ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
Green  bio-based  sustainable  EPDM
 Compounding
Keltan® Eco is the world’s first commer-
cial EP(D)M rubber partly produced
from bio-based feedstock. The ethylene
used for this rubber is produced from
ethanol, derived from sugar cane. To in-
crease the sustainability of EPDM rub-
ber products the potential of greener
alternatives for traditional plasticiser
oils and fillers have been explored. A
variety of (trans-esterified) natural oils
and fat, factice and squalane has been
studied as replacement for traditional,
mineral extender oil. Modified natural
oils and squalane give the best perfor-
mance. Carbon black, obtained from py-
rolysis of waste tires, rice husk ash and
micro-cellulose have been investigated
as replacements for standard fillers.
This study has resulted in sulphur-vul-
canised, Keltan® Eco EPDM with more
than 85% of sustainable ingredients for
automotive sealing applications
Grüne EPDM-Gummi­
mischungen
Grün  biobasiert  nachwachsend 
nachhaltig  EPDM  Compounding
Keltan® Eco ist der erste kommerzielle
EP(D)M Kautschuk der Welt, der teilwei-
se aus natürlichem Ausgangsmaterial
hergestellt wird. Das eingesetzte Ethy-
len wird über Ethanol aus Zuckerrohr er-
zeugt. Zur Erhöhung der Nachhaltigkeit
von EP(D)M-Produkten wurde das Po-
tential von grünen Alternativen für tra-
ditionelle Weichmacheröle und Füllstof-
fe untersucht. Variationen von (trans-
veresterten) natürlichen Ölen und Fet-
ten, Faktisse und Squalan wurden als
Ersatzstoffe für traditionelle minerali-
sche Verstreckungsöle eingesetzt. Modi-
fizierte natürliche Öle und Squalan erge-
ben die besten Eigenschaften. Ruß aus
Pyrolyseprozessen von Altreifen, Reis-
schaleassche und Microcellulose sind als
Ersatzstoffe für Standardfüllstoffe unter-
sucht worden. Die Studie hat resultiert
in Schwefel-vulkanisierten „Keltan®
Eco“-EPDM basierende Compounds mit
mehr als 85 % nachhaltigen Komponen-
ten für Dichtungsanwendungen.
Figures and Tables:
By a kind approval of the authors.
26 KGK · 01-2 2018
Green EPDM Compounds
Introduction
The reduction of greenhouse gas emis-
sions and addressing the limited availa-
bility of fossil fuels are two great chal-
lenges of our generation [2,3]. Keltan®
Eco is Arlanxeo’s response to an urgent
call to increase the eco-friendliness of
synthetic rubber. Keltan Eco is the world’s
first commercial EP(D)M rubber, partly
produced from bio-based feedstock (Fig-
ure 1). The ethylene used in this rubber is
produced from ethanol, which in its turn
is derived from sugar cane [4,5]. Conse-
quently, the carbon footprint of EPDM
products is significantly reduced (up to 7
times lower for an EPDM polymer with
70 wt% ethylene) and Keltan Eco is truly
sustainable, according to a Life Cycle As-
sessment [6]. If all EPDM rubber in auto-
motive sealing systems in all cars glob-
ally produced today would be made from
Keltan Eco, < 3% of the land currently
used for sugar cane production for etha-
nol in Brazil would be required, which
amounts to < 0.04% of all arable land in
Brazil. If second generation feedstock
technology becomes available, this will
be an interesting option to further in-
crease land use efficiency. Currently, five
different Keltan Eco products are com-
mercially available with varying ethylene
and ENB contents and Mooney viscosity.
These products are identical to regular
Keltan EPDM products in terms of techni-
cal performance and as such are true
technical drop-ins. The 14C content of
Keltan Eco EPDM determined via the
ASTM D6866 test confirms the bio-origin
of the ethylene used.
Typically, rubber products not only
consist of elastomer(s), but also of (rein-
forcing) filler(s), plasticiser, crosslinking
agents and other additives. Actually,
EPDM products may easily contain up to
400 phr of compounding ingredients in-
corporated into 100 phr of rubber. Car-
bon black is produced via the incomplete
combustion of a hydrocarbon feed with
natural gas. Silica is produced via the
precipitation from a silicate salt solution.
Inert white fillers, such as clay, talc and
chalk are extracted from the ground in
open mines and milled to fine powders.
Traditional extender oils for EPDM are
refinery fractions of crude oil. All of these
ingredients typically used for EPDM com-
pounding lack sustainability. Numerous
studies have been performed on more
[1]
sustainable rubber compound ingredi-
ents [7,8]. With respect to fillers one may
consider all sorts of natural fibers (jute,
palm, sisal, hemp etc.) and natural flours
and powders (wood, cork, soy etc.) [9-12]
as well as recycle carbon black, produced
via pyrolysis of waste tires [13]. The for-
mer should be viewed as inert, white
fillers which only dilute the compound
but do not contribute to the perfor-
mance, whereas the latter has a promis-
ing performance close to that of tradi-
tional carbon black. Natural oils, such as
palm oil, rice bran oil, ground nut oil,
soybean oil, mustard oil and sunflower
oil, have all been explored as green plas-
ticiser in rubber products, but with lim-
ited success due to the inferior proper-
ties of the final compounds [14-21].
In further efforts to increase the sus-
tainability of EPDM rubber products based
on Keltan Eco, we have explored the tech-
nical potential of green alternatives for
traditional plasticiser oils and (reinforcing)
fillers. The emphasis in this study is on the
technical aspects, such as the compound
mixing, processing, vulcanisation and
properties (after ageing) of the final vul-
canisates. There will be no further discus-
sions on the level of sustainability nor on
the costs of the alternatives ingredients
and the final compounds.
In a first screening a variety of bio-
based oils has been studied as replace-
ments for traditional mineral oil. The na-
tural oils studied, e.g. linseed oil, tung (or
wood) oil, coconut oil and olive oil, are all
triglycerides with fatty acid chains varying
in length and unsaturation. These four
natural oils were selected, because they
provide a nice spread in the level of unsa-
turation (as witnessed by the iodine num-
ber) and the melting point. Butter fat is a
Authors
Martin van Duin, Philip Hough,
Geleen, The Netherlands
Corresponding Author:
Martin van Duin
Keltan R&D
ARLANXEO Elastomers B.V.
P.O. Box 185
6160AD Geleen, The Netherlands
E-Mail:
martin.vanduin@arlanxeo.com
Tel. +31(0)467020853
www.kgk-rubberpoint.de
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triglyceride obtained from cow milk and 1

