FUNDAMENTALS OF COMPOUNDING

EPDM FOR COST/PERFORMANCE

R. D. ALLEN

Uniroyal Chemical Division

Uniroyal, Inc.
Naugatuck, Connecticut
Manuscript received November 16, 1982

INTRODUCTION

EGARDLESS OF THE BASE POLYMERUSED, THE PROBLEM FOR THE

R compounder
satisfactorily
is to formulate a rubber compound that will process
in the equipment available in his plant; that will provide
the required service or performance; that can be manufactured into a
part at the lowest possible cost. An accurate assessment of the service
conditions and a knowledge of the capabilities and weaknesses of
polymers are required so that the best polymer for the job may be
selected.

EPDM POLYMER PROPERTIES

Because of their structure and composition, EPDM polymers are in-
herently resistant to ozone and weathering. Compounds are generally
suitable for severe outdoor or high ozone applications without need
for antiozonants, waxes or other special additives. EPDM compounds
provide good heat and oxidation resistance. Other inherent charac-
teristics of EPDM include resistance to polar fluids, such as alcohols,
ketones, certain esters and acetates; resistance to water and a variety
of aqueous solutions; good low temperature flexibility; high resilience
over a fairly broad temperature range; excellent electrical properties,
i.e. high dielectric strength, low power factor and corona discharge
resistance, and radiation resistance. EPDM compounds do not
possess resistance to hydrocarbon oils and solvents.
Reprinted courtesy of Rubber World, September, 1982.

Journal of ELASTOMERS and PLASTICS, Vol. 15 (January 1983) 19

0095-2443/83/01 0019-14 $04.50/0
@1983 Technomic Publishing Co., Inc.

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Table 1. Inherent Properties of EPDM.

Its low
density (.865 specific gravity) combined with its ability to ac-
cept high levels of extender oils and filler loadings provide the oppor-
tunity to make competitive compounds for a variety of applications.
If EPDM is chosen for the application, the polymer selection process
continues. There are between fifty and sixty EPDM polymers available
from five domestic suppliers. As with other synthetic rubbers, there
are a number of modifications which can be made in EPDM polymers.
Included would be:
o Molecular weight (average)
Molecular weight is not usually reported as such. Mooney
Viscosity, which relates to molecular weight, is commonly
measured and reported. Other structural and compositional fac-
tors, such as ethylene-propylene ratio and branching, also may
influence Mooney Viscosity. The higher molecular weight poly-
mers contribute improved physical properties and are more ex-
tendable. Lower molecular weight polymers are generally easier
processing and are particularly useful in lightly loaded com-
pounds, needed in some high performance parts.
o Molecular
weight distribution
Again this is not usually published or reported information. In
general, broader molecular weight distribution is desirable for
good mill and calender processing. Somewhat narrower mol-
ecular weight distribution is more desirable for extrusion process-
ing. Blending of polymers is a common practice to attain a more
satisfactory processing behavior.
o Comonomer ratio
(ethylene to propylene)
This ratio may vary from 45:55 to 75:25 in commercially available
types. The higher ethylene polymers are, as a rule, more extend-
able. They extrude faster and smoother and provide high green
strength which improves shape retention of the extrudate.
Higher propylene polymers are more suitable for mill processing,

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 21

provide better calendering and have somewhat improved low

temperature properties.
o Third monomer-type and amount
The type of third monomer affects cure rate. The three third
monomers (dienes) in commercial EPDM polymers, in order of
their cure rates (slowest to fastest) are:
dicyclopentadiene
1,4 hexadiene
ethylidene norbornene
Increasing the diene content improves the cure rate. The greater
degree of unsaturation permits compounds with faster cure
rates. EPDM polymers with high levels of ethylidene norbornene
are more suitable for blending with NR, SBR, CR, etc.

The EPDM polymer, or blend of polymers chosen will result from

considering the process to be used; specification requirements or ap-
plication performance needs, and costs of materials and manufacturing.

