accelerated Heat Ageing

R.P. Brown, T. Butler

Europes leading independent

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

Rapra Technology Limited

First Published 2001 by

Rapra Technology Limited

Copyright 2001 Rapra Technology Limited

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

Copyright 2001 Rapra Technology Limited

Appendix 1 - Compound Details ......................................................................................... 23

Ageing of Rubber - Accelerated Heat Ageing Test Results

Compound P4 ............................................................................................................... 165

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Ageing of Rubber - Accelerated Heat Ageing Test Results

2.1 Original Materials

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2.2 New Materials

Compounds P1 P10 are materials submitted by industry participants:

ethylene propylene copolymer

siloxane cellular material

medium nitrile, carbon black filled with EV sulphur cure

nitrile, NF standard 0115/2

EPDM, NF standard 0115/1

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

W type polychloroprene with small amount of SBR, carbon black filled,

thermoplastic rubber Santoprene 101 55 V185 from AES

Ageing of Rubber - Accelerated Heat Ageing Test Results

3 PREPARATION OF TEST PIECES

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5 EXPOSURE OF TEST PIECES

Ageing of Rubber - Accelerated Heat Ageing Test Results

6.3 Prediction of Natural Ageing

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Ageing of Rubber - Accelerated Heat Ageing Test Results

In this expression, aT is the shift factor of an isotherm determined at temperature T, in relation

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Ageing of Rubber - Accelerated Heat Ageing Test Results

Copyright 2001 Rapra Technology Limited

7.1.4 Tensile Strength

7.1.5 Elongation at Break

Ageing of Rubber - Accelerated Heat Ageing Test Results

7.1.7 Compression Set

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Ageing of Rubber - Accelerated Heat Ageing Test Results

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Heat Ageing Test Results

Copyright 2001 Rapra Technology Limited

7.2.4 Tensile Strength

Ageing of Rubber - Accelerated Heat Ageing Test Results

7.2.5 Elongation at Break

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7.2.7 Compression Set

Ageing of Rubber - Accelerated Heat Ageing Test Results

7.2.8 Choice of Analysis Method

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7.2.9 Effectiveness of the Predictions

Ageing of Rubber - Accelerated Heat Ageing Test Results

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Heat Ageing Test Results

Copyright 2001 Rapra Technology Limited

Ageing of Rubber - Accelerated Heat Ageing Test Results

Curing conditions: 35' @ 141 C