was included, because it has a rather low
iodine number, though a relatively high
melting point. Modified natural oils, such
as hydrogenated coconut oil (almost no
unsaturation) and mono-esters produced
via trans-esterification of natural oils, i.e.
ethylhexyl oleate (reaction product of
high-oleate sunflower oil with ethylhexyl
alcohol) and isotridecyl stearate (satura-
ted mono-ester), were included in a se-
cond phase of the oil screening study to
overcome some of the compatibility and
vulcanisation issues experienced with the
natural oils and butter fat. Factice, which
is a highly vulcanised vegetable oil, was
originally introduced to the rubber indus-
try around 1850 as a partial economic
substitute for natural rubber [22,23], but
is used today as special processing agent.
Factice was tested as a full oil replace-
ment, because it consists of highly cross-
linked natural oil and, thus, could over-
come some of the issues encountered
with the natural oils, but was also tested
in combination with natural oils with the
idea that it could act as a sort of sponge to
permit higher loadings of the natural oil.
Finally, 2,6,10,15,19,23-hexamethyltetra-
cosane (squalane) was evaluated. Squala-
ne is a fully saturated C30 hydrocarbon,
which resembles an EPM hexamer and is
sometimes used as a high-boiling solvent
for EPDM in academic studies [24].
Squalane is traditionally obtained via hyd-
rogenation of the triterpene squalene
from shark liver, but more recently a pro-
cess was developed where plant sugar is
converted via genetically engineered
yeast into trans-β-farnesene [25], which is
dimerised and subsequently hydrogena-
ted to squalane [26].
Fig. 1: Production of Keltan® Eco EPDM, enabling EPDM rubber products with up to 90%
sustainable ingredients.
1 Characteristics of Keltan® (Eco) EPDM polymers from ARLANXEO
Keltan bio-based ethylene (wt%) ENB (wt%) ML 1+4 @ 125°C oil (phr)
5470 - 70 4.6 55 0
6471 - 67 4.7 65 15
8550 - 55 5.5 80 0
Eco 5470 + 70 4.6 55 0
Eco 8550 + 50 5.5 80 0
In a second screening sustainable fill- duces the CO2 production by 5 ton per
ers have been investigated as replace- ton of rubber compound [13]. In the
ments for standard carbon black and in- context of this study we choose to use
ert, mineral fillers. Pyrolysis black is eval- the term sustainable ingredient. Rice
uated versus standard furnace black. This husk ash is basically silica, recovered via
pyrolysis black consists of both the origi- burning off the organic fraction of rice
nal carbon black, used in the production husk which is obtained during the rice
of tires, and additional black, formed cleaning process [27]. Micro-cellulose is a
upon pyrolysis of the rubber and plasti- natural fiber, produced through a process
ciser in the end-of-life tire waste. While of chemical disintegration of different
one can argue that pyrolysis black is not woods.
derived from a bio-based source, a pro- In the final study we combined the
portion is in fact derived from natural leads from the first two screening studies
rubber. In addition, (tire) rubber end-of- and explored EPDM compounds with the
life waste is a major environmental issue highest level of sustainable ingredients,
and pyrolysis seems to be a preferred re- while still maintaining the performance
cycling technology, which in the end re- of high-quality EPDM compounds.

2 Characteristics of (bio-based) oil plasticisers.

chemical product supplier molar mass density melting point solubility parameter iodine number
composition (g/mol) (g/cm3) (°C) (J/cm3)0.5 (g/100 g)
paraphinic mineral Sunpar 2280 Sunoco ~ 700 0.89 15.9 0
oil
refined linseed oil Rutteman ~ 880 0.93 -20 17.2 193
Chinese tung oil Rutteman ~ 870 0.94 4 17.2 168
olive oil Albert Heyn ~ 880 0.92 -1 17.2 84
butter fat Friesland Campina ~ 840 0.91 36 17.0 34
refined coconut oil Rutteman ~ 720 0.92 25 17.2 11
hydrogenated Agri-pure AP-620 Cargill ~ 720 0.92 32 17.2 2
coconut oil
isotridecyl stearate Loxiol G40 EmeryOleo 466 0.86 -5 16.6 1
ethylhexyl oleate Tudalen TP 130B Hansen+Rosenthal 394 0.87 0 16.6 0.64
squalane Neossance Amyris 422 0.81 -38 15.3 0.13
factice Rhenopren EPS Rhein Chemie/ ~ 1.0
LANXESS
5.5%ENB-EPDM Keltan 8550 ARLANXEO 300.000 0.86 15.7 11.6

www.kgk-rubberpoint.de KGK · 01-2 2018 27

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
Experimental
Materials
For a brief description and the charac-
teristics of the EPDM polymers, the oil
plasticisers and the fillers used in this
study, see Tables 1, 2 and 3, resp. The
details have been provided by the sup-
pliers. The solubility parameters of the
oils have been calculated using a group
contribution method [28]. First, the oil
plasticisers were screened in sulphur-
vulcanised EPDM compounds with vary-
ing oil and carbon black contents
(33/50, 33/150, 67/100, 100/50 and
100/150 phr/phr) based on an amor-
phous, high Mooney EPDM (Keltan
8550) (Table 4). Next, pyrolysis black
was evaluated in a sulfur-vulcanised,
automotive, solid seal compound based
on a crystalline EPDM (Keltan 5470) (Ta-
ble 5). Rice husk ash and micro-cellulose
were evaluated in a white bull-eye com-
pound based on a 15 phr oil-containing,
crystalline EPDM (Keltan 6471) (Table
6). Finally, the best leads for bio-based
plasticisers and sustainable fillers from
the two screening studies were com-
bined in two highly filled, automotive,
solid seal compounds (Table 7). The first
has low-temperature flexibility for dy-
namic sealing applications and, thus, is
based on an amorphous, high Mooney
EPDM (Keltan [Eco] 8550). The second is
typical of a static seal, where low-tem-
perature flexibility is not required and,
thus, is based on a crystalline, medium
Mooney EPDM (Keltan [Eco] 5470). All
sulphur accelerators were from the Rhe-
nogran family, supplied by Lanxess
Rhein Chemie Additives, and the TMQ
and ZMMBI heat stabilisers were from
3 Characteristics of (sustainable) fillers.
chemical product supplier
composition
carbon black Corax N550 Orion Engineered Carbons
carbon black BBC 500
aluminosilicate Polestar 200R
silica Ultrasil VN 3 Evonik Industries
calcium carbonate Superfine S whiting
amorphous silica
micro-cellulose Arbocel UFC M8
micro-cellulose Arbocel FD 600-30
1) BET measurement using nitrogen adsorption (m2/g); 2) measured by oil (DBP) absorption (m2/g)
28 KGK · 01-2 2018
the Vulkanox family, supplied by Lanxess
Advanced Industrial Intermediates.
Compounding
The rubber compounds have been pre-
pared on an internal mixer (1.5 liter)
from Harburg & Freudenberger. The mix-
er is equipped with PES5 rotors with a
thermostatically temperature-controlled
body using circulating water. Mixing was
carried out according to ISO 2393 follow-
ing an upside-down mixing protocol
with 72% fill factor, 45 °C mixer body
temperature, 8 bar ram pressure and 50
rpm rotor speed. In the first 30 sec. the
rubber polymer was crumbled; next the
compounding ingredients with the ex-
ception of the curatives were added and
mixed for 210 sec., giving a total mixing
time of 240 sec. Thereafter, the vulcani-
sation system was added on a tempered
two-roll mill (20 cm diameter, 50°C and
20 rpm speed) and final dispersion was
accomplished by cutting, rolling up and
rotating the rolled rubber sheet by 90°
through the mill nip three times, respec-
tively. For the comparison of the alterna-
tive, white fillers with silica, the starting
mixer body temperature was 70 or
130 °C. After mixing for 240 sec. the rotor
speed was increased to achieve a batch
temperature of 150 °C and then mixing
was continued for 180 sec. at 150 °C to
complete silanisation.
Testing
The compound Mooney viscosity (1+4)
was measured at 100 °C (ML) (DIN 53523
part 3) and the Mooney scorch character-
istics, such as t2 at 125 °C (DIN 53523
part 4) were measured on a Monsanto
MDR 2000E Rheometer. The cure charac-
particle/fibre surface density comments
size (µm)
0.039-0.055
Black Bear 0.005 - 0.1
Imerys Performance Minerals ~ 2
~ 0.015
~2
Silica Verde do Arroz (formerly <8
Geradora de Energia Eletrica
Alegrete)
J. Rettenmaier & Söhne 14 x 5
J. Rettenmaier & Söhne 45 x 25
teristics of the compounds, such as
scorch time ts2, vulcanisation time tc90
and maximum torque difference ∆S =
MH – ML were determined with a Mon-
santo MDR 2000E Rheometer at 180 °C
(DIN 53529 part 3).
Test plates (2 and 6 mm thick) were
compression moulded at 180 bar and
180 °C. The 2 mm test plates used for
tensile and tear measurements were ob-
tained after curing for tc90 plus 10%,
whereas the 6 mm press plates, used for
hardness and compression set measure-
ments, were cured for tc90 plus 25%.
Evaluation of the cured compounds fo-
cused on the following properties: hard-
ness Shore A or IRHD (DIN 53505), tensile
properties, such as tensile strength (TS),
elongation at break (eab) and modulus
at 100 (M100%) and 300% elongation
(M300%) using a dumbbell #2 (DIN
53504), tear resistance Delft (tear) (ISO
34) and compression set (CS) for 24 or
72 hours at -25 °C, 23 °C, 70 °C, 100 °C
and/or 125 °C (DIN ISO 7743). Hardness,
tensile properties and tear resistance
were also measured at room tempera-
ture after hot-air ageing for 7 days at 70,
100 and/or 125 °C or for 7 and 14 days at
135 °C (DIN 53508). Oil volume swell was
determined for IRM901 and 903 oils for
48 hours at 70 °C (DIN 53521). All test
specimens were prepared according to
DIN ISO 23529 and data evaluation was
done in accordance with DIN 53598.
The level of oil bleeding of the sam-
ples was estimated by manually touch-
ing the surface of the samples and sub-
jectively ranking the surface feel after
storing samples of unvulcanised, milled
compounds for 1 week and test sheets,
compression moulded at 180 °C for 4
area (g/cm3)
40 1)
1.8 Fast Extrusion Furnace
(FEF) black
77 1) 1.75 pyrolysis products of
waste tires; also contains
5% ZnO/S and 1-27% silica
8.5 2)
2.6 soft calcined clay
180 1) 2 precipitated silica
2.8 2) 2.7 superfine calcium
carbonate
1.4 2) 2.2 rice husk ash
1.5 chemical desintegration of
wood
1.5 idem
www.kgk-rubberpoint.de
 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

