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PROLOGUE

Dear Friends and Colleagues:

We want to express our gratitude to those who are collaborating with

Cauchotechnology, as in this case with Eng. Ricardo Leone who has prepared the topic
of EPDM, rubber that is currently becoming one of the favorites due to
its qualities and features.

We can proudly face this series of booklets when we see that the list
The number of topics continues to grow, as do the candidates to carry them out.

We also submit for your consideration, our readers, that in the case of
need topics that they believe should be included in this encyclopedia, such as those that
if you find them necessary to be expanded, please be kind enough to let us know.

ENG. EDUARDO KNOX

Technical-Business Commission

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 Eng. Ricardo Leone

Ricardo Leonenació was born in Montevideo, Eastern Republic of Uruguay on August 16

in 1947. He graduated as a Chemical Engineer from the Faculty of Chemistry at the University
from the Republic of Uruguay in the year 1974. He has completed specialization courses
en caucho y en normativa de calidad.

His professional activity has been divided between teaching activities at the University of the
Republic and as a rubber technician.

As a rubber technician, he has worked since 1972 in various companies in Uruguay.

within them, it has ventured into the following topics: reconstruction of
tires, production of molded parts for industrial and automotive use,
manufacturing of rubber and EVA footwear items, roller coating,
manufacturing of extruded parts and production of pipes for automotive use. In the
Currently, he is a technical advisor for several rubber companies.

As a teacher, he has served as an Associate Professor of Physics, in the

Faculty of Chemistry, teaching courses in Newtonian Mechanics, Optics and
Hydrodynamics. At the same faculty, a course on polymers is currently being taught.
As a complement to his teaching tasks, he conducts research in Physics of
Colloids, having published numerous articles on that topic in physics journals
international. He currently works as a faculty delegate to the Cloister of
Faculty of Chemistry, having also been a member of its Council
for eight years.

For six years, he has been working as a tire specialist auditor for
LATU Sistemas S.A. from Uruguay and the Automotive Quality Institute of Brazil
conducting audits of those manufacturers who aspire to sell their tires in
Uruguay or Brazil.

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 CONTENT

THE ETHYLENE-PROPYLENE RUBBERS (EPM AND EPDM)

Historical Background
2. Manufacturing Processes.
3. Types of Polymers and Properties.
4. Manufacturers
5. Relevant Properties
6. Formulation

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 ETHYLENE-PROPYLENE RUBBERS (EPM AND EPDM)

1. Historical Background.

If we position ourselves in the 1960s and study the situation of the

elastomers we see that at that moment in the market existed as rubbers of
affordable price natural rubber (NR), styrene-butadiene (SBR), polyacrylonitrile-
styrene (NBR), polybutadiene (BR), polyisobutylene-isoprene (IIR) and polychloroprene
Among all of them, there was a wide range of properties regarding
good mechanical properties (NR and CR), good abrasion resistance (SBR and BR)
very good resistance to hydrocarbons (NBR) and regarding resistance to agents
Atmospheric and ozone appear useful in CR and IIR.
Despite this, this last sector of properties is only partially
covered since the polychloroprene only acquires resistance properties to
ozone and atmospheric agents when properly added and still the
protection is not completely satisfactory, and it is compounded by the fact that the cost is high due to
various reasons: high price of the polymer, high density (1230 kg/m3) and absorption of
relatively low loads. The other option, namely polyisobutylene-isoprene rubber
(butylic), while it has good aging properties it has a limited range
Of hardness and processability is often not straightforward.
For all those reasons, a rubber was being sought at that moment.
economic, with good resistance to ozone and weathering. The search started with a
saturated monomer like ethylene (ethene) which had been used for a long time,
being the base for a high crystallinity thermoplastic polymer (polyethylene). For
to achieve an elastomeric behavior, the comonomer was introduced as
propylene (propene) in such a way that the random sequence between both monomers
it allowed reducing the crystallinity and for elastomeric behavior to appear.
this way the ethylene-propylene rubber is born, which from here on we will call EPT or }
EPM. During 1961, the producers start sending the first samples and from
It began to exist commercially in a normal way in 1963.
The resulting product has several interesting properties, for example its
low density (870 kg/m3), its high resistance to ozone and some properties
interesting for chemical resistance and high temperatures. The production process
it is simple, high performance, and the used monomers are common products and
economic in the petrochemical industry.
It also, of course, has disadvantages, of processing, of adhesion and,
especially, of vulcanization.
This last point is key, as the low crystallinity of the polymers means that
its unvulcanized mechanical properties are totally unsatisfactory, and as in
the chain has no double bonds it is impossible to vulcanize with sulfur and is
necessary reticular with peroxides. The peroxide bond is still used, but it has
various inconveniences, especially at that time when it was not known
coagents, which, currently, have contributed greatly to the improvement of that type of
reticulation.
The chemical formulas of the EPM are shown below, being the most
dark are the carbon atoms and the lighter ones are the hydrogen ones.

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 To overcome that difficulty, it is decided to introduce a diene into the molecule that
allow the presence of a double bond in the polymer and thus make it possible to
reticulation through sulfur, at the same time it is necessary to maintain strength
chemistry of the polymer's main chain while maintaining its paraffinic character. This
it is achieved by ensuring that the double bonds are not in the main chain, but rather that
they are part of vulcanizable lateral groups with sulfur. In this way, the
EPDM thermomonomer.
The thermoset to be used must have two double bonds in such a way that one of
They open to join the chain while the other remains intact to be
later vulcanized. The employed dienes have been changing over time.
time, initially it was dicyclopentadiene, then 5 ethylene 2 norbornene and in cases
1,4-hexadiene has rarely been used.

Dicyclopentadiene 5 ethylene 2 norbornene

1,4 Hexadiene

Below we show, as an example, the chemical structure of an EPDM.

which uses 5-ethyl-2-norbornene as a termonomer and how its arrangement results
spatial.

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 The polymer obtained in this way has the desired properties but
Additionally, other remarkably useful properties appear.
derivatives of their structure, for example:
• The high molecular weight obtained through polymerization mechanisms.
used, and consequently the great length of the chains allows for a high
acceptance of loads and consequently an economical rubber compound.
• The saturated skeleton not only produces an elastomer with great
resistance to attack by oxygen and ozone, but it is also very good at its
resistance to high temperatures.
• The amorphous molecular structure allows for its elastomeric behavior
remains even at low temperatures.
• Non-polar structure provides excellent electrical properties, such as low
electrical conductivity and high dielectric strength.

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 2. Manufacturing Processes.

Basically, there are three commercially important production processes, all

they are based on a stereospecific polymerization achieved on the basis of
catalysts of the type developed by Ziegler and Natta in the 1950s.
Esos tres procesos son: en solución, en suspensión y en fase gaseosa.
a. In the solution process, the two monomers, ethylene and propylene are
positions in solution together with the catalyst in a solvent that can
to be a hydrocarbon or a chlorinated hydrocarbon, after finishing the
polymerization (and having added oils or antioxidants if applicable
necessary) the solvent and unreacted monomers are removed by
hot water or steam or distillation. A product is obtained in the form of
of crumbs which, if it is sufficiently clear, can be handled
as such or if it is very amorphous it compacts and is handled only
like bales. This degree of crystallinity is controlled by the type
de polimerización, cuanto más al azar resulta la distribución de los
the more amorphous monomers is the polymer obtained.
In the suspension process, the procedure is the same as in the previous one but
propylene itself is used as a solvent, as the monomers are
soluble in it, but not the polymer which, as it goes on
forming a fall like a suspension. The greatest advantage of this
the process consists in that the molecular weight is not limited by the
viscosity values of the solution as it occurs in the process
previously, furthermore the handling of solvents is not necessary.
c. Gas phase polymerization (of which the most successful one uses)
metalocenes as catalysts) consists of introducing the monomers
and catalyst along with nitrogen in a reactor where the production occurs
polymerization and the formed polymer is extracted periodically. This
the method has the advantage of not using any solvent, the separation is
very simple, very high molecular weights are obtained and the polymer
it is marketed in the form of powder or grains facilitating mixing.

3. Types of Polymers and Properties.

The described manufacturing processes lead to polymers that, although

they contain the same monomers can differ greatly in terms of their
micro and macro structural characteristics, making it necessary to have methods
of tests accessible to the rubber technician in order to characterize the polymer and,
In this way, predict their behavior after processing or during the process.
The relevant properties whose measurement is important directly or
indirectly they are the following.

Mooney viscosity
Ethylen content
Type of day
Content of diene
Extension with oil
Molecular weight and distribution.

• Mooney viscosity.

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 This property is one of the favorites for the rubber technician, as
Normally, the Mooney viscometer is part of the standard equipment in a
rubber laboratory.
Normally, the determination is carried out using the large rotor and with a
preheating for 1 minute, in some cases taking the measurement at 4 minutes
(ML 1 + 4), and in other cases at 8 minutes (ML 1 + 8), for that reason it must be taken into account
be careful with those parameters when comparing data from different providers. In
as for the temperature of the test, it can change, since while some
suppliers prefer a fixed value (for example 1250C) others change the temperature
of essay since 1000a 1500 C depending on the 'rigidity' of the polymer.
The viscosity values are linked to the molecular weight of the polymer as follows.
as well as the microstructure of it. If we use temperature as the only reference
of 1250And an ML 1 + 4 type test, viscosity normally varies from 20 to
140, but it can range from 5 to 200.

• Ethylene content (or ethylene/propylene ratio).

The average ratios of monomers are 55% ethylene and 45%

propylene, but that relationship can be modified with profound effects on the
properties of the compound and its processing. In general, increase the content of
ethylene increases the thermoplasticity of the material enhancing the physical properties to
ambient temperature but decreasing the resistance to low temperature and
increasing the permanent deformation.
The normal values of ethylene range between 45 and 80%, and its influence on
increase in the properties appears in the following table:

Positive Influence Negative Influence

Lower Stickiness in Mill Worse adhesion
Lower Swelling in Extrusion Inferior resistance to low temperatures
Better Surface for Extruding Greater deformation due to compression
Greater resistance in crude Lower elasticity.
Acceptance of higher levels of slower mixing.
load.
Less slippage in the feeding More difficult calendering
of extruders and injectors
Greater Breaking Tension
Higher value of Tear
Better abrasion resistance
Better resistance to high temperatures
Higher cross-linking density in cures
peroxide

• Type of day.

Currently, ethylene norbornene is used almost exclusively, although it is still

Some manufacturers use diciclopentadiene in slowly vulcanized EPDM because
it has good weather resistance properties and compatibility with polyolefins
thermoplastics (TPO) in peroxide curing systems.

• Content of diene.

The normal value of diene (in this case norbornene) is 4 to 5%, but it varies.
widely between 0% (EPM) to 9% in the fastest types (and even 15% in cases
exceptional). The content of norbornene significantly affects many

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properties of the compound in its processing and in the final use The increase of
Diene content influences as shown in the table below:

Positive Influence Negative Influence

Lower deformation due to compression Tendency to prevulcanization
Faster healing speed Lower resistance to high temperatures
Compatibility with unsaturated rubber Difficulty in obtaining low hardness.
Versatility in acceleration
High Modules

• Molecular Weight.

This magnitude is of enormous importance in polymers but in the case of

the EPDM is fundamental as it can vary within very wide limits,
as evidenced by the viscosity values (so linked to the molecular weight) that
they usually range from 20 to 140 (ML 1+4 to 1250C) or exceptionally from 5 to
200.
The influence of the increase in molecular weight is presented in the table.
next:

Positive Influence Negative Influence

Módulo, desgarre, Tensión de ruptura Lower mixing speed
Capacity to absorb loads Lower extrusion speed
Good resistance in raw. Does it worsen when calendering?

