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Paper # 33

Effects of Processing & Test Parameters on


Compression Set

R. J. Del Vecchio* and Ernest Ferro, Jr.

Presented at the Fall 170th Technical Meeting of the


Rubber Division, American Chemical Society
Cincinnati, OH
October 10-12, 2006
ISSN: 1547-1977

*Speaker
ABSTRACT
ASTM D395 describes the specimens to be used in compression set testing of
rubber compounds, and the general method of testing. But both the conditions under
which compression set specimens are molded (time/temperature) and the conditions of
the test (time/temperature) will have some effect on the test results of any given rubber
compound. In addition, individual compounds will differ in their response to the test,
depending on some of the major compounding variables, such as polymer type,
vulcanization system, and reinforcement type and level. However the method does not
specify any details about the molding conditions for the test specimens.
In order to investigate the degree of all these effects, four different polymer types
were used to produce compounds of approximately equal hardness, which were
vulcanized at two different temperatures and at three levels of molding time.
Specimens were then tested according to 395 Method B, using a 70 hr duration at four
temperatures. The variations in test results are analyzed by polymer type, molding
temperature, molding time, and test temperature. The different contributions of the
factors are compared, and a conclusion is drawn for a recommended vulcanization time
for test specimens. Some additional comparisons are made with Method A test results.

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INTRODUCTION
Compression set testing has been a basic part of evaluating rubber compounds
for a very long time, and is one of the comparatively few standard tests that would seem
to have a reasonably direct relationship with a particular function, that is, retention of
sealing force for products such as O-rings. The normal test specimen is a cylinder or
button of nominal 12.5mm height and 29mm in diameter, although testing can be done
on other types of specimens when necessary. There are two methods described in
ASTM D-395; Method A employs a compressed spring to maintain a reasonably
constant compressive force of 1.8 kN on the specimen, while in Method B the specimen
is subjected to a constant 25% compressive strain. In both tests the specimen is
subject to the stress or strain for set time periods at some elevated temperature
deemed suitable for the compound, after which the specimen is removed from the
fixture and allowed to return to room temperature. The specimen height is then
measured and compared to its original height, and the percentage of nonrecovery is
reported as compression set.
The two methods do not provide readily comparable figures: if the button
recovers to 90% of its original height in a Method A test, that would be a compression
set of 10%; but the same 90% height retention in Method B would be calculated as a set
of 40%, because the button would only have recovered 60% of the imposed strain. The
two methods have a major difference in how the specimen is subjected to strain. In
Method A, a button of a 45 durometer compound will deform much more than one of 75
durometer, so strain state during the test duration will be very different, and the softer
button is likely to take a higher set. In Method B, both buttons are subject to the same
strain, although they will experience different stress, and the stiffer button becomes
more likely to take the higher set.
Method B is by far the more commonly used test.
The general assumption is made that lower compression set indicates a lower
stress relaxation characteristic of the elastomer, which means that under a set strain, its
sealing force against the containing walls will decline slowly rather than rapidly. This
may not be a universally valid assumption, that is, two compounds with the same
compression set might still differ significantly in how much their sealing force has

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changed. An actual test on the rate of change of sealing force with time would be
preferable, but so far such tests have not been widely accepted or practiced, since they
require significantly more applied technology to use.
It is also assumed that acceleration of the stress relaxation in the elastomer by
elevated temperature is a valid technique. Again, this cannot apply for all elevated
temperatures, since beyond some point the thermal effects will cause processes to
occur in the elastomer that are very different from the mechanisms of stress relaxation
and aging at operating temperatures. At that point the test is no longer about stress
relaxation, it becomes mainly or purely a test of heat resistance. Therefore, care must
be taken to not use excessively high test temperatures as a means of predicting product
performance for extended time periods.
What D-395 does not specify are the molding conditions for the test specimens.
Thus a manufacturer who vulcanizes his product for 15 minutes at 155C is perfectly
free to cure his test buttons for 20 minutes at 165C. For many compounds, subjecting
the material to higher heat or a longer cure cycle will produce a different enough
distribution of crosslinks to significantly improve compression set. This could be
considered a form of cheating on the test, but at present there is no formal restriction to
hamper anyone from manipulating the vulcanization process in any way they wish. A
recent survey of procedures various laboratories use resulted in the following list of
standard cure for compression set buttons, which is by no means exhaustive.
A. Tc90 plus 2 minutes
B. Tc90 plus 5 minutes
C. Tc90 plus 10 minutes
D. Double Tc90
E. Triple Tc90
F. 20 minutes
G. 30 minutes
To add to the complexity of this, sometimes the cure temperature is the same as
the production process, and sometimes it is higher, often by 10C or more.
The question then arises as to how much effect molding conditions can have on
compression set test results. In order to evaluate such effects, an experiment was
drawn up which varied the vulcanization times and temperatures. To broaden the
enquiry, four different polymer types were chosen, one of which was used with three