weeks, at room temperature in alu- 4 EPDM compound compositions with carbon black resulted in extremely vis-
minum trays. Samples were ranked on a varying oil and black contents used for cous compounds, for which compound
scale of 5 (no oil bleeding), 4 (surface screening of the bio-based oils. ML could no longer be measured. This is
slightly slippery), 3 (greasy surface), 2 K8550 EPDM 100 because factice behaves like an elastic
(grease transfers to finger tips) and 1 (oil N550 carbon black 50/50/100/150/150 solid rather than a liquid plasticiser.
deposited in trays). bio-based or 33/100/67/33/100 Using factice as a 50/50 (w/w) mixture
mineral oil with butter fat resulted in a reduction of
Results and discussion TMQ 1 the compound ML. However, only in the
ZMMBI 1 presence of 50 phr carbon black accepta-
Bio-based oils ZnO active 5 ble values of compound ML (< 100 MU)
The results of the screening study for re- stearic acid 1 are obtained. The ML values of com-
placing mineral oil by bio-based oils in sulfur-80 1.25 pounds with factice/butter fat having 67
EPDM compounds (Table 4) will not be and 100 phr carbon black were still too
MBTS-80 1.31
presented or discussed in detail. They high. In summary, factice can not be used
ZBEC-70 0.7
will be presented in terms of general in large quantities in these natural oil
ZDBP-50 3.5
trends and issues that were encountered, containing compounds. The ML results of
focusing on lack of compatibility and re- Vulkalent E/C 0.5 the compounds where isotridecyl steare-
duced vulcanisation. A type of go/no-go total 198/265/282/298/365 ate, ethylhexyl oleate and squalane were
elimination approach will be followed, used, are typically ~20 MU below that of
eventually resulting in a selection of bio- The compound ML correlates quite nicely mineral oil, probably because these three
based oils that seem to offer a feasible, with the reciprocal of the oil/black ratio, bio-based oils have much lower molecu-
technical alternative for mineral oil. as expected. ML of all the compounds lar weight than mineral oil (Table 2: ~400
with 33 phr oil and 150 phr black, inclu- vs. ~700 g/mol).
Compounding ding that based on mineral oil, was ext- Compression moulded plaques of the
In the screening study of bio-based oils remely high (>150 MU), due to the very EPDM compounds with 33/50, 67/100
to replace mineral oil, compounds with low oil/filler ratio, preventing any practi- and 100/150 (phr/phr) oil/filler based on
varying oil/black ratios were evaluated cal application. The ML values of com- isotridecyl stearate, ethylhexyl oleate
(Table 4). All compounds based on bio- pounds with factice fully replacing mine- and squalane felt completely dry, show-
based oils with 33/50, 33/150, 67/100 ral oil were also very high (>100 MU). ing no signs of bleeding after storage for
and 100/150 (phr/phr) oil/black compo- Particularly, factice levels of 67 and 100 1 week at room-temperature (5 on the
sitions could be mixed well with mixing phr in combination with 100 and 150 phr scale of 1 to 5), and were comparable to
characteristics quite similar to the min-
eral oil references. The compounds based 2
on butter fat smelled like French fries,
which could be considered objectiona-
ble. However, mixing of the 100/50 (phr/
phr) compounds based on the natural
oils, i.e. linseed oil, tung oil, coconut oil
and olive oil, and butter fat showed low
power development and required very
long mixing times compared to the min-
eral oil reference. The resulting com-
pounds appeared to be of relatively poor
quality with varying degrees of sticki-
ness/greasiness and a lack of coherence,
probably because there was too little
carbon black filler compared to the high
level of relatively polar natural oils. The
more polar, natural oils and butter fat
have a lower compatibility with the apo-
lar EPDM (compare solubility parameters
in Table 2), which makes them quite sen-
sitive for these kind of mixing issues.
These incoherent/sticky 100/50 (phr/
phr) oil/filler compounds can obviously
not be used for practical purposes.
The Mooney viscosities (ML) of the
Fig. 2: Bleeding of oil from samples with varying (bio-based) oil types and oil/black com-
compounds with natural oils and butter
positions: top: milled sheets of unvulcanised compounds and bottom: vulcanised com-
fat were quite similar to those with equi- pounds, assessed after one and four weeks, resp., of storage at room temperature (subjec-
valent levels of mineral oil, ranging bet- tive ranking on a scale of 5: no oil bleeding; 4: surface slightly slippery: 3: greasy surface;
ween 35 and 75 MU, though mineral oil 2: grease transfers to finger tips; 1: oil deposited in trays).
usually gave the highest compound ML.