Good resistance to collapse in Pre-vulcanization resistance

extrusion

• Molecular Weight Distribution

By being polymers produced through stereospecific catalysts, they

You can adjust not only the molecular weight but also the distribution of it.
Is it narrow or wide?
When the molecular weight distribution is broad, we have the following
influence on properties and processing:

Positive Influence Negative Influence

Surface roughness of extrusion Greater swelling in extrusion
Resistance to collapse Lower Extrusion Speed
Well mixed in the mill. Poor healing status
Good calendering Minor Physical Properties

• Clarity.

As we have said, the crystallinity of polymers can be varied by means of the

selection of the sequence in which the monomers that constitute the
chain, that is ethylene and propylene. When the sequence is random, the polymer is
amorphous but can become semicrystalline making ethylene and propylene
they form blocks. In any case, very crystalline polymers are never obtained, due to
Thus, the compound does not exhibit high values of mechanical properties unless
that reinforcement loads are used.

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 Despite this, in some cases, block polymers are obtained that
through the addition of reinforcement charges, they can be used in articles
specials without vulcanizing them.
The following formulation shows the properties that can be obtained from
a non-vulcanized product using rubber with that structure:

Material/Property Cantidad/Valor
EPDM A 100
High Density Polyethylene 25
Naphthenic Oil 25
Mixture of kaolin and quartz 150
Smoke Black N 770 60
Help Process 5

Tensile Strength at 200C 7.3 MPa

Break elongation at 200C 440%
Hardness at 200C 88 Shore A

• Physical Form.

The great variation in molecular weight allows for obtaining liquid polymers.
(that can function as crosslinkable and non-extractable plasticizers) up to polymers
in powder with high molecular weight.
Most of the EPDM is marketed in the form of bales but still within
from it can be crumbly crumbs with high absorption speed of
oils and loads, or compact types for mixing, especially in a mill
open.

Conclusions

As can be inferred from the above on one hand the possibilities of

the selection of polymer options is very broad and if the formulator knows how to take advantage of them, they can
obtain excellent results, on the other hand if they are unaware of it they may face many challenges
problems in processing and in the final article. At the same time, this makes it difficult
talk about equivalent types between different manufacturers.
The above shows a huge importance of the chosen polymer in the
process, such that even for the same use of the final product there is no
"better rubber." For example, to obtain excellent physical properties, a factory
that has an internal mixer can use a high molecular weight polymer
with a narrow distribution of it, using high levels of carbon black and oil,
while if the Company has to mix in an open mill to achieve
equivalent properties will have to use a polymer with weight distribution
wider molecular and to compensate for the lower physical properties it must use
a lower level of loads and consequently accept a higher cost of materials
cousins.

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 4. Manufacturers.

The main producers worldwide are the following, with their

corresponding registered trademarks:

Producer Brand
Lanxess (formerly Bayer) Hello AP
Crompton/Uniroyal Royalene
Exxon Mobil Vistalon
DSM Kelton
Dupont Dow Nordel
JSR EPDM
Kumho KEP
Polymers Europe Dutral Ter

5. Relevant Properties

The properties of pure polymer vary greatly depending on the

composition and structure of it, for that reason some of the properties
The values indicated in the following table are given by their extreme values.

Property Values Units

Density 855 - 880 kg/m3
Viscosity Money 5 - 200 ML 1 + 4 @ 1250C
Ethylene Content 45 - 80 %
Content of Dieno no 0 - 15 %
Conjugated
Solubility Parameter 7.9 a 8.2
Specific Heat 2.22 J/kg.K
Thermal conductivity 1755 kW/m.K
Expansion coefficient 2.5 x 10-4 (0C)-1
linear thermal
0
Transition Temperature -40 to -60 C
Vitreous

Although in the compound formulated with fillers, plasticizers, accelerators, etc.

Is it possible to obtain specific property values using formulations?
appropriate, we provide the following in the table below, for guidance purposes, the
properties achievable in a compound.

Property Values Units

Hardness 30 - 90 Shore A
Breaking Tension, max. 20 MPa
Breaking Elongation, max. 900 %
Tear Stress Given B, max. 55000 N/m
Deformation by Compression 45 % (vulcanized with
ASTM D395B sulfur

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 24 h @ 1500C 10 % (vulcanized with
peroxide
Resilience Yerzley at 230C 77 %
Air permeability 8.6 x 10-11 [Link]
Dielectric Constant 3
Power Factor 0.25
Dielectric Strength 26 kV/mm
Volumetric Resistivity 1 x 1016 Ohm-cm
Flame resistance Poor
Resistance to the environment: Environment Excellent
Resistance to the environment: Oxidation Excellent
Resistance to the environment: Radiation Excellent
Resistance to the environment: Water Excellent
Resistance to the environment: Ozone Excellent
Resistance to Hydrocarbons Poor
Resistance to Oxygenated Solvents Excellent
Resistance to diluted acids and bases Excellent

6. Formulation

To present the topic of formulation, it is necessary to distinguish between those products

those who actively participate in the vulcanization process and those who do not.
In any case, in both instances there is a very strong interrelation of the
ingredients to use with the type of polymer in terms of molecular weight, ratio
ethylene/propylene and amount and type of diene.

• Fillers and Plasticizers:

The scarce or nonexistent translucency of the polymer makes the use of

loads since otherwise acceptable values of the ...
mechanical properties.
All types of loads are used, as happens in others.
rubbers, but the carbon blacks are of particular importance.
What is particularly interesting is the amount of loads to
employ, since their values can be so high that the
polymer is, in some cases, only 15% of the total weight of
composed.
Almost exclusively, oils are used as plasticizers.
oil, these can be paraffinic or naphthenic types, since the
aromatics are not very compatible with EPDM. That choice remains more
limited when the acceleration is based on peroxides, as to avoid the
For peroxide consumption, only paraffinic oils should be used.
Regarding the viscosity of the oil to be used, it is chosen according to
the terms of use and cost. For example, to vulcanize at temperatures
In pressureless systems, very high viscosity oils are used.
trying to take advantage of the lower volatility at high temperatures, normally
associated with high molecular weight.
For light-colored articles, the use of is also recommended.
paraffin oils due to their less color change in front of ultraviolet.

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 The combination of black smoke-paraffinic oil allows the formulator
adjust within broad margins the properties of the compound and the
process parameters.
To exemplify the above, the following graphs are presented, where
contour lines are shown for different properties as a function of the level of
black of smoke and oil. They have been selected to show the behavior
three black smoke: one highly reinforcing (N 347), another semi-reinforcing (N
660) and finally one of large particle and very little reinforcing (N 990).
As properties, some that exemplify properties have been chosen.
mechanical properties (hardness, tensile strength, elongation at break, tearing and
deformation by compression) and other processability (Mooney viscosity,
swelling and extrusion appearance.

Tensión de Ruptura ASTM D 412 Matriz C (MPa)

Break Elongation ASTM D 412 D C (%)

Shore A Hardness

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Tear ASTM D 624 C. (N/mm)

Permanent Deformation by Compression ASTM D 395 Method B 22 h @ 1000C

(%)

Mooney viscosity ML 1+4 @ 1000C

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 Swelling in Extrusion (%)

Appearance in the Extrusion ASTM 2230

For non-black articles, silicon dioxide is used as a reinforcing filler.

precipitate, as semi-reinforcing kaolins or as extender calcium carbonates
in its various forms (ground, precipitated, diatomaceous earth, etc.), just like
it occurs with the most common tires.
The reinforcing capability of silica strongly depends on its surface.
specific, which ranges from 200 m2/g a 30 m2/g. For molded pieces where it
Good mechanical properties are sought, high specific surface silica is used.
in relatively low doses, but this is achieved at the cost of processability
especially regarding extrusion. Silica is used for extruded articles with
low specific surface area in high doses (150 phr) allowing for smooth extrusions with
under swelling. Sometimes similar results can be achieved through the
combination of very active silicates with precipitated and/or treated calcium carbonates
on the surface.
If the mechanical demands are not so high, kaolins can be used.
reinforcers or less reinforcers. Exclusive use of inert loads is not possible.
as calcium and/or magnesium carbonates since the low crystallinity of the polymer makes
the existence of a reinforcing load is necessary.
Below are some graphs showing the evolution of
a specific property based on the amount of load measured in parts per 100
of elastomers, for different loads. The formulation used is of a cured EPDM.
quick vulcanization with sulfur and without the addition of oil.

Mooney viscosity Tensile Strength (MPa)

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 ML 1+4 to 1000C

Compression Deformation (%) Shore Hardness

ASTM D 395 Method B 22 h @ 1000C

The used loads are indicated by code, but their physical nature
Chemistry is indicated in the table below.

Code Composition
A Wet processed calcium carbonate
B Natural calcium carbonate from sediments
sailors
C Precipitated coated calcium carbonate
D Reinforcing kaolin
E Soft Kaolin
F Micronized talc
G Precipitated silica particleφ 0.08 micrones
H Precipitated sodium aluminosilicate
J Precipitated silica particleφ 0.022 microns

The best values of mechanical properties with clear loads are obtained
when the coupling agents between the polymer and the white filler are incorporated.
These agents are the known silanes. The selection of them must be made
taking into account whether the vulcanization is done with peroxides or with sulfur. A good
the selection of the same allows achieving a breaking tension of 20 MPa, losses
for abrasion DIN of 115 mm3and permanent deformations due to compression of 22

17
hours at 700C at 13%, which are excellent values, comparable to those obtainable
with black smoke.
The great resistance to oxidation of EPDM rubbers allows obtaining
continuous light color extrusions, vulcanizing by hot air and using dioxide
titanium as a whitener without noticeable yellowing.
The dosage rule for loads is that to achieve good extrusion it is
it is necessary to use high levels of loads along with high levels of plasticizers, this
naturally results in a decrease in physical properties.
The load absorption capacity strongly depends on the type of
used polymer, those polymers with higher molecular weight and more distribution
narrow of the same can take greater load levels without the occurrence of a
significant decrease in its physical properties.

• Vulcanization Systems.

Since its inception, the weak point of EPDM has been its vulcanization, which is why the
EPDM vulcanization systems have evolved over time.
For this reason, a historical development will be carried out to understand it.
acceleration theme.
The first EPM or EPT polymers that did not contain and do not contain dienes,
they must be vulcanized exclusively with peroxides, we will return to
the topic of vulcanization with peroxides later.
The first polymers that appear with an incorporated diene use the
dicyclopentadiene and are referred to as 'normal curing', indicating that
they vulcanize with sulfur slowly and develop low modulus values. For
obtaining reasonable mechanical properties and curing speeds was necessary
the use of very large amounts of accelerants led to
expensive compounds and, especially, the use of high levels of accelerators which
gave rise to migrations of the same or their byproducts after the
vulcanized. To circumvent the second problem, several types are used.
accelerators in the way of obtaining the total amounts but never exceeding
the solubility limits of any individual accelerator.
Naturally, vulcanization with low sulfur or with donors of the same.
it is very difficult, which indirectly limits the maximum temperature of
service of the article.
The other drawback, and not a minor one, is that if it is intentionally mixed or
accidentally with unsaturated rubbers (such as SBR, NR, etc.) in the competition
due to the vulcanization accelerators, they are mostly used by
the other rubbers leaving the EPDM as an unvulcanized phase, in others
both terms rubber are incompatible with each other.