REINFORCEMENTS

EPDM rubbers are amorphous terpolymers. As is true of other non-

crystallizing polymers, EPDM requires reinforcement to be of practical
value. Mechanical properties of the unfilled rubber are quite poor. The
effects of a filler in a compound depend on particle size, particle
shape, the nature of its surface, the degree of dispersion of the filler in
the rubber and the tendency to form agglomerates or structure. Car-
bon blacks are the most useful materials for the reinforcement of
EPDM. Silicas, clays, talcs and some other mineral fillers may also be
used.
Carbon blacks and other fillers must be well dispersed in order to at-
tain their full effectiveness as reinforcing agents in EPDM rubbers.
High tensile strength, good tear resistance and improved abrasion
resistance are generally associated with good reinforcement. Well
mixed batches also provide better, more uniform processing for extru-
sion, calendering, molding, etc.
Since comparatively few applications for EPDM compounds require
extraordinary mechanical properties, the semi-reinforcing carbon
blacks, which are more easily dispersed, are more widely used. Non-
reinforcing fillers, such as calcium carbonate and ground coal, may be
used as diluents in the interest of lowering compound cost.

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Table 2. Reinforcing Fillers.

PLASTICIZERS
Naphthenic oils have been the most widely used plasticizers for
EPDM compounds because they provide the best compatibility and
have offered reasonable cost. In applications where higher temp-
eratures are encountered or in colored compounds, paraffinic oils are
usually chosen because of their lower volatility and improved ultra
violet light (UV) stability. Some paraffinic oils, if used at farily high
levels, tend to bleed from cured, high ethylene EPDM compounds. To
ensure compatibility where such oils must be used, it is usually ad-
visable to base the compound on a polymer having a somewhat lower
ethylene content. It is also possible to alleviate the problem in a com-
pound based on a high ethylene polymer by replacing part (20-25 phr)
of it with a lower ethylene type.
Aromatic oils tend to give poorer properties and have an adverse in-
fluence on weathering and UV resistance. They must not be used in
conjunction with peroxide curing systems.
Stearic acid, zinc stearate or other internal lubricants are often in-
cluded in the compound to aid processing, i.e. mill release, mold flow
and release. Depending on the type process aid, an excessive amount
in the compound may affect adhesion (or bonding), knitting (in
molding), splicing and other aspects of manufacturing opposed to the
effect desired.
EPDM compounds are, by nature, not tacky. If there is need in the
process for building tack it would be necessary to add a tackifier to the
compound. Some care must be taken in making the selection because
of potential compatibility problems and effects on cure rate, if the
tackifier has excessive unsaturates. There are tackifiers available
which have been developed specifically for EPDM compounds.

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Table 3. Plasticizers and Processing Aids.

EPDM rubbers are terpolymers in which a small amount of a non-

conjugated diene is used. The diene introduces unsaturation which is
pendant, or in a side chain. The substituent double bond provided by
the diene permits sulfur vulcanization. EPDM polymers may also be
cross-linked with peroxide systems.

CURING
As previously stated, the type and amount of third monomer affects
cure rate.Hence, the choice of cure system will be influenced by the
polymer. It should be recognized that, if one substitutes one EPDM
polymer for another in an existing formulation without changing the
cure system, the rate of cure and properties will almost certainly be af-
fected. This is particularly true if the two polymers utilize different
third monomers. The properties can also be affected by other dif-
ferences in polymer structure and composition.
In this presentation, the cure systems discussed will be for EPDM
polymers in which ethylidene norbornene is the third monomer. It
should be remembered that, in general, polymers with dicyclopenta-
diene or 1,4 hexadiene will require somewhat more active accelerators
and/or higher levels to provide satisfactory cure rates.
As already mentioned, it is the pendant unsaturation which allows
sulfur vulcanization in EPDM compounds. Common accelerators may
be used. Faster accelerators and generally higher levels are employed
than with highly unsaturated polymers such as NR, SBR and NBR. A
particular combination selected for an EPDM curing system depends
on several considerations, such as processing methods, properties re-
quired, the filler loading, cost and compatibility. A few generalizations
are possible. Usually, the cure system will contain a thiazole (MBT,
MBTS, etc.) in combination with a thiuram and/or a dithiocarbamate.
Sulfur donor type accelerators may replace part or all of the elemental

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Table 4. Solubility Limits.

sulfur if heat resistance and/or compression set requirements are

severe.
For somemolded goods applications, accelerator bloom may be
unacceptable. To assure a non-blooming compound, it is necessary to
maintain the levels of the various chemicals below their solubility
limits. Limits for the most commonly used accelerators are shown in
Table 4.
It has long been known that low sulfur or sulfur donor cure systems
give good heat resistance and improved compression set. For example
(see Table 5), outstanding heat resistance may be attained by using a
cure system with 3 to 4 phr of a thiazole (MBT, MBTS or CBS) in
combination with small amounts of TMTD and dithiodimorpholine
(DTDM), and 1.0 to 1.5 phr of zinc dibutyldithiocarbamate (ZDBDC),
with a level of elemental sulfur below one part.
Another sulfur donor, low sulfur system that may be used for good
heat resistance, but better compression set than the &dquo;high thiazole&dquo;
system entails using two to three phr levels each of TMTD, two
dithiocarbamates, DTDM and a low level of sulfur. This system will
result in blooming.