www.kgk-rubberpoint.de KGK · 01-2 2018 29

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
3 Fig. 3: Overlay
the respective reference compounds
based on mineral oil (Figure 2: top). The
compounds based on linseed oil, coconut
oil and hydrogenated coconut oil with
33/50 and 67/100 (phr/phr) composi-
tions were also dry, but the 100/150
(phr/phr) compositions showed slight
greasiness when touched by fingers,
achieving a rating of 4.5 on the scale of 1
to 5. For butter fat, only the 33/50 (phr/
phr) compound was dry; the other butter
fat compounds were greasy (2 and 3 on
the 1 to 5 scale). Obviously, the occur-
rence of bleeding of the natural oils and
butter fat out of the compounds, espe-
cially at high oil levels (100 phr), is the
result of a lack of compatibility of the
polar oils for the apolar EPDM. Combina-
tions of factice with butter fat (50/50
w/w) and with hydrogenated coconut oil
(33/67 w/w) did not prevent the blee-
ding of the oil out off the compounds.
In summary, the more polar nature of
the natural oils and butter fat compared
to the apolar EPDM, as witnessed by the
relatively high solubility parameters (Ta-
ble 2: 17.0 – 17.2 vs. 15.7 {J/cm3}0.5), leads
to reduced compatibility, resulting in
poor compound quality and bleeding of
the oil out of the compounds. This is es-
pecially the case in those compounds
with high oil/black ratios. For butter fat
4 Fig. 4: Experi-
30 KGK · 01-2 2018
of MDR 2000E
rheometer cur-
ves at 180 °C for
sulphur vulcani-
sation of 33/50
(phr/phr) oil/
black EPDM
compounds with
varying oil plas-
ticisers.
there seems to be an extra effect related
to its melting point being above room
temperature. The use of factice results in
very high compound viscosities (ML) and,
when used in combination with natural
oils, does not reduce the bleeding. The
good compatibility of isotridecyl stea-
rate, ethylhexyl oleate and squalane is
because these oils have somewhat lower
polarities more close to that of EPDM, as
witnessed by their solubility parameters
(Table 2: 16.6, 16.6 and 15.3, resp. vs.
15.7 {J/cm3}0.5).
Vulcanisation
Rheometry of the EPDM compounds
showed that the various natural oils and
butter fat have a detrimental effect on
the vulcanisation compared to the min-
eral oil references (Figure 3). For a given
compound composition the rheometer
torque difference ∆S (= MH-ML) decreas-
es in the order: mineral oil > coconut oil
>> butter fat > tung oil >> olive oil > lin-
seed oil. ∆S also decreases with increas-
ing levels of natural oil or butter fat. The
compounds with hydrogenated coconut
oil, isotridecyl stearate, ethylhexyl oleate
and squalane have rather similar ∆S val-
ues as the mineral oil reference com-
pounds. The presence of high levels of
unsaturation in the bio-based oils easily
mental, norma-
lised rheometer
torque difference
∆S of EPDM
compounds with
varying oil types
and varying oil/
black levels ver-
sus calculated,
normalised ∆S.
explains these results. Natural oils and
fats are triglycerides of C12 – C18 fatty
acids, both saturated (stearic, palmitic,
myristic and lauric acid) and unsaturated
(mono-unsaturated: oleic and palmit-
oleic acid; di-unsaturated: linoleic acid;
tri-unsaturated: linolenic and eleostearic
acid). The unsaturation in these oils will
compete with the EPDM unsaturation for
sulphur vulcanisation, resulting in a de-
crease of the rubber vulcanisation effi-
ciency. Indeed, the rheometer ∆S se-
quence observed parallels the level of
unsaturation of the natural oils, as wit-
nessed by their iodine numbers: mineral
oil < coconut oil < butter fat < olive oil <
tung oil < linseed oil (Table 2), with the
exception of tung oil, as will be explained
below. Obviously, higher levels of natural
oil will also result in more competition
for sulphur vulcanisation. Hydrogenated
coconut oil, isotridecyl stearate, ethyl-
hexyl oleate and squalane are virtually
without unsaturation (Table 2) and,
therefore, do not compete with EPDM for
sulphur vulcanisation, resulting in ∆S
values comparable to the mineral oil ref-
erences. The rheometer scorch times ts2
follow the same trend as ∆S, both as a
function of the oil type and oil content,
probably for the same reasons. In view
of the previous discussion it is difficult to
explain why the rheometer vulcanisation
time tc90 decreases in the series olive oil
> butter fat > mineral oil > linseed oil >
tung oil ~ coconut oil.
Figure 4 shows a plot comparing the
experimental, normalised rheometer ∆S
versus the calculated, normalised ∆S. The
experimental, normalised ∆S is defined
as ∆S of an EPDM compound with a par-
ticular natural oil, divided by ∆S of the
corresponding compound with mineral
oil and ranges from zero (no vulcanisati-
on of compound with natural oil) to unity
(vulcanisation identical to mineral oil re-
ference). The calculated, normalised ∆S is
calculated as the molar ratio of the unsa-
turation in EPDM vs. the total amount of
unsaturation in both EPDM and the oil,
and, therefore, combines the effects of
the level of unsaturation in the oil and
the amount of oil used in the compound.
This parameter also ranges from zero
(infinite unsaturation in oil and/or infini-
te amount of oil) to unity (no unsaturati-
on in oil and/or no unsaturated oil). The
data in Figure 4 show an excellent, linear
correlation with a slope close to unity
with the exception of the tung oil data.
This shows that the decrease in the rheo-
meter ∆S for the natural oil based com-
www.kgk-rubberpoint.de