The cure with Sulfur

The following are discussed some of the dosages of

accelerants used along with usage comments for each of them:

Amount in Weight
Standard Plus High Good
Material d Quick Temperature Deformation
a for
Compression

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Polymer 100 100 100 100
Smoke Black N 550 75 75 75 75
Paraffin Oil 25 25 25 25
Zinc Oxide 5 5 10 5
Stearic Acid 1 1 1 1
Sulfur 1.5 1.5 0.5
MBT 1.5 1.5 3.0 0.5
TMTD 0.8 0.8 0.8 1.0
TeDEDC 0.8 0.8 1.0
ZnDBDC 1.5 1.5
NiDMDC 2.0
DTDM 0.8 1.0

The introduction of norbornene as an unconjugated diene increased

substantially the vulcanization speed appearing the "quick cure" types
in which the level of norbornene was around 4%. Subsequently the
an increase of the amount of norbornene to 8% or more resulted in an even greater increase
greater in the healing speed leading to types of 'very fast healing'. The
The figure below shows the evolution of the rheometric curves for the
grade changes compared to a curing curve of an SBR. The
used formulations were:

Material Amount in Weight

Polymer (SBR or EPDM). 100.00
Zinc Oxide 5.00
Stearic Acid 0.50
Black N 550 70.00
Naphthenic Oil 60.00
TBBS 1.00
DPG 0.40
Sulfur 2.50

And the reograms obtained with arc 30and temperature 1700What are the following:

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 These changes in the polymer make it possible to substantially modify the
acceleration systems, making the use of sulfur donors viable. At the same
time the curves the vulcanization results are similar to those of rubbers
unsaturated allowing the co-vulcanization of both, in such a way that it is made
much more flexible the formulation.
The following table shows some formulations that exemplify it
said before.

Amount in Weight phr

Use More High Good
general Quick Temperature Deformation
Material
in by
Compression
n
Polymer 100 100 100 100
Smoke Black N 550 200 200 200 200
Paraffin Oil 120 120 120 120
Zinc Oxide 5 5 5 5
Stearic Acid 1 1 1 1
Sulfur 1.5 1.5 0.5
TBBS 1.2 1.2
MBT 1.5
TMTD 0.7 0.8 0.8 0.7
ZnDBDC 0.7 2.0 0.7
DTDM 2.0 2.0
DPTTHS 0.8 0.8
TeDEDC 0.8

In all cases, the addition of zinc oxide and acid is advisable.

stearic usually 5 / 1 for 100 parts of rubber.
Given that in its early days one of the problems associated with EPDM was its
vulcanization special accelerators have been developed, which have then been
maintained even when the types of EPDM of 'cure' have appeared in the market
quick
Among them, the copper dialkyl dithiophosphate stands out for its importance.
diethyl dithiocarbamate of tellurium which when used in doses of 0.5 to 0.8 phr
they significantly improve the curing state, reduce the vulcanization time, and,
especially, they improve the deformation under compression. It is also important
the system based on Zinc O,O-Dibutyl phosphorodithiolate. It was developed for
avoid the use of accelerants that produce nitrosamines, but has found
application in EPDM for providing good pre-vulcanization time values, high
cure speed and good mechanical properties. For example, it is used in a
system of this type:

Accelerant Amount phr

- 20 -
 ZBPD 2.70
TMTD 1.00
TBBS 2.00
Sulfur 1.00

The treatment with peroxides.

In the case of EPM copolymers, curing must be done with peroxides.

that there are no double bonds to which sulfur can bond, but in some
cases using terpolymers are vulcanized with peroxides to optimize some
properties such as resistance to high temperatures or permanent deformation due to
compression.
The following are used as peroxides:

Chemical Name Dose phr Temperature

Decomposition0C)

2,5-dimethyl-2,5-ditert-butyl
1.5 190
peroxy hexine

2,5-dimethyl-2,5-di-tert-butyl
1.5 180
hexano peroxide

1,3-bis(t-butyl peroxide
1.7 180
diisopropyl benzene

Dicumyl peroxide 2.7 170

3,3-bis(tertiary butyl peroxide)

butanoic-n-butyl 3.4 160
ester
1,1-bis(tert-butylperoxy)-
3.0 150
3,3,5-trimethylcyclohexane

As can be seen from the previous table, the differences between them lie in the
dosing and in the temperature of activity.
The most commonly used are dicumyl peroxide and 1,3-bis(tert-butyl peroxide.
diisopropyl benzene.
Vulcanization with peroxides presents difficulties, first of all the curve
The devulcanization shows a slow growth module that is hardly modifiable in
second place is very sensitive to the presence of substances that may react
with peroxide and consequently using it for purposes that compete with vulcanization
In that way, there are ingredients that should not be used, such as oils.
saturated and most antioxidants (one exception is TMQ).
Peroxides hardly allow for a complete development of the module and it is
it is necessary to use substances that increase its values, these are the
called coagulants. For the case of EPDM, the simplest coagulant is sulfur
in doses that are around 0.3 phr. Although sulfur is a very effective co-agent.
cash, has the drawback that the byproducts generated in the reaction have
a very unpleasant smell, which is why it has been replaced by other types of products
more specific.

21
 There are countless coagents ranging from the simplest ones like the already
cited sulfur to others highly sophisticated. Below we present a table
with coagents commonly used.

Chemical Name dose phr

Sulfur 0.30
Ethylene glycol dimethacrylate (EDMA) 1.00
Trimethylol propane trimethacrylate (TRIM) 1.50
Trialil cianurate (TAC) 1.50
N,N'-m-phenylenedimaleimide (HVA 2) 1.20
1,2 cis polybutadiene 5.00
Triallyl isocyanate (TAIC) 3.00

The above is naturally just a brief summary as the possibilities

Peroxides and coagulants merit a study in their own right.
Curing systems with peroxide are difficult to delay, although in some
cases yield the inclusion of 2,6 ditertiary butyl 4-methyl phenol.
The addition of zinc oxide and stearic acid is not necessary although
Zinc oxide is usually added because it improves resistance to high temperatures.
temperatures, stearic acid does not help in terms of the curing system but its
incorporation functions as an internal lubricant, although it can absorb part of the
peroxide, in those cases it can be replaced by calcium stearate.

Cured with Resins

Although it is not commonly used, it should be mentioned that EPDM can also
vulcanizarse con resinas fenólicas reactivas en dosis de 15 phr combinadas con 4 phr
of chlorosulfonated polyethylene that acts as a coagulant.

• Protection Systems

The saturated nature of the main chain makes EPDM (and even more so the
EPM) are very resistant to ozone, for that reason the inclusion of anti-ozonants is not
it never happens. The situation regarding antioxidants is somewhat different.
use, especially when the compound will be exposed to high temperatures;
in those cases, vulcanization with peroxides is generally used
fundamentally the polymerized trimethyl quinoline (TMQ) since it does not consume
peroxide.

• Help process

The processability of EPDM polymers is very good, especially regarding

due to molding and extrusion, it is not common to use process aid.
In any case, in special situations, products like factice are used in the
extrusion to remove trapped air or to prevent the collapse of the profiles, no
despite them, the same effect is usually achieved through adequate
selection of the polymer.
In the case of complicated extrusions or injection molding, it is sometimes
it is necessary to resort to flow agents. They can be esters of fatty acids of high
molecular weight used in 2-4 phr; or calcium salts of fatty acids with
amides. In some cases when there are problems with the stickiness of the compound to
the cylinders of the mill or the paddles of the mixer the addition of an organosilane,
despite its high price, it delivers excellent results. Finally, in the case of the

22
Extrusion of low molecular weight polyethylene wax additives not only
it contributes to improving the extrusion speed but also enhances the surface finish
Homogenizing agents allow for compatibilization between elastomers.
with very different polarities to achieve combinations of properties
sophisticated, such as a mixture of acrylonitrile-butadiene with EPDM for
achieve resistance to oils and ozone.

• Sticky Agents

EPDM rubbers are characterized by very low tack in raw form (even
when its adhesion after vulcanization is very good). It can be improved somewhat
through the use of resins, although it is impossible to reach the values that are
are obtained with other rubbers such as natural or polychloroprene.
The recommended resins are of the non-reactive phenolic type. They do not
it is recommended to use rosin resins as their acidity generally interferes with the
vulcanized. The homogenizers produce an increase in stickiness, in case
For peroxide treatments, one should use the light-colored ones that do not consume peroxide.

• Sponges

Sponges can be obtained in sheets through a pre-curing system in

mold and subsequent curing in a hot air oven, which produces very
low density (up to 200 kg/m3) using relatively high doses (10 phr) of
azodicarbonamides, however those plates do not constitute the article
most important sponging for EPDM. As we will see later, the most
Important in the use of expanded EPDM are the extruded sponges.
For the selection of the foaming agent to be used in the extrusion sponges is
determine the treatment system to be used, as it determines the temperature
of the process.
In general, it is sought that they are of closed cell to ensure absorption.
the water should be minimal, for this organic foaming agents are used which can be of the type
of azodicarbonamides or p,p'-oxybis(benzenesulfonhydrazides) or dinitroso pentamethylen
tetramine.
The choice of product is determined by the process conditions as in
based on this, the expansion temperatures, the speed of it and the
amount of gas released, as this last aspect has economic importance. It must
It should be kept in mind that in this type of products, not only the composition matters.
chemistry of the same but the particle size plays a fundamental role in the
decomposition rate, also the decomposition temperature of those
product can be significantly reduced through the use of additives (kickers)
notable among which are urea, glycols, zinc oxide, etc.
Another factor to consider in the design of free sponge formulations
expansion is that the growth of the module during vulcanization must correspond to the
evolution speed of the gas, since if the vulcanization is too slow, it runs the risk of
risk of losing the gas before it hardens or if it is too fast it may happen that the
pressure generated by the gas does not succeed in overcoming the rigidity of the material. For the same reasons
reasons the viscosity of the mixture becomes critical, all of which makes the formulation
the spongy products and their reproducibility are delicate topics.
The other important case in the expansion of EPDM or EPM appears when
the polymer is used as a modifier of the properties of EVA in sheets for
shoe soles, there they almost exclusively use azodicarbonamides
activated.

23
 • Electrical properties.

The low electrical conductivity and high dielectric rigidity make the EPM and
EPDM finds important uses in everything related to electrical insulation.
combined with high resistance to weather and high temperatures. In general in
these cases use peroxides as vulcanizing agents with or without coagents, since the
sulfur could react with the copper of the cable.
EPDM has found an important application sector in insulators.
high voltage replacing traditional glass ones that are very fragile and that
are easily damaged by vandalism, with serious consequences for the
community.
Nevertheless, EPDM can be formulated by the addition of
smoke black to achieve resistivity values as low as 18 ohm-cm if one
they use highly conductive smoke blacks like N 472. Without resorting to blacks of
special fumes can obtain antistatic compounds through the use of
common smoke blacks like N 339 in high doses, on the order of 100 phr.

Various

Other additives are used in very specific applications, such as additives.

to reduce the flammability of the product whether chlorinated paraffins or oxides of
aluminum.

• Blends with Other Polymers

The mixture with other polymers greatly expands the range of

properties to be covered by a material, the slightly polar nature of EPDM and its
special characteristics of vulcanization make it necessary to distinguish between two
types of mixtures: with polar polymers (generally elastomers) or with
nonpolar polymers (generally polyolefins).

You mix with Unsaturated Elastomers.