Table 5. Cure Systems for EPDM (ENB).

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In black EPDM compounds to be used for open steam cured extru-

sions, bloom is usually not a problem. Some cure systems which may
bloom when mold cured, may not bloom when cured in open steam.
Since steam curing cycles are typically longer and at lower tempera-
tures than for molding, the cure system may be quite simple and more
economical. For example. 0.5 to 1.5 phr MBTS or MBT, 1.5 phr
TMTD and 1.5 phr sulfur may be quite adequate. A dithiocarbamate,
such as zinc dimethyldithiocarbarr~ate (ZDMDC) may be added if an
increased cure rate is needed.
Peroxide cure systems may be necessary if the application requires
resistance to temperatures of 150°to 175°C and very low compression
set. Peroxide systems are generally quite expensive compared to
sulfur cure systems, and are used only where part performance is
rather critical. There are several peroxides in common use. They are
usually supplied on carriers, hence are less than 100 percent active.
The most frequently used peroxides are:
.
dicumyl peroxide
· 2,5 dimethyl-2,5-di(t-butyl peroxyl) hexane
· a,a’ bis (t-butyl peroxy) diisopropyl benzene
A so-called coagent is often used with the peroxide to enhance
some compound property characteristic,
or such as compression set,
heat resistance, tear resistance, and adhesion.
The commonly used activator systems are also functional in EPDM
compounds. The best known and most economical is zinc oxide,
stearic acid combinations for sulfur cure systems. For many com-
pounds 3 phr zinc oxide is adequate, and offers a cost savings com-
pared to the customary use of 5 phr. Stearic acid may not be
necessary with some sulfur systems, but it is usually left in as a pro-
cessing aid, in any case. Neither zinc oxide, nor stearic acid is required
to activate a peroxide system, but zinc oxide provides improved heat
resistance.
In sulfur cured EPDM compounds, an antioxidant is usually un-
necessary unless the service or specification requires heat resistance at
temperatures above 125°C. For either sulfur or peroxide systems, an
appropriate antioxidant should be used if the application involves ex-
posure above 150°C. Because of their structure and composition,
EPDM polymers are inherently resistant to ozone. Therefore, EPDM
compounds are normally suitable for outdoor or ozone exposure with-
out need for waxes and/or antiozonants.
There are many other additives which may be used in the com-
pound to serve a specific need. For example, coupling agents in

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mineral filled compounds to improve physical properties; colorants;

flame retardant additives; adhesion promoters; process aids; desic-
cant to scavenge moisture if the compound is to be LCM or
microwave cured, chemical blowing agents for making sponge, and
many, many more.

APPLICATIONS
The inherentproperties of EPDM polymers have led to their usage in
a considerable variety of applications. We will discuss some of the
more significant uses and show some formulations to illustrate con-
cepts in compound development for the specific application.
Rubber sheeting has been used for some years in roofing, but in
rather limited quantities, due to cost compared to cheap asphalt. The
situation has changed dramatically and the economics for EPDM
sheeting are now much more favorable. The formulation suggested
for this application is based on a polymer that offers good physical

T~Mp 6. Fluid
~MM/ storage,
~on~c, water ~ea~en~ tanks,
M~r treatment ~on~
Table
wall and foundation waterproofing, ,~l’ashing and
expansion joint covers.

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 27

properties when fairly highly extended, good green strength and good
calendering. The filler loading is designed to provide good pro-
cessability and reinforcement to meet the required tensile and tear
strength properties. Because of long term aging conditions, a low
volatility, paraffinic oil and a sulfur donor, low sulfur cure system are
employed. Since the application involves making lap seam splices in
the field, the cured compound is non-blooming to facilitate adhesion.
Test data show the green strength, cured physical properties, heat,
water and ozone resistance, characteristics required for good perfor-
mace in the roof sheeting application.
When EPDM was introduced as a commercial polymer, the
automotive industry was quick to recognize areas where part perfor-
mance could be improved by its use. Major uses have included sponge
and dense weatherstripping for doors, windows and trunk lids.

Table 7. Physical Properties.