pounds is fully explained by the competi-
tion for sulphur vulcanisation with EPDM
and that the unsaturation in the natural
oils has the same molar reactivity to-
wards sulphur vulcanisation as ENB in
EPDM rubber. The tung oil exception is
probably related to the fact that tung oil
consists for ~80% of oleostearic acid,
which is a conjugated triene, whereas the
unsaturated fatty acids in the other natu-
ral oils and butter fat are monoenes (oleic
and palmitoleic acid), non-conjugated
diene (linoleic acid) or non-conjugated
triene (linolenic acid). Assuming a 30%
efficiency for tung oil brings the tung oil
data in Figure 4 to the same line as for the
other (bio-based) oils.
Unfortunately, vulcanised plaques of
the compounds with natural oils, hydro-
genated coconut oil and mixtures of fac-
tice with natural oils showed much more
bleeding after storage for 4 weeks at
room temperature than the correspond-
ing unvulcanised compounds (Figure 2:
compare top with bottom). Bleeding was
especially high for the compounds with
low carbon black levels, because of insuf-
ficient porous black to absorb all the
natural oil. Of the 33/50 (phr/phr) natu-
ral oil/black compounds only the butter
fat sample was considered to be just ac-
ceptable (4.5 on scale from 1 to 5). All
67/100 (phr/phr) vulcanisates with natu-
ral oils were (very) greasy (2 to 4) and of
the 100/150 (phr/phr) vulcanisates only
the linseed oil and tung oil samples
Fig. 5: Plots of some physical properties (top left: modulus at 300% elongation; top right: tensile strength; bottom left: compression set at
125°C and bottom right: oil swell in IRM 901 oil at 70°C) versus crosslink density (rheometer ∆S) for compounds with varying (bio-based) oil/
carbon black compositions (33/50, 33/150, 67/100, 100/50 and 100/150 phr/phr); lines are just to guide the eye.
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ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
showed no bleeding. Again bleeding is
the result of poor compatibility between
the apolar ERPDM rubber and the rela-
tively polar, natural oils. There seems to
be no clear explanation for the differenc-
es in bleeding between the various natu-
ral oils; in addition there seems to be no
correlation with the crosslink density.
The vulcanisates with mineral oil and
squalane were completely dry (5 on the
1 to 5 scale). For ethylhexyl oleate a dry
sample was obtained for the 33/50 (phr/
phr) composition and slightly greasy
samples for the 67/100 and 100/150
(phr/phr) compositions (5 and 4.5 ratings,
resp.). For isotridecyl stearate dry vulcani-
sates were obtained for the 33/50 and
67/100 (phr/phr) compounds. These im-
provements in compatibility are related
to the smaller mismatch in polarity
In summary, the unsaturation present
in natural oils competes with EPDM for
sulphur vulcanisation. Higher levels of
unsaturation in the oil and and higher
levels of unsaturated oil result in lower
crosslink densities. Because squalane,
isotridecyl stearate, ethylhexyl oleate
and hydrogenated coconut oil have very
low levels of unsaturation, the com-
pounds based on these oils have crosslink
densities very close to the mineral oil
references. It could be argued that sul-
phur vulcanisation might reduce bleed-
ing of polar oils out off the EPDM com-
pounds by linking the unsaturated oil
molecules to the rubber network. How-
ever, calculations on a molar basis show
that, although the level of unsaturation
in the natural oils is sufficiently high to
compete with EPDM for sulphur vulcani-
sation, the fraction of the relatively small
oil molecules thus linked to the network
is negligible. Indeed, extractions with
tetrahydrofuran for 2 days at room tem-
perature performed on the 33/50 (phr/
phr) oil/black vulcanisates yielded resi-
due weights for the natural oil com-
pounds (80 – 83%), which were similar
within experimental error to the mineral
oil reference (80%) and also to the theo-
retical residue weight (81%). Only for
linseed oil a much lower residue weight
was determined (63%), which shows that
the EPDM in the compound with the
natural oil with the highest unsaturation
level was so poorly crosslinked that it
partly dissolved.
Properties (after ageing)
In general, excellent correlations were
found between the physical properties of
the vulcanised compounds before ageing
and the rheometer ∆S as a measure for
the crosslink density, which are in full
agreement with trends commonly ob-
served in rubber chemistry and technol-
ogy studies [23, 29, 30]. Some illustrative
examples are shown in Figure 5. For vul-
canisates with a given oil/carbon black
composition but with varying oil type,
the hardness and the moduli at 100 and
300% increase with the rheometer ∆S,
KGK · 01-2 2018 31
 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
whereas the elongation at break (eab),
the compression sets (CS) at 70, 100 and
125°C and the volume swell in IRM 901
and 903 oils decrease with the rheometer
∆S typically in the sequence of linseed oil
< olive oil < tung oil < butter fat < coconut
oil < hydrogenated coconut oil ~ isotride-
cyl stearate ~ ethylhexyl oleate < squalane
< mineral oil. For the 33/150 (phr/phr)
oil/black vulcanisates the tensile strength
(TS) increases with ∆S. For the 33/50
(phr/phr) oil/black vulcanisates TS goes
through a maximum versus ∆S. For the
other compound compositions TS shows
signs of peaking at a higher ∆S. The tear
resistance (tear) shows an optimum vs.
∆S for all compositions. CS at -25°C is an
exception as it hardly correlates with ∆S.
It is close to 100% for the compounds
based on the natural oils. For the refer-
ence mineral oil compounds values below
70% are observed. Solidification of the
oils at -25°C is the most probable expla-
nation (cf. melting points in Table 2). In-
deed, a DSC experiment showed that the
33/50 (phr/phr) butter fat compound dis-
played an extra melting point at +6 °C as
well as the typical EPDM glass transition
temperature at -59°C. In summary, all
physical properties correlate with the
rheometer ∆S as a measure for crosslink
density in a well-known and expected
way, and, thus, correlate with the levels of
unsaturation in the (bio-based) oils as
discussed in the previous section.
For a given oil the physical properties
are usually found to correlate with the oil
and carbon black levels (compare various
lines in Figure 5), again in a way that is
commonly observed in rubber technolo-
gy studies [23,29,30]. Higher oil levels
result in lower hardness, moduli and TS
and in higher eab, CS at various test tem-
peratures and oil swell. It is noted that
the unsaturated bio-based oils not only
act as plasticisers, but also reduce the
crosslink density. Therefore, for a given
6 Fig. 6: Plot of
32 KGK · 01-2 2018
oil type the level used affects the me-
chanical properties in two ways, by coin-
cidence in a parallel fashion. Higher lev-
els of carbon black result in higher hard-
ness, moduli, TS and tear, in somewhat
higher CS at various temperatures and in
lower oil swells. For some reasons the
correlations between oil content and
tear resistance and between carbon
black content and eab (not shown) are
not easy to explain.
In a small side study with the 33/50
(phr/phr) butter fat/black compound at-
tempts were made to compensate for the
decrease of the crosslink density, due to
the competition for sulphur between
EPDM and the unsaturated, bio-based
oils. Countermeasures included increas-
ing the ENB content of the EPDM from
5.5 to 9.0 wt%, increasing the sulphur
content in the compound from 1.25 to
2.5 phr and increasing the amount of the
sulphur curative package, i.e. doubling
the amount of sulphur plus accelerators.
Each measure resulted indeed in an in-
creased crosslink density, as witnessed by
the higher rheometer torque difference
∆S, and in corresponding improvements
of the physical properties with higher TS,
lower high-temperature CS’s and lower
oil swells. Although these measures did
result in the desired changes, the abso-
lute effects were too small to be useful,
since the final vulcanisate properties did
not reach those of the mineral oil refer-
ence compound. However, combining an
increase of the ENB content from 5.5 to
9.0 wt% with either increasing just the
sulphur content or doubling the sulphur
curative package did result in a butter fat
compound with properties quite similar
to those of the mineral oil reference. Only
CS at -25°C could not be repaired by these
(combined) measures, which confirms
that the low-temperature CS of these
EPDM compounds is not only limited by
the crosslink density, but also by the so-
tensile strength
versus modulus
at 100% elonga-
tion as measure
for crosslink den-
sity for 33/50
(phr/phr) oil/
black vulcanisa-
tes before and
after ageing for
1 week at 70,
100 and 125°C.
lidification of the bio-based plasticisers
(see above).
The effects of the type and the
amount of bio-based oils on the vulcani-
sate properties are fully explained in
terms of their effects on the crosslink
density and, thus, are not that exciting.
Even the beneficial effects of increasing
the ENB content of the EPDM and/or
adding more sulphur (and accelerators)
on the vulcanisate properties are simply
the result of increased crosslink density.
Some properties after ageing show a dif-
ferent behavior though and, especially,
the tensile and tear strengths results af-
ter ageing are actually quite confusing
on first sight. The properties of the min-
eral oil reference vulcanisates change
upon ageing and change more with
harsher ageing conditions (original un-
aged → 70°C → 100°C → 125°C), leading
to a higher hardness and higher modulus
at 100% and a lower TS, eab and tear. The
compounds based on (hydrogenated) co-
conut oil, isotridecyl stearate, ethylhexyl
oleate and squalane show similar trends,
but not as strong. The compounds based
on squalane have properties after ageing
that are closest to the mineral oil refer-
ence. Interestingly, for the squalane com-
pounds the hardness change upon age-
ing decreases with increasing ageing
temperature, showing virtually no hard-
ness change at 125°C. Surprisingly, TS
and tear of the olive oil vulcanisates ac-
tually increase upon ageing. TS and tear
of the aged vulcanisates based on butter
fat and tung oil seem only to show some
scatter around the starting values of the
non-aged samples, almost suggesting
some sort of heat stabilising effect of
these two bio-based plasticisers.
These seemingly confusing ageing re-
sults for TS and tear can be rationalised
again in terms of the crosslink density.
Obviously, the rheometer torque differ-
ence can not be used as a measure for
the crosslink density of aged vulcani-
sates, so the modulus at 100% elonga-
tion (M100%) is used for that purpose.
Figure 6 shows a plot of TS versus the
corresponding M100% for the 33/50
(phr/phr) oil/black vulcanisates both be-
fore and after ageing at various condi-
tions. All data fall on one curve with the
exception of the tung oil data, which is
probably again explained by the high
content of oleostearic acid (see previous
section). Such a maximum of TS vs.
crosslink density is well-known from oth-
er rubber technology studies [29 and 30]
and is explained by a balance between
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 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