EPDM is mixed with unsaturated elastomers such as

styrene butadiene (SBR), natural rubber (NR), acrylonitrile butadiene
(NBR) or chloroprene (CR) with very different objectives.
When the majority rubber is EPDM if mixed with SBR
generally seeks to lower the price of the compound by sacrificing
resistance to ozone and other atmospheric agents, when mixed
With natural rubber, it is possible to aim to lower the price or also
improve mechanical properties, on the other hand when mixed with CR
or, especially, NBR attempts to improve resistance to hydrocarbons
sacrificing to some extent resistance to weathering and ozone.
Conversely, when EPDM is the minority rubber, it is used.
to increase in the corresponding rubber the resistance to the
exposed to the elements and especially to ozone, acting as an antioxidant.
no messing around, vulcanizing or not.
Regarding the obtaining of the mixture, we must take into account
it counts two different factors, the incompatibility due to difference
of polarities between the rubbers and the differences in behavior
in front of the vulcanization.

24
 The differences in polarity become very large in this case.
from NBR and CR, and to achieve a uniform mixture it is necessary
to resort to homogenizing resins, the differences in polarity with
natural rubber and SBR are much lower, and consequently can
avoid homogenizers, although they usually produce a
improvement in the properties.
The problems of the healing system depend on whether one chooses to
systems based on peroxides or based on sulfur. The systems based on
sulfur requires that the EPDM cure very quickly, that is to say with
high doses (≥ 8%) of norbornene as non-conjugated diene, in that
under conditions, there is no difference in vulcanization speed between the two.
elastomers.
When vulcanized using peroxides, it can be used
any type of EPDM or even EPM and there is no problem with
insaturation since it does not affect the curing speed with peroxides,
On the other hand, care should be taken with those substances that can
absorb peroxide as antioxidants, some black soot,
unsaturated resins or plasticizers (especially of the aromatic type).
In the case of reticulation with peroxide, it must be remembered that it cannot
use butyl (IIR) as a second elastomer since it does not vulcanize with
peroxides.

Mixes with Saturated Plastomers

If EPDM is the majority polymer, the polyolefin can

to participate or not in the vulcanization process. In the event that not
the participant generally refers to very low weight polyolefins
molecular whose function is to assist in the process of improvement
especially the surface and the extrusion speed of items
extruded.
For the polyolefin to participate in the curing process, it must
to be performed using peroxides and the function of the polyolefin is to increase
the hardness of the product, on the other hand, does not affect the viscosity in the
process conditions, since at those temperatures the polyolefin
it will be melted. As a polyolefin, low-density polyethylene is usually used.
density (LDPE).
The most interesting cases occur when the polymer
the majority is the polyolefin, in those cases it usually
reticulating, for which it is essential to do so with peroxides.
In those cases, a feel of the polyolefin is achieved.
"goma" ("rubber feeling") that can be important, fundamentally
for aesthetic reasons, in these cases, there is no attempt to improve resistance
ozone has chemical properties but only the deformation
permanent by compression.
In these cases, the EPDM will be vulcanized with peroxides and by
it is not so important if it is standard, fast, or very fast charge,
therefore for economic reasons it is normal to use EPM or EPDM with
dicyclopentadiene as a non-conjugated diene
An example of that use is the addition of 30 phr of EPDM (or
EPM) in expanded mixtures of ethylene-vinyl acetate (EVA) to be
used in sports shoe soles, where it improves flexibility,
resilience and abrasion
That mixture EVA-EPDM constitutes a alternative
economically very interesting compared to the EVA alternative
chlorinated polyethylene.

25
 7. Process

These polymers are very different from rubber in every way.

natural, therefore, as could be expected, the processing is governed by parameters
different, the reasons for these differences are basically due to the lack of
"nerve" of rubber, low stickiness, insensitivity to "chewing" and high levels of
loads and oils to be used.

a. Mixed
i. Internal Mixer

If the amounts of loads and oils are low (for example when the
the sum of both ingredients is less than the amount of polymer when mixed
In an internal mixer (for example, Banbury), the process is similar to that of the rubbers.
common, that is, the rubber is put at the beginning, immediately (1/2 minute
) the additives are added, half of the carbon black and half of the oil
(it makes no sense to leave the rubber working alone since it is not
chewable, that is to say, that the viscosity does not decrease due to the work
mechanical, as happens with the natural), and after 2 or 3 minutes the
rest of the charges and is unloaded at 6 minutes. This same process
modified must be used in compounds for sponge, where they are used
high amounts of plasticizers, for example, below we provide a
typical process of this last case.

Time Proceso
0' Rubber
½’ Zinc oxide, stearic acid, half black, accelerators
1 minute Half oil, half black
3' A quarter of oil, sulfur
4' A quarter of oil, leaveners
6’ Download. Temperature less than 1200C

If the polymer percentage is low, the use of the process is not viable.
conventional mixing since in the early stages the mixer remains very
empty. In those cases, the 'upside down' process is used in English or 'patas'
"upside" or "inverted" in Spanish.
It consists of first loading the carbon black into the Banbury and
oil to obtain a paste (along with the other additives) and to the medium
Add the polymer by mixing for up to four minutes, when it
produce the download. The condition to be able to apply this procedure is
that the amount of polymer is low and that the black/oil ratio allows
obtain a paste. The process is very simple, the mixing times are
40% lower than those of the conventional system, whereas the
dispersions are not as good as in the normal system and are not advisable
carry it out on mixtures that have active charges (for example black N 339).
Combinations of one system or another can be used according to the
needs of the compound.
Normally, the mixing of EPDM in Banbury is done in two
stages, that is to say that in a second step the accelerators are incorporated.

26
 The incorporation of accelerators can be done in the mill that is
find under the internal mixer, either in powder form or better yet
as concentrated pre-mixed accelerators in rubber. The other option is
carry out a second real stage, where the compound is heated again
in the internal mixer or open mill and the accelerators are added and
mix. In general, this system produces better dispersions than that of a
single stage.
Both tangential and the type are used as internal mixers.
interlocked, with somewhat better dispersion in these last ones but using
greater amount of energy for the same purposes.

ii. Mixed in Open Mill

When mixing in an open mill, it is essential to ensure that the cooling is maintained.
may the mill be as good as possible and that the cylinders can be brought quite close together
in such a way that the separation between them is very small. It starts by passing the
rubber with the gap between rollers adjusted between 1 and 2 millimeters and in
how much band shape begins to add the black smoke-oil mixture
like a paste. If the amounts of black and oil did not allow for the execution
one paste because one of them is much larger than the amount of the other
add both in small alternating amounts over the bite of the
mill. As the load is absorbed, it can be gradually increased
separation between rollers, finally the accelerators, sulfur and
other additives. It is common for the partially mixed compound to be overdone.
With the quick roller, this can usually be avoided by heating.
quite a bit more the rear roller than the front one, but normally not
it constitutes a very serious problem.
The following is a typical specification for milling mixing.
from a compound of EPDM with 180 parts of carbon black and 100 of oil
paraffinic.

0’ Load rubber and pass it through the mill bite to form a band.
2’ 00” Add zinc oxide and stearic acid. Cut to help penetrate.
sweep the tray and add the sweeping
4' Put black smoke in the tray and add the oil on top and mix.
until obtaining a paste
Start adding that paste onto the rubber.
10' Take out a reserve to leave a small bank, enlarge the gauge a bit if necessary.
It is possible to add the previous dough. As the bank grows, increase.
more the caliber. When it is hard to penetrate, take out a large reserve and replenish with the
reserve that was left out.
24' 00'' Thoroughly mix the tray and finish incorporating the black and oil.
28' 00'' On the rubber that is on the roller, add the sulfur, let it incorporate,
sweep and add the sweeping.
30' 00'' Remove all the rubber with the sulfur, load the reserve that was outside and
add accelerators, sweep and add sweeping.
32' 00'' Load the reserve. Bring everything down.
34' 00'' Cut twice on each side wrapping diagonally.
37' 00'' Pass three times at the tip.
38' 00'' Cut into sheets.
40' 00'' Finish.

27
 When the arrangement of ethylene and propylene units is not random
but they are arranged in blocks, the polymers obtained in this way have a 'nerve'
(that is, a resistance in crude) important, in those cases if the mixing is
Make with an internal mixer, it should be sought that its temperature is
find above 1500C. In the case of open mills, it is not
it is recommended to mix these polymers.
Cuando se procede a mezclar en molino abierto compuesto con cantidades
very large loads and plasticizers is convenient, in many cases,
start mixing on a container of the already mixed compound and continue adding
about the same black-oil paste and the polymer in an alternate form.
Regarding the weighing operation, prior to the mixing one.
It is carried out normally according to the automation of the installations.
existing. The only point to highlight is that if polymers are used in form
from dust obtained in gaseous phase, it is possible that said operation is carried out
completely automatically using the same management systems
powder used for the loads.

b. Quality Control of Mixtures.

Quality control through testing is usually sufficient.

rheometric, whether in rotor rheometers (ODR) or without rotor (MDR). In
in some cases, it is convenient to conduct some tests based on capillary rheometer for
determine some process properties that may be very important,
especially in the case of materials to be extruded.

c. Extrusion

Regarding extrusion, two aspects must be considered: on one hand,

own extrusion and secondly the vulcanization system.
The production system used for vulcanization is very important, since
if it is about hot air vulcanization, the use of is discarded
peroxide acceleration since air inactivates the peroxide and the extrudate
remains unvulcanized on the surface. Even when vulcanized with steam, it should
ensure the complete removal of air in the autoclave, through a good
air sweeping inside the autoclave. In the case of extrusion of very
complicated it is possible that air may remain in some areas of the profile, for
to avoid that difficulty, it is suggested to pass the profile through a paste made of 100.
parts of ammonium nitrate, 100 of water and 4 of a detergent, in that way
the extrusion is coated with a layer of ammonium nitrate which when
heating releases inert gases that are expelled the air that could exist
stuck.
In any case, the most important manufacturing processes for the
Profile production involves continuous vulcanization processes, whether
microwave, hot air, salt baths (for which peroxides can be used
since the air is excluded), fluidized bed or direct gas furnaces. In
for all of them, the vulcanization is at atmospheric pressure and this raises
conditioning factors to the type of polymer and composition of the mixture.
For that type of products, polymers with molecular weight are preferred.
high or very high, narrow distribution of it, thermomonomer content
high and of the norbornene type. The high molecular weight gives the compound a
better resistance to collapse, which is critical in many profiles. In some
it is necessary to resort to extended types with oil, in order to
take advantage of the high viscosity values of the base polymer. In all the
In cases, it is essential that the distribution of the diene be as homogeneous as possible.
possible

28
 For all non-pressure healing systems, the main problem is
eliminate the porosity of the product. Porosity may be due to air
trapped during the extrusion process or to volatiles generated when rising the
temperature.
One of the main sources of volatiles is: water vapor.
due to moisture in the raw materials, especially in the loads. For
to remove water vapor, products that are compounded are added
chemical compounds with water, the classic is the use of calcium oxide
dispersed in an inert medium (e.g. mineral oil), the dose to be used
varies between 2 and 15 phr depending on the moisture provided by the materials
primarily or due to the viscosity of the mixture, the lower the viscosity, the greater it is
the amount of calcium oxide necessary. Calcium oxide interferes with the
Healing system therefore needs to be kept to a minimum.
The other volatiles are mainly due to light fractions of the
used petroleum oils, therefore it is especially important in
mixtures with high plasticizer content use low plasticizers
volatility, which is generally associated with high viscosities.
The removal of trapped air is a more serious problem the smaller the
viscosity of the compound, since at high viscosity, air is expelled
mechanically, especially in feeding. This allows for
high hardness compounds (and consequently high viscosity) can
extruding in conventional cold extruders. When the viscosities are
the mechanical efforts are insufficient to expel the air and it
they must use extruders with degassing. An extruder with
degasification behaves like two extruders, the first from the inlet
the degassing zone is a cold extruder, while the part that
it behaves like an extruder from the vacuum zone to the outlet
hot; the degassing zone remains at high temperature for
promote the volatilization of those ingredients that produce gases (except
in the case of low viscosity compounds where heating is not possible
too much so that the viscosity does not decrease so much that the material comes out through
the vacuum intake). Below we present in tabular form the
temperatures in degrees Celsius to set in the extruder depending on the
desired hardness of the extrusion.