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different cure systems.
Then to add further to the level of exploration of the testing process, four different
test temperatures were used, but all tests were 70 hours in duration for the sake of
simplicity.
The main body of the experiment was focused on Method B, but a limited amount
of Method A data was also generated for purposes of comparison.

EXPERIMENTAL
The four polymer types were:
A. SBR (three cure systems)
B. EPDM
C. NBR
D. CR
These were selected since all have at least reasonable heat resistance and can
logically be tested at the same temperatures with no concern about polymer breakdown.
All were compounded to nominal 65 Shore A Durometer, and a conventional sulfur cure
was used for the SBR, EPDM, and NBR compounds, while the CR was vulcanized
using its own particular system. In addition, the SBR compound was cured with a full
efficient vulcanization system (EV) as well as a peroxide system.
See Table 1 for the formulation details. The compounds were formulated to be
as similar as possible, using the same types of carbon black at as close to the same
loading as would achieve equal hardness, with the same very basic antidegradant
protection, the same process aid, etc. The goal was to ensure that compression set
resistance would be primarily a function of the polymer type rather than any of the other
possible compounding variables such as reinforcement and plasticizer. The use of
three very different cure systems in the SBR was to explore how that factor alone might
affect properties.
The two temperatures chosen for vulcanization were 150 and 165C. Cure times
were Tc90, Tc90 plus 5 minutes, and Tc90 plus 10 minutes. These were arrived at by
educated guess as Tc90 being a very minimal cure and an additional 10 minutes being
ample for extra time, with a point midway between as a possibly sufficient. The four test
temperatures were room temperature, 70, 100, and 125C. Room temperature testing

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provides information on how much of the stress relaxation takes place without
acceleration, while the increasing temperatures of the other tests will clarify how much
acceleration and/or change in the results is accomplished by heat.
Thus the pattern for the vulcanization time and the test temperatures was as
below, which was repeated for each the two cure temperatures and each of the six
compounds. This was a full factorial designed experiment using one factor at 2 levels
(cure temperature), one at 3 (cure time), one at 4 (test temperature), and one at 6
(compound) for a total of 144 runs (each using two buttons).

Cure time Test temp


Tc90 RT
Tc90 70
Tc90 100
Tc90 125
Plus 5 RT
Plus 5 70
Plus 5 100
Plus 5 125
Plus 10 RT
Plus 10 70
Plus 10 100
Plus 10 125

In addition Method A testing was done using three compounds (all SBR), one
cure time (Tc90 plus 10), one molding temperature (165C), and all four testing
temperatures.
Standard processing and physical tests were performed using the following
methods:
MDR Rheometry ASTM D 5289
Hardness ASTM D 2240
Tensile, elongation and modulus ASTM D 412 method A
Heat aging ASTM D 573
Compression Set ASTM D 395 methods A and B
Rheometer and basic physical test data are shown in Table II below.
Method B Compression Set data are in Table III, Method A data are in Table IV.