an increased number of network chains 5 Automotive, solid seal EPDM compound composition used for evaluating pyrolysis carbon
that are bearing the stress vs. the net- black versus standard furnace black.
work chains becoming less extensible compound formulation FEF black pyrolysis black
and, thus, more prone to rupture. The Keltan Eco 5470 EPDM 100 100
observation that for all compounds the N550 carbon black 120
hardness and the moduli increase and BBC 500 carbon black 135
eab decreases upon ageing, indicates
Superfine S whiting 85 85
that ageing results in continued
crosslinking of the EPDM rubber. Proba- Flexon 876 paraffinic oil 80 80
bly, desulphuration of the labile, longer PEG 4000 2 2
sulphur crosslinks exerts sulphur, which CaO-80 10 10
is used for further vulcanisation. For the ZnO active 5 5
mineral oil vulcanisate an increase in stearic acid 1 1
crosslink density due to ageing results in sulfur-80 1,8 1,8
a decrease of TS (right flank of TS curve in CBS-80 2,1 2,1
Figure 6). For the coconut oil and butter TMTD-80 0,5 0,5
fat vulcanisates TS increases and then ZDMC-80 1,2 1,2
decreases upon ageing (around maxi- ZDBC-80 2,5 2,5
mum of TS vs. M100% curve). Finally, for total 411,1 426,1
the olive oil compound increased MDR rheometry @ 180°C
crosslinking due to ageing results in a TS ML (dNm) 1,1 1,6
increase (left flank of TS curve). Plots
MH-ML = ∆S (dNm) 18 17
similar to that in Figure 6 have been con-
ts2 (min) 0,6 0,7
structed for the tear strength of the
tc90 (min) 1,7 3,7
33/50 (phr/phr) oil/black compositions
and for TS and tear of the other com- vulcanisate properties
pound compositions. These findings sug- hardness (IRHD) 68 68
gest a new way of producing (EPDM) modulus @ 100% (MPa) 2,8 2,0
rubber products with optimum heat age- modulus @ 300% (MPa) 8 6
ing resistance. By on purpose slightly tensile strength (MPa) 11 10
under-curing a compound, vulcanisates elongation at break (%) 440 501
with a somewhat sub-optimum TS are rebound resilience (Schob) (%) 35 34
obtained (just on left side of TS optimum compression set 24 hr @ 100°C (%) 63 59
in Figure 6). Upon heat ageing further after ageing for 168 hr @ 100°C
crosslinking occurs, which results in a
hardness (IRHD) 78 78
small increase of TS and upon further
modulus @ 100% (MPa) 6,8 5,4
ageing in a small decrease of TS (passing
TS maximum). Overall, such a sub-opti- tensile strength (MPa) 11 11
mum vulcanised EPDM product will elongation at break (%) 183 207
show rather good TS retention upon age-
ing. Obviously, sub-optimum vulcanisa- related to the changes in the crosslink longer vulcanisation time tc90. This is a
tion of the original compound is not density, as a result of continued crosslink- known phenomenon of the use of pyrol-
beneficial for the elasticity and oil resist- ing upon ageing. ysis black, probably due to the fact that
ance. As usually, one has to find the best pyrolysis black not only consists of car-
balance in properties for the particular Sustainable fillers bon black, but also contains around 5
EPDM application. wt% of zinc oxide and zinc sulfide (Table
In summary, the properties of the Black fillers 3). The presence of zinc oxide/sulfide is
EPDM vulcanisates with (bio-based) oils Our first study with respect to alterna- obviously related to the presence of zinc
simply follow correlations with the tive fillers was to replace the standard oxide and other zinc salts, like zinc soaps
crosslink density as known from rubber FEF N550 carbon black by pyrolysis black and accelerators, in the original tire com-
textbooks, which in its turn is deter- in an automotive, solid seal formulation. position. In principle, some of the addi-
mined by the competition for sulphur Previous compound studies have shown tional ZnO could be left out from the EP-
vulcanisation between EPDM and the differences in the reinforcement behav- DM compound formulation. Compared
unsaturated oils as shown in the previ- ior, because of the somewhat lower sur- to other commercially available pyrolysis
ous section. As a result, increasing the face area and structure of the pyrolysis blacks the particular pyrolysis black used
EPDM ENB content and the amount of black compared to N550 [13]. Therefore, in this study actually shows a rather lim-
sulphur (and accelerators) provides an the pyrolysis black level was chosen as ited increase of tc90. For the same rea-
easy way to compensate for the loss in 12.5% higher than the N550 level (Table son pyrolysis black also contains silica
crosslink density and, thus, to “repair” 5). The rheometer data show that the from the original tire formulation, the
the vulcanisate properties. Plots have scorch time ts2 and the final state of cure level varying with the tire type used as
been constructed showing that the ∆S are quite comparable, but that the raw material for the pyrolysis process. As
changes of TS and tear upon ageing are compound with pyrolysis black shows a an aside, it is worth noting that the Pol-