Hardness 25-55 Hardness 55-70 Hardness 70-95

Food Area 30 30 80
Area Before the Void 30 30 80
Void Zone 40 80 80
Area Behind the Void 60 50 80
Area Near the Head 80 60 90
Head 105 95 95
Matrix 105 105 105
Screw Cold Cold 80

The vulcanization temperatures will depend on the curing process.

employee but they range from 180 to 2400C, the great resistance to oxidation of the
EPDM makes it possible that even using those values the physical properties of the
products are not significantly affected, this is even more important in the
latest generation direct heating furnaces, in which the gases
from the combustion are introduced directly into the furnace producing
very high temperatures and very short vulcanization times.

29
 In the extrusion process, the loads (and within them the blacks of
Smoke acquires enormous importance because it not only determines the
physical properties of the product but are determining factors of the
swelling in the extrusion and the appearance of the extrudate (observe the
charts on page 12). In this regard, it is important to highlight the use of
special smoke blacks that provide excellent surface appearance to
profile.
When vulcanization is carried out with a preheating using
microwave, the non-polarity of EPDM makes it impossible to absorb energy from
the electromagnetic radiation, in that case must be introduced into the compound
polar materials that are responsible for absorbing microwave energy,
they can be polar rubbers like polychloroprene or polyethylene
chlorosulfonated.
The requirements for the compounds vary greatly depending on the hardness.
necessary, especially the extreme hardness issues.

i. Low Hardnesses.

In this case, it is necessary to resort to very high molecular weight polymers.

many cases extended with oil, to accept high levels of
plasticizers without the viscosity reaching very low values. To achieve
a good diet avoiding the slipping in the feeding mouth
it is advisable to use polymers with high ethylene content (sometimes
It also helps to sprinkle the material feed strip with silica.
precipitated). The vulcanization system must be as fast as possible to
so that the compound can vulcanize before having time to collapse, for that
It should be used as a measure the t.50reometric (bubble time) instead of t90
(optimal curing time). In many cases, it is important for the polymer to have
a high 'nerve' so that deformations in transport are minimized.
of the profile.

ii. High Hardness.

To achieve high hardness, polymers with very low are used.

viscosity, average ethylene content to have pre-vulcanization times
long. To achieve high hardness without an excessive increase in viscosity
the use of mixtures with polyethylene is extremely appealing, but in that
if necessary, vulcanize with peroxides so that both polymers are
reticulated, which has the problems we mentioned before.

d. Calendered

The EPDM are generally calendered in a simple form, forming sheets.

good appearance. The use of polymers with a distribution is recommended.
wide of the molecular weight.
If you want to obtain products with textile insertion, the process can be seen
difficulty due to the low stickiness of this type of polymers, in general
Phenolic type tacky resin additives work well.
If good adhesion to textiles is desired, the use of
specific adhesives, designed to adhere polar elastomers to fabric
followed by a second layer of an adhesive of the type used to bond
EPDM a metal can also use a single layer of adhesive based on
silicone polymers dissolved in methanol, in this latter case it should be
be very careful with humidity as it deactivates the adhesive.

- 30 -
 e. Molding.

All normal molding systems can be used for EPDM.

that is compression, transfer, and injection.
In the case of injection and transfer, the choice is fundamental.
suitable viscosity of the polymer, in general, it is sought that the viscosity
the compound is low so that the mold filling is done with
ease. Normally, process aids are not necessary since the
The fluidity of the material is very good, although it can be improved if necessary.
through the incorporation of zinc metal salts or low polyethylene
density, especially in mixtures loaded with low contents of loads
active.
For injection, a flexible curing system is essential.
poder ajustar fácilmente la relación entre el tiempo de cura y el tiempo de
prevulcanized. This is difficult to achieve in the case of crosslinking with
peroxides, for this reason sulfur treatments are usually preferred. If the
requirements of physical properties, especially deformation due to compression or
resistance to high temperatures, makes the use of peroxides necessary due to
to vulcanize at very high temperatures in order to shorten the cycles of
cure, but at the same time, maintain a long pre-vulcanization time
It is necessary to use peroxides that decompose at high temperatures.
The issue of corrosion and mold fouling, while not as critical.
as in halogenated elastomers it can be important, especially
when TMTD, calcium carbonate, oxide, or are used in the formulation
zinc stearate and high doses of oils.
The embedding can be reduced by using release agents.
internal or external. Among the latter, release agents are recommended.
semipermanents that vulcanize over the mold.
If the mold is going to be subjected to very prolonged use, it may be
reasonable to build it in stainless steel, or if the service is not that
demanding, it can be thought of coating it with a layer of chrome or of
Teflon.
In the event that the embedding needs to be removed, there is a series of
possible methods each with their advantages and disadvantages, they are
summarized in the table below.

Cleaning Method Advantage Disadvantage

Chemical Compounds
High cost, in very molds
vulcanize over the mold
Simplicity dirty must be repeated several times
what they take out the inlay
times
upon demolding
Acid chemical bathroom with It is necessary to remove from the
sulfuric acid and acid Low Cost press and does not work in
chromic iron molds
It is necessary to remove from the
Caustic Products Low Cost press and it does not work in
aluminum molds
Chloride bath of It is necessary to remove from the
High Cost
methylene press
Mechanical cleaning in
press with materials Low Cost Not very effective
abrasives
Sandblasting, Low Cost It is necessary to remove from the

- 31 -
 glass spheres, press and the material of
walnut shells shot blasting depends on the
marmolina mold material
Very effective,
Sandblasting with clean anhydride, it is not
solid carbonic ("ice necessary High investment in equipment
dry remove from
press

f. Adhesion

There is a tradition that speaks of 'the poor adhesion of EPDM rubbers'.

that is not correct and different cases must be distinguished when talking about the
stuck.
.
i. Adhesive EPDM vulcanized to vulcanized EPDM.

This pasting can be done by different methods (and,

naturally, with different results).
Union through a compound of raw EPDM and subsequent
vulcanized. This method is used in the joining of two gaskets
automotive and the method usually used is a
transfer molding (the compound used normally
it is one of low viscosity, with high doses of resins of
stickiness). No prior treatment of the
surfaces to be joined, should only be cut to be
clean.
A similar union can be made using a compound of
EPDM but applied like cement and vulcanizing the joint
while both surfaces are kept pressed against each other
against another. The union values obtained in this case
they depend heavily on the effectiveness of the method used to
to keep both surfaces together, but still in the best of the
In most cases, the obtained values are lower than those of the method.
previous.
The simplest method is to use a cement as mentioned.
in the previous point, but without vulcanizing (that is, cold), in that
it can be joined using vulcanized rubber adhesives
cold (which is not easy in EPDM). Another alternative is
using contact adhesives based on polychloroprene
sometimes they can be cold reticulated
through isocyanates) however, the obtained bond is not very
good, except for the case of the sponge seals. Finally
they can be easily joined using cyanoacrylates,
in that case, the union achieved is very good in terms of
traction, quick to do (from 5 to 60 seconds), the only
The inconvenience is the fragility or rigidity of the union that can be
a serious problem if the seal bends there.

ii. EPDM rubber adhesive vulcanized to metal substrates or

plastics.

32
 The procedures to be used are the same as those described.
previously, except in this case the stiffness before
the mention of cyanoacrylates is a minor inconvenience now
that flexibility of the union is not needed.

iii. Non-vulcanized EPDM rubber adhesive to metal substrates.

The bonding of unvulcanized rubber to metal is the problem

basic that appears when manufacturing EPDM-metal supports,
Wheel or roller bearings, seals with a metal casing. The
rubber metal union is excellent, just as good as with others
types of rubber on the condition of using the adhesive system
correct.
The treatment of the metal is equally important, which
generally consists of degreasing, mechanical cleaning
by shot blasting, new degreasing. Shot blasting can be
make with sand, metal granules or walnut shells according to
the type of metal to stick. In small pieces the previous system
can be replaced by chemical toilets (acid or caustic)
depending on the metal) and sometimes phosphated. The baths
Chemicals are very convenient, especially in parts.
girls for cost and they provide very good adhesion values but in
changes require constant and careful control of the
chemical characteristics of the bath.
Normally, a two-adhesive system is used, one
of priming and one of gluing. Sometimes a third is used.
cement cover made based on the own compound to be glued to
which has a 3% non-reactive phenolic resin added to it, and whose
its only function is to provide stickiness to keep the rubber together
to the metal while it vulcanizes, but does not increase the
adhesion (and often decreases it).
iv. EPDM unvulcanized rubber adhesive to vulcanized EPDM

In this case, only the vulcanized compound should be sanded.

and apply a layer of cement of the same compound with a
resin additive (3%), apply the compound without it
vulcanize and ensure good pressure while vulcanizing.

8. Special types

The different manufacturers have developed some types of EPDM with

very specific properties, for example, we mention the following: types
liquids, with silicone graft, maleated modified EPDM, with
nylon or styrene-acrylonitrile (SAN) graft, etc.

Liquid Types.

Very low molecular weight EPDM has been developed in such a way that
they result in liquids at room temperature, having a consistency like
a molasses. The advantage of these liquid polymers is that they work

33
 as plasticizers before vulcanizing but then co-vulcanize and
it loses its plasticizing function behaving like rubbers.
this way materials with acceptable viscosity are obtained, and still
with good adhesiveness, reaching hardness elevated.
Surprisingly, liquid EPDM in mixtures with EPDM rubbers and
natural with high doses of TMQ allows obtaining compounds that
they are basically made of natural rubber but have a resistance to
ozone very high without being staining.
Next, we show the surprising increase in
ozone cracking resistance that occurs when
it incorporates a liquid EPDM, a regular EPDM, and high doses of
antioxidant TMQ, this constitutes a very economically viable alternative
interesting concerning the use of non-staining anti-ozonants that are very
expensive.
It should be noted that the TMQ, especially those
products of very high molecular weight (and in that case are presented
in the form of powder) are very slightly staining in the mixture
and they are not at all by contact,

Material Mix 1 Mix Mix

2 3
Natural Rubber 100 80 80
EPDM B 20 10
Liquid EPDM 10
TMQ 5 5 5
White Load 55 55 55
Zinc Oxide 5 5 5
Stearic acid 1 1 1
Sulfur 2.5 2.5 2.5
MBTS 1.0 1.0 1.0
DPG 0.3 0.3 0.3
Breaking Tension 20.7 14.5 15.8
MPa
Stretching of 547 563 707
Break %
Shore A Hardness 45 50 44
Hours for 21 71 >547
cracking. Ozone
50 ppm 400It is stretched
20%

Injected with Silicone

Silicone-grafted EPDM polymers have been developed.