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RESULTS AND DISCUSSION
Method B results
The substantial amount of data generated requires a variety of approaches to
digest and analyze. Percentage of set in Method B ranges from under 10% to over
60%, a very broad range that indicates clearly that the experimental factors have major
effects on the test results.
The simplest form of examination is to simply compare average sets organized
according to the major factors alone. For instance, a decrease in set as molding time
increases would be expected. The respective averages of the Tc90, plus-5, and plus-
10 molding times for all compounds at both molding temperatures and at all the test
temperatures were 35.4%, 27.8%, and 24.8%. This confirms the anticipated result.
Further, the larger drop in set going from the least time to the median time indicates that
Tc90 is in fact a marginal cure time.
Just how differently the compounds would react to set testing is not precisely
predictable, but it is entirely predictable that they would show some contrasts, and they
do. Overall sets by compound were: SBR- 30.2%, EV cure- 12.0%, peroxide cure-
17.3%, EPDM- 39.6%, NBR- 44.0%, and CR- 33.1%. The effect of alternate cure
systems on the SBR is fairly dramatic, and the superior performance of the EV system
compared to the peroxide system is interesting. (Inclusion of a coagent in the peroxide
system might improve its compression set resistance to the level of the EV system.) The
contrasts between the polymer types when using comparable cure systems is more
subtle, although still meaningful.
Set would be expected to increase with the test temperature, and the grand
averages by increasing test temperature are 14.2%, 20.0%, 36.6%, and 46.6%, again
confirming the normal model for the process. However, it is noteworthy that room
temperature set is about 70% of the set achieved at a temperature almost 50C warmer.
Clearly the stress relaxation mechanism operates at very detectable level even without
thermal acceleration. On the other hand, the more than doubling of the set figures
going from 70C to 125C, again about a 50-degree differential, demonstrates that
increasing heat can have very marked accelerating effect.

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The last factor was molding temperature, and the averages of all compounds at
the 150C versus 165C molding temperatures are not significantly different from each
other. This indicates that when the molding times are related to the Tc90 at the given
temperature, roughly equal states of cure are achieved, as theory would predict. (This
may not necessarily apply across an extreme contrast in temperature range, such as 40
degrees Centigrade or more.)
Interestingly, there are no correlations between room temperature sets and any
of the heat-accelerated sets. This suggests that the primary mechanism of stress
relaxation at room temperature may not actually be affected by heat, even though heat
clearly has the effect of increasing set.
The question then can be asked as to whether heat resistance plays a major part
in compression set resistance. If so, then a correlation between standard heat
resistance testing and set should exist. However, the very best correlation between
any heat resistance and set tests is between change in M-100 from test slabs and the
set of button specimens cured at 165C for Tc90 plus 5, and that correlation has an R-
squared of only 55%. By contrast, the correlation between change in M-100 and
change in Elongation for the compound has an R-squared of 90%.
Thus it appears that Method B set is a result at room temperature of one stress
relaxation mechanism, but a different mechanism takes over as higher temperatures
become a major factor. And further, the heat-related mechanism that affects set is not
closely related to the mechanism of simple heat aging of test slabs.
All of this is, in a sense, unfortunate, because it indicates strongly that
acceleration of compression set testing through use of elevated temperatures reveals
little if anything about room temperature set; and because it also indicates that
compounding to improve heat resistance will have little if any effect on elevated
temperature compression set.
A detailed analysis of the data reveals two significant contrasts. While every
compound displays lower set at the longest cure time, the differences in set with
increasing cure time are very small for all the SBR compounds, and then increase
significantly in the order of EPDM, then CR, then NBR. This difference must relate to
some combination of the polymers inherent properties and crosslink structure.

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Also, average set increases for all compounds at the test temperature increases,
but the three compounds whose cure systems are the full sulfur type show a much
greater increase than the two alternate SBR cures and the CR cure. This contrast is
readily relatable to the sensitivity of polysulfidic crosslinks.

Method A results
The three SBR compounds were used in this comparison, cured at the single
combination of time and temperature of Tc90 plus ten minutes @ 165C. Table IV
shows the same trends between the cure systems as was observed in Method A tests,
with the full sulfur system highest in set and the EV system lowest. The set figures are
much lower for Method A, which is due to the way in which they are calculated, using
the original height as the base. If the very approximate conversion of the Method A set
to a scale similar to Method B is made by the simple expedient of multiplying by 4 (the
ratio of the Method B deformation of 0.125 to the nominal height of a button of 0.5), then
the figures become very comparable. For example, the room temperature Method B
sets of the three compounds cured the same way were 10.24, 8.66, and 15.04%, and
the 4x values for Method A are 10.36, 7.92, and 12.16%. (This means the actual
permanent deformation of the buttons is reasonably comparable.)
This parallelism in level of permanent deformation would not necessarily be
expected, given the differences in the Methods as explained earlier. However, Table V
provides the actual dimensions of samples in one of the Method A tests, at 125C. The
initial deflection under load for the buttons is about 0.355 inches, not that far from the
Method B imposed deflection of 0.375, so for these particular compounds at about 65
Shore A hardness, the initial strain state of the specimens in Method A is at least in the
same ballpark as in Method B. This makes the roughly comparable results in actual
permanent deformation more understandable. If the compounds had been 85 Shore A
or 45 Shore A, then the initial strain state would have been appreciably different, and
the final set would also have been different.
The change in deflection from the beginning of the test until the 70 hrs at
temperature were completed was not really large, although the tendency for the sample
to grow in height due to thermal expansion may have had an effect there. As a minor