www.kgk-rubberpoint.de KGK · 01-2 2018 33

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
yAromatic Hydrocarbon (PAH) content of
the pyrolysis black used is below the de-
tection limit, whereas for furnace blacks
PAH levels are detectable. The data in
Table 5 indicate that all the physical
properties before and after ageing and
the elastic properties of the vulcanisates
are similar when the pyrolysis black con-
tent is increased by 12.5%. The overall
conclusion is that pyrolysis black can be
considered as a technical alternative for
medium reinforcing furnace blacks.
White fillers
A white bull-eye EPDM compound with
silica and clay as white fillers in presence
of silica coupling agent was used to eval-
uate the performance of rice husk ash
and micro-cellulose as bio-based fillers
with the idea to replace the reinforcing
silica (Table 6). The compound Mooney
viscosity (ML) of the first silica control
compound, mixed with a starting mixer
body temperature of 70°C, is rather low.
This is probably due to polymer degrada-
tion, since it took an excessively long time
(around 17 min.) to reach a batch tem-
perature of 150°C, which is required to
reach completion of the silanisation reac-
tion. Therefore, all additional experi-
ments were performed with a starting
body temperature of 130°C, which gave
reasonably reproducible results for the
silica control compounds. Nevertheless,
for both the rice husk ash and micro-cel-
lulose compounds lower compound ML
were measured, suggesting a lack of cou-
pling of these fillers to the rubber. The
addition of maleated EPM to the micro-
cellulose compound resulted in a com-
pound ML which is comparable to that of
the silica reference, suggesting an im-
proved coupling of the cellulose fibers to
the EPDM rubber matrix. The rheometer
data show that the vulcanisation kinetics
of the compounds with the bio-based,
white fillers are comparable to those of
the silica reference compound (similar ts2
and tc90 values). The ∆S values of the bio-
based filler compounds are significantly
smaller than that of the silica compound
though. This probably does not reflect a
lower state of cure for the former, but a
lack of reinforcement, since the hardness,
TS, eab and tear of all the compounds
with bio-based, white fillers are (much)
lower, compared to the silica reference.
Comparing the physical properties of the
compounds with the bio-based, white
fillers shows that rice husk ash actually
yields the poorest performance. The two
micro-cellulose grades show similar prop-
34 KGK · 01-2 2018
erties. The addition of maleated EPM to
the micro-cellulose compound results in
improved eab and tear, which is probably
due to better dispersion/coupling of the
cellulose fibers. The properties after age-
ing are quite similar for all white fillers,
when expressed as relative changes (data
not shown), with micro-cellulose Arbocel
UFC M8 being a positive exception (low-
est relative change in tensile properties
upon ageing). The CS values at 23 and
70°C are comparable for all fillers, but CS
at 100 °C is the lowest for the silica con-
trol and one of the micro-cellulose sam-
ples. The overall conclusion of this limited
screening of some bio-based, white fillers
is that they do not have the reinforcing
properties of silica. Indeed, a similar per-
formance has been observed in other
studies on bio-based fillers in rubber
compounds [9-12], although rice husk
ash seems to be finding applications in
tire treads [31]. This disappointing result
is probably due to a lower surface area/
structure of the bio-based fillers com-
bined with a lack of reactivity to silane
coupling. Still, these bio-based, white
fillers will be used as green alternatives
for inert white fillers in the final study on
compounds with maximised sustainabil-
ity content as presented in the final sec-
tion.
Maximising content of sustainable
ingredients
In this study the best options from the
screening studies in the previous sec-
tions were combined in a final effort to
maximise the content of sustainable in-
gredients in EPDM compounds. Two
highly filled, automotive, solid seal EP-
DM compounds have been used for that
purpose. The first compound has low-
temperature flexibility for dynamic
sealing applications and, thus, is based
on an amorphous EPDM (Table 7). The
second compound is typical of a static
seal, where low-temperature flexibility is
not required and, thus, is based on a crys-
talline EPDM. It is noted that these two
automotive, sealing compounds are mo-
re highly filled than typically practiced in
industry to maximise the sustainable
content of the compounds. Squalane is
used as plasticiser, replacing the mineral
oil. As in the previous section the content
of pyrolysis carbon black was chosen
12.5% higher than the corresponding
furnace N550 black content. Rice husk
ash was used as an inert filler (see previ-
ous section), replacing the calcium car-
bonate whiting. The total amount of
green ingredients, viz. the sum of the
bio-based part of the Keltan Eco EPDM
rubber, the green oil and the white filler
plus the sustainable black filler (Table 7)
amounts to 86% for the dynamic, auto-
motive seal and as high as 90% for the
static, automotive seal, due to the higher
weight content of sugar-cane-derived
ethylene in the crystalline EPDM used in
the latter compound.
Table 7 shows that
the compound ML of both sustainable
compounds are significantly below those
of the reference compounds by about 10
MU, which is due to the lower molecular
weight of squalane, as discussed above.
The Garvey strip extrusion results show
that the extruder throughput of the sus-
tainable compounds is comparable to
those of the reference compounds, but
the head pressure is much lower for the
former. As a result, the extruder through-
put normalised to the pressure is signifi-
cantly higher for the sustainable com-
pounds, which is in agreement with the
lower compound ML. The total score for
edge, corner and surface for the Garvey
die ranking is the maximum of 12 for all
extruded strips, showing excellent pro-
cessing also for the sustainable com-
pounds with squalane, pyrolysis black and
rice husk ash. The scorch sensitivity of the
sustainable compounds is substantially
less than that of the reference com-
pounds, as witnessed by the much longer
Mooney scorch time ts5. The rheometer
ts2 value of both sustainable compounds
are similar to those of the reference com-
pounds. The same now holds for tc90 val-
ues, which is not consistent with the
longer tc90 values presented in the previ-
ous section. The rheometer torque differ-
ence ∆S of the sustainable compounds is
comparable to those of the reference
compounds, which explains why hard-
ness, eab and CS at 23 and 70°C are also
comparable. Interestingly, the CS at -25°C
of the dynamic automotive seal based on
the amorphous EPDM with squalane as
plasticiser is much better than that of
the paraffinic oil reference (42 vs. 71%).
This is because squalane has a much
lower glass transition temperature com-
pared to mineral oil (-105 vs. around
-70°C) and, thus, is a superior plasticiser
at (very) low temperatures. The tensile
and tear strengths and CS at 100°C of the
sustainable compounds are somewhat
inferior. The test results after ageing of
the sustainable compounds are clearly
inferior to those of the reference com-
pounds. This is fully accountable to the
use of squalane as bio-based oil, since
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 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

6 White bull-eye EPDM compound composition, used for evaluating rice husk ash and micro-cellulose versus silica.
compound formulation silica silica rice husk ash micro-cellulose 1 micro-cellulose 1 + micro-cellulose
maleated EPM 2
starting mixer temperature (°C) 70 130 130 130 130 130
Keltan 6471 EPDM 115 115 115 115 115 115
Keltan 1519R maleated EPM 5
PoleStar 200R clay 110 110 110 110 110 110
Ultrasil VN 3 silica 30 30
rice husk ash 30
Arbocel UFC M8 micro-cellulose 30 30
Arbocel FD 600-30 micro-cellulose 30
titanium dioxide 9 9 9 9 9 9
Sunpar 2280 mineral oil 70 70 70 70 70 70
Si 69 coupling agent 2 2 2 2 2 2
TEA 2 2 2 2 2 2
ZnO 5 5 5 5 5 5
stearic acid 1 1 1 1 1 1
sulfur-80 0,6 0,6 0,6 0,6 0,6 0,6
DPTT-70 1,14 1,14 1,14 1,14 1,14 1,14
DTDM-80 1,2 1,2 1,2 1,2 1,2 1,2
MBT-80 1,2 1,2 1,2 1,2 1,2 1,2
TMTD-70 1,14 1,14 1,14 1,14 1,14 1,14
ZDBC-80 2,5 2,5 2,5 2,5 2,5 2,5
total 351,8 351,8 351,8 351,8 356,8 351,8
compound properties
ML 1+4 @ 100 °C (MU) 18,8 28,9 17,6 24,0 28,3 23,8
ts5 @ 125 °C (min) 14,2 13,6 10,4 13,8 14,8 14,6
ML (dNm) 0,28 0,52 0,23 0,34 0,40 0,32
MH - ML = ΔS (dNm) 5,7 8,2 5,7 6,3 6,7 6,7
ts2 (min) 1,4 1,2 1,3 1,4 1,4 1,5
tc90 (min) 3,5 3,1 2,6 3,2 3,3 3,2
vulcanisate properties
hardness (Sh A) 42,1 49,3 41,5 46,7 47,1 48,1
modulus @ 100% (MPa) 1,5 1,8 1,4 1,9 2,0 1,6
modulus @ 300% (MPa) 3,9 4,7 3,9 4,6 4,0 4,0
tensile strength (MPa) 7,2 9,4 5,4 6,1 6,3 5,7
elongation at break (%) 683 647 574 487 718 551
tear resistance Delft (N/mm) 27,1 31 23,3 26,4 29,2 22,5
compression set 72h @ 23 °C (%) 12,1 10,5 11,1 12,8 13,5 12,2
compression set 24hr @ 70 °C (%) 19,9 18,2 18,1 19,7 22,2 20,3
compression set 24 hr @ 100 °C (%) 43,2 36,4 44,7 37,5 41,5 40,7
after ageing for 168 hr @ 100 °C
hardness (Sh A) 46,6 53,8 45,6 50,5 50,7 51,4
modulus @ 100% (MPa) 1,9 2,7 1,9 2,5 2,7 2,0
modulus @ 300% (MPa) 5,1 6,7 4,4 5,5 5,1 4,8
tensile strength (MPa) 6,6 8,7 4,8 6,6 5,8 5,3
elongation at break (%)] 468 459 381 407 466 365
tear resistance Delft (N/mm) - 31,1 20,3 24,6 28,7 21,3