In this type of polymers, properties of EPDM and silicone are combined.

- 34 -
 giving the properties that are shown comparatively in the table to
continuation

Property Silicone EPDM with grafted EPDM

na silicone
Heat resistance A B C
Cold Flexibility A A B
Oil Resistance B C-D D
Electrical properties as such A A A
Electrical properties after immersion C B B
in water
Resistance to water vapor D A-B A
Properties Mechanics Temperatura C B A
Environment
High-Temperature Mechanical Properties B B D
Deformation by Compression A B C
Resistance to Acids and Alkalis D B B

The grading is: A excellent, B good, C average, D poor

Injected types for plastic modification.

Several EPDM manufacturers have developed various EPDM in the

which have been chemically inserted with other groups resulting in polymers whose
Utility is the modification of thermoplastic materials.
Below we present a table with different types, structure,
function and applications.

Structure Function Applications

EPDM with improved resistance to mixing with nylon alone
anhydride impact and adhesion reinforced with spheres of
maleic to the material of glass
reinforcement
Inserted EPDM Increases resistance Blend with SAN, PET
with SAN to the weather, to UV and to acrylics, ABS
impact
EPDM Increases resistance Mix with PET
Modified with the impact and
SAN maintains tenacity
Embedded EPDM increases hardness,Hoses
with Nylon rigidity.

PET = Polietilen tereftalato

SAN = styrene-acrylonitrile
ABS = acrylonitrile-butadiene-styrene

- 35 -
 .

9. Applications and Uses.

The global production of EPM and EPDM is distributed according to the following uses:

Use Percentage

Automotive 26
Modification of Polymers 22
Roof membranes 18
Additives for Oils 10
Cables 9
Household Items 3
Non-automotive hoses 2
Miscellaneous 10

Taking into account the previous data, we will proceed to discuss the uses in
each of those sectors, formulations and typical processes of them.

Automotive Industry

Given the volume of the tire sector, we will study it separately from the
remains, even when the penetration of EPDM in the tire market has
minimum income

Tires

Few are the tire compounds where it has penetrated.

significantly the EPDM rubber, for example the sides of
covers, where they generally work mixed with rubbers
unsaturated or with halobutyls, providing an adequate
ozone and weather resistance. Instead, they are used alone in the
formulation of protectors for truck where the use is maximized
low cost of the mixtures, given by their absorption capacity
of loads without losing resistance to high temperatures that
they develop inside a truck tire.
Below are typical formulations for both.
products and the properties obtained for them.

Truck Protectors.

Material phr
EPDM C 100
N 660 (GPF) 175
Naphthenic Oil 100
Stearic acid 1
Zinc Oxide 5
Sulfur 1.5

- 36 -
 MBT 0.5
TMTD 3.0
Vulcanized 10' to 1600C
Hardness 63
Breaking Tension MPa 12.0
Break Elongation % 550

Tire Side

phr
Material
White Black
EPDM D 15
EPDM E 20
Chlorobutyl 35
SMR 5 80 50
Titanium Dioxide 35
N 660 (GPF) 40
Naphthenic Oil 5 12
Stearic acid 2 1
Zinc Oxide 35 5
Microcrystalline Wax 5
Sulfur 3.5
TBBS 0.35
Alkyl Phenyl disulfide 0.8
MBTS 1.0

2. Non-Tire Automakers

The uses of EPDM in automobiles are very numerous, due to

example: flocked wrapping paper, combined sponge-compact wrapping paper with
or without metal insert, cables inside the engine compartment,
high voltage insulators, brake pads and many more.
In the case of the clowning, its enormous is especially exploited.
resistance to ozone cracking. The reason is very simple the
exposure of those articles to ozone is very large and the use of
unsaturated elastomers protected with effective antiozonants remains
discarded since they cause contact staining on
the vehicle's paint. The other alternatives, for example
polychloroprene, are much more expensive than EPDM and less
effective.
The seals can be compact with hardnesses ranging from
40 to 80 Shore.
The process is continuous and can be air vulcanized.
hot, bath salts, microwave, direct heating ovens or
fluidized bed.
In the region, due to lower investment, ovens are used for
hot air working at a temperature on the order of 2000C. In
In some cases, the gasket has a metal core made of a sheet.
shaped and pre-cut that allows for its attachment to the body.

- 37 -
 Below we provide an example of a formulation for profiles.
hardness 70. These formulations are very general and must
to be adapted to the machinery used in the factory for the process, this
it is especially valid for the case of the sponge, in which the
equipment turns out to be very critical.

Compact Extrusions

Material phr
EPDM F 100
Zinc Oxide 10
Stearic acid 1
Smoke Black N 550 130
Paraffin Oil 100
Sulfur 1.50
MBT 1.5
TMTD 0.7
ZnDBDC 1.5
TeDEDC 0.3
Calcium Oxide 5

Properties
Rheometry Arch 10a 1700C
T1 1.0 min
T90 6.0 min.
Vulcanized 6' to 1700C
Shore Hardness 68
Breaking Tension 12.8 MPa
Breaking Elongation 400%
Tear Given B 45 kN/m

Sponge Weatherstrips

Material Phrase
EPDM G 100
Black N 550 70
Zinc Oxide 5
Stearic acid 1.2
Naphthenic Oil 70
Vaseline 5
MBTS 1.1
TMTD 0.9
ZnDBDC 1.1
Sulfur 1.8

38
 Calcium Oxide 9
p.p'-oxybis benzene sulfonyl 5.8
hideazida)

The vulcanization conditions are: pre-curing 3’ at 160 0C and

vulcanized 5' at 1800C for a circular cord that after vulcanization has
a diameter of 12 mm. It results in a density of 450 kg/m3.
For continuous sponges, the balance between the
decomposition rate of the foaming agent and the vulcanization rate.
The curing speed can be adjusted by changing the dosage of diethyl.
tellurium dithiocarbamate or pentamethylenethiuram hexasulfide; this must
to adjust for each production process and is critical in the regularity of the
profile obtained.
In our countries with high humidity, it is necessary to
calcium oxide additive to retain moisture, otherwise the
the skin of the profile becomes perforated. The dose to be used should be the minimum
possible due to cost reasons and because it interferes with vulcanization (it can
vary from 3 to 15 phr) .
EPDM is indispensable in the manufacturing of curved or straight pipes.
for automotive radiators, it is combined for its high resistance to
the high temperatures, to the liquids used in the radiators and a
poor resistance to oils, but suitable for talking
that resist sporadic contact with oils.
Below is a typical formulation of a radiator hose
that meets the specifications of a car manufacturer.

Radiator Hose

Material phr
EPDM H 140
Black N 770 90
Black N 550 120
Zinc Oxide 5
Stearic acid 1
Paraffin Oil 110
TMTD 3.0
DTDM 2.0
ZnDBDC 2.0
ZnDMDC 2.0
Sulfur 0.5

39
 Vulcanization Properties 30' at 1600
Module at 200% MPa 1.4
Breaking Tension MPa 10.2
Break Elongation % 360
Hardness 72
Deformation Permanent for 47
Compression ASTM D 395 Method B.
70 hours at 1210C.
Aged 168 h at 1210C
% breakdown voltage change +25
% change in elongation at break -36
Hardness change +5
Liquid cooling immersion for 168 hours at
boiling point.
breakdown voltage change percentage +9
percentage of elongation at break -6
Hardness change -15
Volume Change % +30

In molded or extruded parts for automobiles, EPDM

it finds application in various sectors of it, for example the
following:
Brake pads.
Cables
Spur stops
Vacuum tubes.

The formulation of brake pads for the

what is fundamental is the resistance to high temperatures and a high degree of
elasticity, therefore a treatment with peroxides is usually performed, as it
show the following formula:

Brake pad

Material phr
EPDM I 140
Black N 770 40
Black N 550 30
Zinc Oxide 5
TMQ 2
Dicumyl Peroxide at 40% 7
TRIM 2
Vulcanization Properties 30' to 1660
Module at 300 % MPa 1.2
Breakage Tension MPa 15.5
Break Elongation % 240

- 40 -
 Hardness 67
Deformation Permanent for
Compression ASTM D 395 Method B. 11
22 hours at 1750C.
Aged 22 hours at 1750C
% of breakdown voltage change -1
% change elongation at break -18
Change of hardness +2
0
Brake fluid immersion for 22 hours at 175 C
% breakdown voltage change -5
% change elongation at break +4
Change of hardness -2
Volume Change % +2.9

Note the high dose of peroxide along with the coagent for
increase the crosslinking, there is a use of antioxidant to improve resistance
at high temperatures but one must choose one that does not interfere with the
vulcanization based on peroxide. The dosage of loading is low to achieve
good mechanical properties. The other point to highlight is the time of
vulcanized that is very long.

b. Household Items

EPDM rubbers have a strong presence in the appliance sector.

domestic, the reasons for this are their relatively low cost, their high
resistance to oxidation and ozone, the possibility of coloring it and that those
colors remain quite well, and especially the resistance to the
detergents.
This last property has made them employed in all the
rubber parts of washing machines, especially in the door seals of the
washing machine with a horizontal axis. In this case, we are talking about a
white formulation like the following:

Washing Machine Door Seal

Material phrase
EPDM J 100
Precipitated Silica 175 m2/g 40
Paraffin Oil 10
Stearic Acid 1
Zinc Oxide 5
Sulfur 1.5
MBT 0.8
TMTD 0.8
ZnDBDC 3
PEG 4000 3
Titanium Dioxide 20

41
 c. Construction

In construction, there are two well-defined sectors where EPDM

It has been incorporated very importantly, they are the window profiles.
and the sheets for roof waterproofing.
In the window profile sector, it strongly competes with PVC.
being significantly more expensive than this, however its properties of
weather resistance makes it much more durable, therefore the
the choice of the polymer used will depend on whether the criteria prevail
short-term cost or quality. Regarding formulation, it is always sought
an economy of the same which is limited by the demands of the
process since this type of article is generally vulcanized in
I continue in systems without pressure, an example is the following formula:

Weatherstrip for Windows.