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additional bit of data, the samples were remounted in the fixtures under load a day later,
and the average deflection then was only slightly less than it had been at the first
mounting, even though the set taken in the test made the sample height significantly
less before its being remounted. This may relate to the nonrecoverable deformation
that rubber samples show when first subject to strain, the well-known Mullins effect.
The EV cured specimens deflected least in the fixture at the end of the oven
cycle, which is a clear indication that they maintained a counterpressure to the spring
force better than either of the other compound variations. So in this case, the lower
permanent set of those specimens did correlate with a higher retained sealing force
under the conditions of the test.
The overall ratio of 4x Method A set to Method B set changes with increasing test
temperature, going from about 1.14 at room temperature to 1.38 at 125C. This
indicates that the interaction of higher temperature and constant load makes the test
more aggressive than the constant deflection Method B technique. However, the
consistency of the comparative performance of the three compounds in both the Method
A and Method B tests demonstrates that both methods have similar effects on the
samples, at least in the case where sample hardness happens to result in an initial
Method A deflection somewhere near the imposed deflection of Method B. It is
extremely likely that with much harder or softer compounds a dramatic contrast in
results between the two test methods would be seen.
Recommendation
Since the effect of changing cure time on compression set results is, as
expected, clearly significant, the present lack in ASTM D395 of any form of specified
cure conditions in making test specimens is a weakness in the specification. Therefore,
either D395 should be revised to include some inputs on appropriate levels of time and
temperature for the molding of the specimens, or at the very least, require the
conditions used to make the specimens to be disclosed as part of the test results report.

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CONCLUSIONS
1. When specimen cure time is related to Tc90, moderately different cure
temperatures can be used without significant effect on test results.
2. Increasing cure time does have the effect of decreasing observed set.
3. Room temperature set and heat-accelerated set are each the result of
different stress relaxation mechanisms and do not correlate well.
4. Elevated temperature effects on accelerating compression set do not
correlate with basic heat aging tests on molded slabs.
5. Crosslink type has major effects on compression set, with polysulfidic
crosslinks displaying substantial temperature sensitivity.
6. Polymer types can also have different set characteristics, even when as much
as possible of the remaining compounding variables are kept constant.

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TABLES

Table I - Formulations
CS-1 CS-2 CS-3 CS-4 CS-5 CS-6
SBR-1502 100 100 100
Nysyn 33-5 100
Neoprene W 100
Royalene 525 100
Stearic Acid 1 1 1 1 1
Zinc Oxide 5 5 5 5 5 5
Agerite Resin D 2 2 2 2 2 2
N-550 Black 25 25 25 17.5 24.5 25.25
N-990 Black 50 50 50 35 49 50
Sulfur 1.8 1.8 1.3 0.25
Altax 1.2
Methyl Tuads 0.3 1
DPG 0.2 1.5
Vanax A 2
Akrochem BBTS 1.55 2 1.5
Butyl Tuads 1.7
Proaid AC-1142 2 2 2 2 2 2
Akrochem DC40C 3.5
Total 188.35 190.9 187.5 165.8 186.3 188

Table II Rheometer and Physical Test Data


CS-1 CS-2 CS-3 CS-4 CS-5 CS-6
MH (165C) 23.91 20.88 19.18 30.97 16.45 20.24
ML 1.99 1.99 2.38 2.28 1.74 3.3
TC90 (seconds) 636 840 681 547 98 203
TS1 (seconds) 183 159 44.4 156.6 34.2 33.6
MH (150C) 25.36 22.8 17.01 31.98 17.32 20.61
ML 2.39 2.25 2.63 2.69 2.04 3.5
TC90 1578 2269 2552 1391 197 458
TS1 510 424.2 123 447.6 61.2 57.6