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Radiator and heater hoses, air emission hoses, and various tubing
specifications have required EPDM. Brake components, including
boots, diaphragms, seals and cups utilize high quality EPDM com-
pounds. In addition, many gromments, isolators, mounts and other
suspension parts have been used.
A typical radiator hose compound is based on a blend of polymers
in which the major portion is high ethylene type, which offers high
green strength for desired shape retention. The use of the small
amount of a lower ethylene type is to assure oil compatibility. The car-
bon blacks provide the desired smooth extrudates and the modest
physical properties required. Ground whiting is incorporated to lower
the cost. A non-volatile oil is necessary to meet the heat resistance re-
quired. The cure system is chosen to provide an acceptable rate of
cure, and to meet the specification requirements for heat resistance,
compresion set and coolant resistance. Satisfactory performance at a
reasonable cost is provided for the radiator hose application.
A master cylinder reservoir seal typifies an automotive brake com-
ponent where outstanding performance is a necessity (Table 10). The
compound for this application employs a low molecular weight

Table 8. Radiator Hose

Compound.

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Table 9. Radiator Hose.

polymer with an E/P ratio near 50/50 to provide good processability.

Shrinkage of the seal due to extraction of plasticizer by brake fluid is
undesirable. Therefore, the level of oil must be kept to a minimum,
which in turn limits the level of carbon black. The combination of
dicumyl peroxide and the coagent, trimethylol propane trimethacrylate
imparts excellent heat resistance and very low compression set. A
relatively high cost EPDM compound is needed to assure adequate
performance in this part.
To illustrate the extreme extent to which some EPDM polymers can

Table 10. Master Cylinder Reservoir SeaL

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30

Table 11. Highly Extended, Low Cost Com-

pound.

Specific Gravity
Royalene 400
D. High molecular weight
Royalene 622
A. E/P 75/25 100 RHC/40 naphthenic oil
Unaged Physical Properties 30’ @ 160 °C Cure 8’ @ 182 °C Cure

be extended and still be practical for some uses, a formulation for a

low cost extrusion compound is used (Table 11). A blend of a high
molecular weight and a high ethylene, oil extended polymer, is chosen
to provide the desired processability. The oil extended types facilitate
mixing. This compound can be used for low cost hoses, tubing or
weatherstripping. Its green strength is adequate for shape retention
unless the profile is extremely intricate or delicate. The total oil con-
tent, including the oil present with the polymers plus that added during

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compounding, is 220 phr. The oil combined with the high loading of
carbon black and ground whiting provides the low cost. Even at this
level of extension, the compound has excellent resistance to ozone,
the essential performance requirements for the intended applications.
There are many additional applications for EPDM polymers. EPDM
is a very effective non-staining, non-migrating antiozonant which has
been in almost all white sidewall tires for the past 14 to 15 years. As a
replacement for part of the conventional sidewall rubber (NR, SBR,
etc.) used in white sidewalls, EPDM imparts a marked improvement in
cracking resistance. When used in this way, EPDM may represent 15
Table 12. Applications for EPDM.

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32

to 30 percent of the polymer blend, depending upon the type EPDM

and other polymers used. This use, in blends, has not been restricted
to tires.
Although EPDM polymers do not possess the excellent low air
permeability of butyl rubber, they are being used at fairly low levels (5
to 20 percent) in inner tubes to improve low temperature properties, as
well as aging and processing characteristics.
EPDM compounds have found wide use in appliance applications
such as inlet and drain hoses, boots, seals and mounts.
There are numerous uses in building and construction, e.g. glass
sealers, curtain wall gaskets and tapes. Pond and ditch liners have
been installed in areas where water conservation is important.
Agricultural equipment also utilizes EPDM compounds in hoses,
seed tubes and as cushioning over metal parts on some types of
harvesting equipment.
Where resistance to certain fluids is necessary, EPDM compounds
are used as tank linings.
The use of EPM and EPDM in wire and cable is now well established.
A wide variety of extruded and molded mechanical goods is also made
from EPDM. Some examples are dock fenders, belting, gaskets, seals,
o-rings, faucet washers, etc. EPDM finds some use also in roll cover-
ings.
In summary, EPDM polymers are very useful in making compounds
with varying levels of quality which are being used in almost all in-
dustries. Of course, it is not the universal polymer. It is the com-
pounder’s responsibility to recognize the polymer’s capabilities and to
enhance them within the confines of cost and processability to meet
the customer’s performance requirements.

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