Material phr
EPDM K 100
Black N 550 140
Precipitated Calcium Carbonate 40
Paraffin Oil 100
Stearic Acid 1
Zinc Oxide 5
Azufre 1.5
MBTS 0.8
TMTD 0.8
ZnDBDC 1
Calcium Oxide 10

In the sector of roofing sheet coverings, it competes with others.

elastomers such as butyl, chlorosulfonated polyethylene, or polychloroprene, but the
The excellent balance between service and cost that EPDM offers makes it almost
insurmountable for this use. In contrast, it competes in less demanding markets.
unfavorably due to price compared to other types of products such as the
tar paper or tar-coated aluminum sheets. Despite that, when the
The requirements are high, the choice remains EPDM.
In the formulations of sheets for roofs, they go through a stage
In calendering, polymers with a weight distribution are generally used.
very wide molecular, which favors the process. A typical formulation is
the following:

Ceiling panels

Material phr
EPDM N 100
Black N 550 120
Paraffin Oil 80
Stearic Acid 1
Zinc Oxide 5
Sulfur 1.0
MBT 1.5
TMTM 2.0

42
 Mechanical and Industrial Articles

It is difficult to give examples of molded articles that are formulated with

EPDM since the list is very long, in general we can say that they are used
when the demands on atmospheric agents and/or high temperatures or
Oxygenated solvents are the ones that prevail. They are not used instead when
the article is in contact with hydrocarbons or the mechanical requirements are
very high. Many times they are used for their electrical properties, such as
for example, it occurs with insulators for high voltage lines,
spark plug caps for automobiles, etc., in this sector compete with the
same items made with silicone rubber, but in that case the
Economic advantages are on the side of EPDM.
Only as an example, we present the formulation of a
EPDM compound with very good mechanical properties designed to be
injection molded

Material phr
EPDM M 100
Black N 660 40
Naphthenic Oil 20
Stearic acid 1
Zinc Oxide 5
Metallic Stearates Mixture 3
Sulfur 1.00
TMTD 0.75
ZnDBDC 0.75
DTDM 1
TBBS 1.20
Rheometric properties Arch 10, 1700C
Viscosity lb-in 4.20
lb-in module 37.8
T1 2.90
T90 6.85
Breakage Tension MPa 14
Rupture Elongation 480
Shore Hardness A2 62

EPDM begins to enter a sector that was dominated until recently.

for the chloroprene in vibration damping supports, of bridges or joints
dilation. The advantages of EPDM in these uses lie in its better
behavior in front of ozone and weather, lower density and higher
possibilities of absorbing charges, with the economic improvement that this means.
On the other hand, it presents many economic advantages compared to the
polychloroprene, not only is the price of the elastomer lower, but
It admits higher levels of loads and oil, and has a density of 870.
kg/m3against 1230 kg/m3of polychloroprene.
It has traditionally been held that the best properties
The mechanics of polychloroprene make it the preferred choice for that type of use, not
nevertheless, the following two compounds show that appropriately
formulated EPDM is a good candidate to replace polychloroprene,
except when resistance to lubricating oils is needed.

43
 Compounds for Bridge Supports.

Material phr phr

EPDM K 100
Polychloroprene 100
Precipitated Silica 15
Black N 660 30 70
Naphthenic Oil 25
Diisononyl phthalate 10
Magnesium Oxide 4
Stearic acid 0.5 1
Zinc Oxide 5 20
TMQ 1
TMTD 0.8
ZnDBDC 0.8
DTDM 1.5
MBTS 0.5 1.2
ETU 1 0.8

Rheological properties Arch 10, 1700C

Viscosity lb-in 21.0 8.5
lb-in module 47.0 36.4
T1 1.8 3.6
T90 24.0 10.8

Vulcanized 20% above T90

Shore A2 hardness 62 62
Breakage Tension MPa 16.7 13.3
Alargamiento de Ruptura % 420 650
Tear Given C kN/m 39.2 35.4
Permanent Deformation Method B 27.7 15.3
22h to 700C %
Water Absorption D 471 7 days at 18.0 0.4
700C %
Change of Properties Aged 7 Days to 700C
Change Breakage Tension MPa -1.2 +0.6
Change in Elongation at Break % -50 -10
Hardness Change +3 +2

The previous data shows that chloroprene is slightly

better than EPDM for tensile strength and tearing, but it is noticeably
inferior in terms of vulcanization characteristics, permanent deformation
for compression, water absorption, and aging.
It is interesting for those compounds to compare their behavior.
hysterical of both materials, the graphs below show the
results of plotting tension against elongation over a distance of
stretching and another for retraction for both compounds.

- 44 -
 The area enclosed within the curve for CR is 15.30 units while
that for EPDM it is 13.60 units, which shows a lower behavior
hysteresis for EPDM than for CR.
To simulate a bridge support, three stainless steel plates were prepared
200 x 200 x 2 mm, separated by two layers of rubber 8 mm thick each
One. The rubber-metal union was carried out using standard adhesion systems in
the industry.
The two outer plates were held steady while a force was applied.
from extraction to the central plate, plotting force in Newtons against displacement
lateral in millimeters. The results are shown in the following graph, needing to
it should be noted that there was never a separation of the rubber from the metal

A good linear behavior of the EPDM is observed, even better than the
polychloroprene.

One aspect that is often overlooked in the case of the joints

the pressure applied to them can produce the extraction of plasticizers from the
material due to the simple effect of pressure. While this occurs in many
elastomers, in the case of EPDM it can be very important considering the high
levels of plasticizers used, as well as the nature of petroleum oils

45
hacen muy contaminantes en algunos casos, por ejemplo cuando se usan como sellos
in containers with oxygen under pressure. In these cases, it is advisable to assess the possibility
to completely eliminate petroleum oils or use EPDM as plasticizers
retractable liquids.

e. Hoses and pipes

In addition to the already seen automotive radiator hoses, the

EPDM is used in domestic and industrial hoses. For example
For household hoses, we present the following formulation:

White Hose

Material phr
EPDM J 100
Precipitated Silica 175 m2/g 60
Calcium Carbonate 40
Reinforced Kaolin 20
Paraffin Oil 50
Stearic Acid 1
Zinc Oxide 5
Sulfur 1.5
MBT 0.75
TMTD 0.75
ZnDBDC 3
PEG 4000 4
Titanium Dioxide 20

Rheological properties Arc 10, 1700C

Viscosity lb-in 8.0
Module lb-in 33.8
T1 1.00
T90 4.52
Shore Hardness A2 67

The limitation in the production of this type of article is economic already.

which is significantly more expensive than its PVC substitute, even though its
duration is much longer.
The other sector where EPDM has established itself strongly is the
steam hose, where the properly formulated product with
sulfur donors provide excellent service up to 1500C. As an example
we present the following formula that can be continuously vulcanized in
hot air oven.

Steam Hose

Material phr
EPDM K 100
Black N 550 80
Naphthenic Oil 25
Stearic Acid 1

46
 Zinc Oxide 5
DTDM 2.0
TBBS 1.2
TMTD 0.8
ZnDBDC 2.5
Calcium Oxide 6

Rheological properties Arc 101700C

Viscosity lb-in 5.90
Module lb-in 42.0
T1 2.10
T90 6.15
Breakage Tension MPa 17.2
Break elongation % 380
Shore A Hardness 77

f. Cables

The good properties of low electrical conductivity, very good

dielectric strength and resistance to high temperatures make EPDM
widely used in the special cables sector, on the other hand for reasons of
cost does not compete with other materials when the demands are not very
elevated. Below we provide the example of a formulation where there has been
used aluminum hydroxide as a filler in such a way that it passes the
requirements regarding flame spread.

Flame Retardant Cable.

Material phr
EPDM L 100
Paraffin 5
Hydrated Aluminum Oxide 150
Zinc Oxide 5
Vinyl-tris-(2-methoxy-ethoxy) silane 1.5
Dicumyl Peroxide 3.0
HVA-2 1.0

g. Microporous shoe soles

Despite its bad reputation as 'difficult to adhere after vulcanization'

EPDM and EPM have found important uses as additives in the
manufacturing of microporous sheets based on ethylene vinyl acetate (EVA),
In this type of articles, the permanent deformation due to compression is improved.
and resilience, but the most important thing is that it gives the product a feel
rubbery feeling that pure EVA lacks. Furthermore, it is not observed
no loss in the adhesion values of the insole to the upper of the
footwear. Below we show two formulas to appreciate the effect of the
inclusion of EPDM.

Microporous Plates

47
Material phr phr
EVA 18% 100 70
EPM P ---- 30
Precipitated Silicon Dioxide 175 m2/g 30 30
Zinc Oxide 2 2
Stearic acid 1 ---
Zinc Stearate 2 2
Azodicarbonamide 5 5
Dicumyl Peroxide 40% 4 6
Paraffin Oil --- 15

Vulcanized 10' at 1650C

Density kg/m3 200 170
Shore Hardness 42 47
Resiliencia % 42 47
Compression Deformation 22 hr to 26.2 17.6
Temp.. Ambiente 50%

h. Roller Coating

The roller coating sector would apparently be forbidden.

the EPDM given its very low stickiness, which can be improved a little
through the addition of phenolic resins, but surprisingly it
They achieve excellent results with EPDM rollers.
To do this, the calendered sheets should be warmed up before the
glued at 50-60 0And to make sure that they are very thin (not
more than 1.5 mm, depending on the hardness, the harder, the finer
they must be).
Working with EPDM, a range of hardness can be covered that goes
from 30 to 90 Shore A, maintaining reasonable processability. For the
lower hardnesses should resort to very high weight elastomers
molecular, often extended with oil. For greater hardnesses,
they must use low molecular weight polymers and consequently low
viscosity, in some cases it is advisable to make mixtures with EPDM
liquids
EPDM rollers are basically used in three circumstances: i.
when the service temperatures are very high (up to 1500C) whether in
dry air or in vapor); ii._ when the printing cylinder is in contact
with inks based on oxygenated solvents such as, for example, ethyl acetate
or isopropyl alcohol, which occurs in printing presses on paper or on
polyethylene; and iii._ when there is an environment where the roller is located
important concentration of ozone, for example near the treatment plants
corona effect in the printing of polyethylene bags.
The adhesion to metal poses no problem using a double
adhesive layer, primer, and cement.
We present two formulations of hardness 45 and 70 that
and excellent results:

EPDM rollers

48
Material phr phr
Hardness 45 Hardness 70
EPDM M 100 100
Black N 550 50 100
Naphthenic Oil 70 70
Stearic Acid 1 1
Zinc Oxide 5 5
Phenolic resin 4 4
Sulfur 1.2 1.5
MBTS 0.8 0.8
TMTD 1.2 0.8
DPG 0.8 1.2
ZnDBDC 1.5 2.0

Rheological properties Arc 10, 1700C

Viscosity lb-in 2.25 3.1
lb-in module 22.7 33.2
T1 1.10 0.87
T90 3.65 3.20

The spectrum of hardness covered by the EPDM rollers can be

very wide if extended rubbers with oil are used for the hardness
low and liquid EPDM for the highs. For example, the following formulation
gives excellent results for hardness 30 Shore A2, even though it must
use a minimum 2 mm anchor layer between this compound and the
metal since the soft rubber has poor adhesion to the metal.

Material phr
EPDM O 175
Black N 990 40
Naphthenic Oil 120
Stearic Acid 1
Zinc Oxide 5
Sulfur 1.2
MBTS 0.8
TMTD 0.6
DPG 0.6
ZnDBDC 1.5

Rheometric properties Arc 101700C

Viscosity lb-in 2.00
Module lb-in 10.50
T1 2.02
T90 4.55

In the highest hardness range, values can be reached.

Shore A hardness of 90, in order to reduce the viscosity to
acceptable values and consequently maintain processability
reasonable, the use of liquid EPDM is resorted to by vulcanizing with peroxides.
The compound to be handled corresponds to the following composition:

Material phr
EPDM M 70

- 49 -
 Liquid EPDM 30
Black N 339 30
Black N 990 180
Paraffin Oil 10
Stearic Acid 1
Zinc Oxide 3
Phenolic Resin 7
TMQ 1
Dicumyl Peroxide 40% 7.0

Rheological properties Arch 101700C

Viscosity lb-in 9.20
lb-in module 45.2
T1 1.27
T90 6.15

The previous material shows excellent adhesion to metal using the

classic bonding systems primer and cement, and when vulcanized
Direct steam autoclave packaging does not show inactivation of peroxide.
on the surface. Note the combination of black smoke from very fine particles.
large (N 990) to achieve a good grinding along with N 339 for
improve abrasion resistance.

i. Modifications to Plastics.