the weight loss of the sustainable com-
pounds upon ageing for 168 hr @ 135°C is
similar to the original squalane content
(19.2 versus 20.2 wt% and 20.2 versus
20.9 wt% for the dynamic and static seal
compounds, respectively). There is hardly
any weight loss for the reference com-
pounds with Sunpar 2280 mineral oil up-
on ageing. It seems that despite an at-
mospheric boiling point of around 350°C,
squalane is still too volatile at 135°C com-
pared to regular mineral oil. This seems to
be no issue for ageing at temperatures up
to 125°C (see previous sections), but be-
comes critical at 135°C and, thus, is a
topic for further investigations.
To have a fully sustainable EPDM com-
pound with 100% sustainable ingredi-

www.kgk-rubberpoint.de KGK · 01-2 2018 35

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

7 Composition of highly filled, automotive, solid seal compounds based on amorphous or crystalline EPDM, used to maximise the content of
sustainable ingredients.
compound formulation dynamic, automotive seal static, automotive seal
traditional sustainable traditional sustainable
Keltan 8550 EPDM 100
Keltan Eco 8550 EPDM 100
Keltan 5470 EPDM 100
Keltan Eco 5470 EPDM 100
N550 carbon black 155 147
BBC 500 carbon black 174 165
Superfine S whiting 77 110
rice husk ash 77 110
Sunpar 2280 mineral oil 98 100
squalane 98 100
CaO 5 5 5 5
PEG 1000 1,5 1,5 1,5 1,5
ZnO active 3 3 3 3
stearic acid 1 1 1 1
sulfur-80 0,8 0,8 0,8 0,8
DPG-80 0,5 0,5 0,5 0,5
TBBS-80 0,625 0,625 0,625 0,625
CBS-80 1,25 1,25 1,25 1,25
ZBEC-70 1,7 1,7 1,7 1,7
TP-50 2 2 2 2
CLD-80 1 1 1 1
Vulcalent E/C 0,8 0,8 0,8 0,8
total 449,2 468,2 476,2 494,2
percentage bio-based/sustainable (%) 0 86 0 90
compound properties
extruder throughput (g/min.) 32,6 32,8 35,2 34,8
extruder head pressure (bar) 27 21 26 21
die swell (%) 11,9 18,9 8,0 9,0
Garvey die ranking (total score) 12 12 12 12
ML 1+4 @ 100 °C (MU) 59,5 47,8 55,0 44,5
ts5 @ 125 °C (min) 18,0 26,4 19,1 28,0
ML (dNm) 1,82 2,63 1,33 2,31
MH - ML = ΔS (dNm) 13,2 13,6 14,1 14,4
ts2 (min) 1,0 1,1 1,2 1,1
tc90 (min) 2,8 3,2 3,6 3,3
vulcanisate properties
hardness (Sh A) 67,3 66,9 67,9 68,9
modulus @ 100% (MPa) 3,5 2,3 3,2 2,4
modulus @ 300% (MPa) 9,5 - 8,3 7,3
tensile strength (MPa) 9,5 7,5 9,5 8,3
elongation at break (%) 304 291 368 349
tear resistance Delft (N/mm) 28,4 20,6 31,6 25,6
compression set 24 hrs @ -25 °C (%) 70,8 42,3 97,6 97,8
compression set 72 hrs @ 23 °C (%) 9,2 12,7 27,2 25,4
compression set 24 hrs @ 70 °C (%) 12,1 13,1 13,7 17,3
compression set 24 hrs @ 100 °C (%) 27,2 36,7 29,1 44,9
after ageing for 168 hr @ 135 °C
hardness (Sh A) 72,8 83,3 75,8 84,8
modulus @ 100% (MPa) 6,1 - 5,2 -
tensile strength (MPa) 9,7 7,7 9,7 10,1
elongation at break (%) 179 7 226 46
mass change upon ageing (%) -0,6 -20,2 -0,7 -19,2
after ageing for 336 hr @ 135 °C
hardness (Sh A) 74,8 93,4 76,7 93,6
modulus @ 100% (MPa) 7,3 - 6,2 -
tensile strength (MPa) 10,2 11,1 10,3 13,7
elongation at break (%) 161 14 207 26

36 KGK · 01-2 2018 www.kgk-rubberpoint.de


ents, the residual 10 – 15% non-sustaina-
ble content of the EPDM compounds in
Table 7 should be further addressed. A
major step would be to develop a second
generation Keltan Eco EPDM not only
based on green ethylene, but also on
green propylene, which would bring the
total bio-based content of EPDM rubber
to ~95% and of the EPDM compounds al-
so to ~95%. Currently, the production of
propylene based on green resources is
being explored [32], amongst others via i)
production of methanol from wood, fol-
lowed by conversion of methanol to pro-
pylene, ii) sugar-based routes either via
ethanol to ethylene and then via metath-
esis to propylene or via isopropanol to
propylene and iii) direct fermentation of
glucose using genetically engineered mi-
cro-organisms to a mixture of olefins, in-
cluding propylene. The finishing touch
will then be a green diene for EPDM. As
an example to stimulate interest, it is
mentioned that first experiments with an
amorphous EPDM with 7 wt% 2,4-dime-
thyl-2,7-octadiene [33] (natural terpene
supplied by Dérivés Résiniques & Terpé-
niques) as diene showed fair sulphur vul-
canisation characteristics and corre-
sponding vulcanisate properties, similar
to a 4.5 wt% ENB-EPDM. The final step
towards a fully sustainable EPDM rubber
compound will require the development
of bio-based rubber additives, especially
the curatives, which considering their
chemical structure will be a more chal-
lenging development.
Conclusions
In an effort to develop EPDM compounds
based on Keltan Eco EPDM with the high-
est level of sustainable ingredients a se-
ries of bio-based oils and sustainable
fillers were screened. Typical issues en-
countered when exploring the relatively
polar and unsaturated natural oils in
EPDM compounds are the lack of com-
patibility (mixing issues and oil bleeding)
and the competition for sulphur vulcani-
sation (reduced crosslink density and cor-
responding inferior vulcanisate proper-
ties). Modified natural oils, such as hy-
drogenated coconut oil and trans-esteri-
fied mono-esters, have improved
compatibility and/or vulcanisation per-
formance. Squalane (“EPM hexamer”)
provides the best bio-based alternative
for mineral oil plasticiser in this study,
since it is as apolar as EPDM and is fully
saturated. As far as sustainable fillers are
concerned, pyrolysis black was shown to
have a reinforcing efficiency 90% of that
www.kgk-rubberpoint.de
ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
of furnace N550 black. Rice husk ash and
micro-cellulose do not show reinforcing
properties, but can still be used as inert,
white fillers, substituting traditional,
mineral white fillers. Combining these
leads has resulted in automotive solid
seal EPDM compounds based on Keltan
Eco with more than 85% sustainable con-
tent and properties reasonably compara-
ble to the reference EPDM compounds.
Acknowledgements
We would like to acknowledge dr. Nikhil
Kumar Singha of the Rubber Technology
Centre of the Indian Institute of Technol-
ogy in Kharagpur (India) for a useful liter-
ature survey on green rubber compound-
ing ingredients. Next, we would like to
thank Rutteman, Friesland Campina,
Amyris, Cargill, Hansen+Rosenthal and
Emery Oleo Chemicals for supplying us
with the samples of the bio-based oils
and Black Bear, Sílica Verde do Arroz and J.
Rettenmaier & Söhne for the alternative
filler samples used in this study. We also
express our gratitude to both the AR-
LANXEO Polymer Testing group in Lev-
erkusen (Ge) and the former Keltan Rub-
ber Processing & Testing Laboratory in
Geleen (NL) for performing all the mixing
and testing.
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