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Table II continued

Tensile slabs cured Tc90 @ 165C


Tensile MPa 15.5 13.7 13.0 8.0 12.9 19.1
Elongation % 296 282 404 268 408 228
Durometer Shore A 67 65.9 63 66.3 66.4 69
100% Modulus 4.6 4.2 2.8 3.2 2.8 7.3
Heat aged 70 hr/100C
Aged Tensile Loss % 1.37 -2.11 -9.03 3.87 -5.52 -7.79
Elongation Loss % -45.27 -35.46 -2.47 -43.65 -54.41 -21.92
Durometer Increase 8.5 5.2 2.8 5.4 5 3.1
M-100 Change % 95.76 42.69 -0.24 64.52 105.65 26.47

Table III Compression Set Data (Method B)


CS-1 CS-2 CS-3 CS-4 CS-5 CS-6
Cure Time @ Test Temp Percent Compression Set
150C Deg C
Cured for Tc90 23 10.54 8.56 13.64 11.11 13.79 39.00
Tc90 + 5 23 10.32 8.59 13.16 11.02 15.41 35.65
Tc90 + 10 23 10.24 8.66 15.04 10.67 15.04 31.27
Cured for Tc90 70 19.49 8.63 16.86 29.76 47.08 20.07
Tc90 + 5 70 16.93 8.17 18.48 25.88 28.57 12.56
Tc90 + 10 70 15.81 7.84 17.69 20.55 23.22 10.51
Cured for Tc90 100 45.63 14.57 16.48 62.44 76.23 45.46
Tc90 + 5 100 40.32 12.20 18.87 56.30 57.42 34.39
Tc90 + 10 100 37.00 10.94 16.72 53.15 48.30 30.81
Cured for Tc90 125 60.08 19.21 30.65 71.15 81.67 55.09
Tc90 + 5 125 53.94 17.58 27.69 67.45 64.05 44.77
Tc90 + 10 125 52.17 15.75 26.81 63.38 53.76 44.58

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Table III continued
CS-1 CS-2 CS-3 CS-4 CS-5 CS-6
Cure Time @ Test Temp Percent Compression Set
165C Deg C
Cured for Tc90 23 9.68 6.97 9.31 8.43 20.93 35.94
Tc90 + 5 23 9.44 6.97 10.33 8.39 14.55 21.27
Tc90 + 10 23 10.11 7.00 9.72 8.39 14.54 19.11
Cured for Tc90 70 9.68 6.97 9.31 8.43 20.93 35.94
Tc90 + 5 70 9.44 6.97 10.33 8.39 14.55 21.27
Tc90 + 10 70 10.11 7.00 9.72 8.39 14.54 19.11
Cured for Tc90 100 43.44 18.91 14.39 66.79 83.10 52.73
Tc90 + 5 100 37.89 12.83 12.99 53.56 49.28 30.21
Tc90 + 10 100 31.63 10.15 12.41 47.48 36.39 24.42
Cured for Tc90 125 57.77 22.87 27.82 72.30 90.96 61.3
Tc90 + 5 125 50.98 18.29 23.49 64.36 58.55 47.82
Tc90 + 10 125 45.67 16.40 19.95 59.00 46.79 41.86

Table IV - Compression Set Data (Method A)


SBR compound Sulfur EV Peroxide
Room Temp. 2.59 1.98 3.04
70 Deg C 4.79 2.28 5.15
100 Deg C 9.07 2.78 4.90
125 Deg C 14.06 5.16 8.17

Table V - Method A Specimen Dimensions (125C test)


SBR compound Sulfur EV Peroxide
Original height (inches) 0.502 0.504 0.514
Loaded (room temp) 0.356 0.355 0.355
70 hr (hot) 0.336 0.348 0.332
Recovered 0.431 0.478 0.472
Reloaded (room temp) 0.346 0.362 0.341

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REFERENCES
The Compression Set Behavior of Nitrile Rubber, H. J. Jahn & H. H. Betram, presented
at the ACS Rubber Division Meeting, Cincinnati, OH, Oct 3-6, 1972

Investigation of the Structure-Property Relationships of Improved Low Compression Set


Nitrile Rubbers, D. M Chang, presented at the ACS Rubber Division Meeting, Las
Vegas, NV, May 20-23 1980

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