The EPDM are used, like other rubbers, as

thermoplastic modifiers to improve impact resistance of
the same. The use of elastomers in blends with thermoplastics is a
very old idea and is based on the fact that the elastomer acts in two ways
different mechanisms either by absorbing the impact energy or by
avoid the propagation of microcracks that appear in the thermoplastic to
consequence of the impact.
The requirements for the elastomer in that application are that it be compatible.
with the thermoplastic and that it disperses homogeneously within the
same. The EPDM (especially the grades obtained in the gas phase) to
having a very small particle size comply with the second
requirement.
At the same time, their chemical nature makes them compatible with
thermoplastics such as polypropylene, and in this way they have reached a
very great success as modifiers of this material. The dosing
used is from 8% for moderate demands up to a maximum of 40%
when the impact resistance requirements are very high, in this
the last case usually results in a decline in terms of ease of
painting of the article.

j. Additives for Oils.

A significant use of EPDM in terms of volume is its application as

additives for lubricating oils, although in this case it does not work as a
rubber.

50
 EPDM is used to increase the viscosity of mineral oils.
while its saturated chain makes it very resistant to high temperatures
temperatures found in the engine.

10. Toxicity and Management

From the perspective of contact with EPDM, none has been detected.
no type of allergies in humans.
Regarding its handling, there are no special recommendations for the
types in bales, while for powdered types it is necessary to take
precautions to prevent static charges from developing in the
containers, which is achieved through proper grounding
of the teams.
Regarding fire behavior and temperature, it can be stated
that the thermal decomposition of the product occurs in the environment of
at 300ºC resulting in carbon monoxide, carbon dioxide
and water.
The autoignition temperature of the pure material, that is to say, the one
temperature at which the material can catch fire without the need for
it ranges between 350 and 3800C.
It is advisable not to exceed 200 ºC in the internal mixer.
camera, as the ignition of residues from some monomer can occur
without reacting, what would have remained in the polymer.
Regarding the handling of EPDM rubber compounds, the products of
toxic substances that may appear are generally linked to
the additives used in the formulation of EPDM.
In the event of a fire involving EPDM or
compounds of this rubber must be extinguished using foam, carbon dioxide
carbon or sand. It is possible to produce the evolution of toxic gases when burning and
there is generally simultaneous exudation of oil.

11. Appendices

a. Glossary.

Composition Acronym Type Material Provider

Polyethylene CSM Polymer Hypalon 40 Dupont-Dow

chlorosulfonated

Chlorinated polyethylene CM Polymer Tyrin 0136 Dupont-Dow

Polychloroprene CR Polymer Butaclor MH 31 Distugil

Chlorobutyl CIIR Polymer Chlorobutyl Exxon

1068
Substances Aflux 42 Help Process Rhein Chemie
Polars and
Surfactants

51
Esters of Help Process StruktolWB 212 Schill&Seilacher
Fatty acids of
High Weight
Molecular

Esters of Maxiflow DF Help Process Rubber Service

Fatty acids of
High Weight
Molecular
Soaps of Maxiflow SP Process Help Rubber Service
Football
Organosilicon Struktol WS Process Help Schill&Seilacher
180
High Resins Homogenizing Struktol 60NS Schill&Seilacher
Polarity e

Candle of LDPE Epolene Eastman

Polyethylene Waxes
Kaolin mix Load Sillitin Z Hoffman
and quartz

Precipitated Silica SiO2 Load Extrusil Degussa

Amorphous

Kaolin Load Dixie Clay Vanderbilt

Reinforcer
Kaolin Load McNamee Clay Vanderbilt
Semireinforcing

Precipitated silica Load Zeosil 175 Rhodia

Dipentamethylene DPTTHS Accelerator Robac P25 Robinson

Thiuram Brothers
Hexasulfur
Tetramethyl TMTD Accelerator Vulkacit Bayer
Thiuram disulfide Thiuram

Diphenylguanidine DPG Accelerator Vulkacit D Bayer

Dipentamethylene DPTTS Accelerator Tetrone A Dupont

Thiuram
tetrasulfide
Zinc dibutyl ZnDBDC Accelerator Vulkacit LDB Bayer
dithiocarbamate

Zinc dimethyl ZnDMDC Accelerator Vulkacit LDA Bayer

dithiocarbamate

Dimethyl nickel NiDMDC Accelerator Niclate Vanderbilt

dithiocarbamate

52
4,4' dithio DTDM Accelerant Sulfasan R Flexsys
dimorpholine
Diethyl telluride TeDEDC Accelerator Tellurac Vanderbilt
dithiocarbamate

Dialquil CuDMDC Accelerator Rhenocure Rhein Chemie

diphosphate of CUT
copper
Zinc –O,O-butyl ZBPD Accelerator Vocol ZBPD Flexsys
phosphorodithioate

Disulfide of MBTS Accelerator Vulkacit DM Bayer

Mercapto
Benzothiazole
Mercapto MBT Accelerator Vulkacit Bayer
Benzothiazole Mercapto
Phenyl ether Accelerator Vultac 5 Arkema
disulfide
Tert-Butyl TBBS Accelerator Santocure NS Flexsys
Benzothiazole
Sulfenamide
Ethylenethiourea ETU Accelerator Vulkacit NPV/C Bayer
treated urea Treated urea Accelerator BIK Crompton/Uniroya
l
N,N'-m-phenylen WHAT 2 Activator SR 525 A Sartomer
dimaleidimina

Vinyl Silano Activator Silane A172 Dupont Dow

Trimethylol TRIM Activator SR 350 Sartomer

propane
trimethylolpropane triacrylate
Tetramethyl thiuram TMTM Acelerante Vulkacit Bayer
monosulfide Thiuram MS

Trimethyl quinoline TMQ Antioxidant Flectol H Flexsys

polymerized

Brominated Octyl Resins SP 1055 Schenectady

Phenol
Phenolic No Resins SP 1077 Schenectady
Reactive
Azodicarbonamide ADCA Bleach Celogen AZ Crompton/Uniroya
a + activators l

p,p'-oxybis Whitening Celogen OT Crompton/Uniroya

benzene sulfonyl l
hydrazide)

53
Dinitroso Eraser Porofor DNO/F Bayer
pentamethylene
tetramina
Compound Mold Cleaner Struktol MC-A Schill & Seilacher
curable of
rubber
Trihydroxide of Various Hydral 710 Alcoa
Aluminum
CaO in Oil CaO Various Prosec Proquitec

Properties of Used EPDM

Code Relationship Mooney viscosity and thermonome Observaciones

Eteno/Pro- conditions -ro y
peno Quantity
EPDM A 70/30 85 to 1000C (ML 1+4) ENB 8.0% High Crystallinity
EPDM B 57/43 53 to 1000C (ML 1+4) ENB 9.5%
EPDM C 80/20 80 to 1000C (ML 1+8) ENB 4.7%
EPDM D 53/47 97 to 1000C (ML 1+8) ENB 3.5%
EPDM E 68/32 60 to 1250C (ML 1+4) DCP 3.0%
EPDM F 58/42 65 to 1500C (ML 1+8) ENB 6.5%
EPDM G 58/42 65 to 1250C (ML 1+4) ENB 8.5%
EPDM H 75/25 36 to 1250C (ML 1+4) ENB 5.0% High Crystallinity + 40
paraffin oil phrase
EPDM I 52/48 73 to 1250C (ML 1+4) ENB 5.0% + 40 ml oil
paraffinic
EPDM J 58/42 55 to 1250C (ML 1+4) ENB 8.0%
EPDM K 60/40 77 to 1000C (ML 1+4) ENB 9.0%
EPDM L 78/22 32 to 1000C (ML 1+8) HD 5.5%
EPDM M 73/27 90 to 1000C (ML 1+4) ENB 5.0%
EPDM N 63/37 60 to 1250C (ML 1+4) ENB 4.0%
EPDM O 66/34 66 to 1250C (ML 1+4) ENB 8.0% + 75 ml oil
paraffinic
EPM P 68/32 39 to 1250C (ML 1+4) 0%
EPDM 46/54 ---------------- ENB 9.0%
Liquid

- 54 -
b. Location Map of EPDM in relation to other rubbers (Temperature-
Oil).

250
FQ FK

200
EPD EAM
CS ACM
150

CR EC
IIR NBR
100 SB
NR
50

0
200 180 160 140 120 100 80 60 40 20 0
Hinchamiento en Aceite ASTM #3

- 55 -
 CAUCHO 23 TECNIA

c. Comparative Properties of EPDM with Other Rubbers.

Polymer Rubber SBR Butyl EPDM CR NBR Silicone Viton

Natural
Name Styrene-Butadiene Rubber Isobutylene- Ethylene- Propylene Chloroprene Acrylonitrile- Polysilicone Fluorinated
Chemist Butadiene Isoprene Butadiene
Designation AA AA AA BA, CA, DA BC, BE BF BG, FC FE, HK
ASTM BK, CH GE
Tension of 30 22 20 20 25 25 10 20
Break MPa
Range from 30-100 40-100 40-80 30-90 20-90 25-95 25-85 60-90
Hardness
Density 0.92 0.94 0.92 0.87 1.23 0.98 1.14 1.86
Adhesion a A A B A A A A B-C
Metal
Fabric Adhesion A B B B A B C-D B-C
Resistance a A C B B B B D B
Tear
Resistance a B-A B-A B B A A D C-B
Abrasion
Deformation B B C B B B A B
by Compression
Resilience a A B D B B C A C
Temperature
Ambiente
Resilience in A B B B B C A B
Hot
Rigidity A A A AA B C AA B
Dielectric
Isolation B-A B B AA C-B D AA B
electric
Waterproofing B C AA B B A D A
a Gases
Resistance a C-B C-B A A B B B B-A
Diluted Acids
Resistance a C-B C-B B B C B C B
Acids
Concentrated
Resistance a C C C C C-B A B A
Hydrocarbons
Aliphatic
Resistance a D D D D C B D A
Hydrocarbons
Aromatic
Resistance a D D D D D C D B-A
Hydrocarbons
Chlorinated
Resistance a B B A A D-C D D D
esters y
ketones
Resistance a D D D D B A B A
Oils
Lubricants
Resistance a D D D D C A C AA
Fuels
Resistance a D D B B A A A A
Oils
Animals y
Vegetables
Resistance a B B A AA B B B A
Absorption of
Water

56
hacen muy contaminantes en algunos casos, por ejemplo cuando se usan como sellos
in containers with oxygen under pressure. In these cases, it is advisable to assess the possibility
to completely eliminate petroleum oils or use EPDM as plasticizers
retractable liquids.

e. Hoses and pipes

In addition to the already seen automotive radiator hoses, the

EPDM is used in domestic and industrial hoses. For example
For household hoses, we present the following formulation:

White Hose

Material phr
EPDM J 100
Precipitated Silica 175 m2/g 60
Calcium Carbonate 40
Reinforced Kaolin 20
Paraffin Oil 50
Stearic Acid 1
Zinc Oxide 5
Sulfur 1.5
MBT 0.75
TMTD 0.75
ZnDBDC 3
PEG 4000 4
Titanium Dioxide 20

Rheological properties Arc 10, 1700C

Viscosity lb-in 8.0
Module lb-in 33.8
T1 1.00
T90 4.52
Shore Hardness A2 67

The limitation in the production of this type of article is economic already.

which is significantly more expensive than its PVC substitute, even though its
duration is much longer.
The other sector where EPDM has established itself strongly is the
steam hose, where the properly formulated product with
sulfur donors provide excellent service up to 1500C. As an example
we present the following formula that can be continuously vulcanized in
hot air oven.

Steam Hose

Material phr
EPDM K 100
Black N 550 80
Naphthenic Oil 25
Stearic Acid 1

46