PRÜFEN UND MESSEN

TESTING AND MEASURING

Eco-friendly oils · Aromatic oil · Rubber

compounds · Vulcanization · Mechani-
cal properties
The performances of new six eco-
friendly oils and standard aromatic oil
in rubber compounds such as NR, SBR,
NR/SBR and BIIR/NR blends is compa-
red. Cure characteristics of the com-
pounds and physico-mechanical pro-
perties of the vulcanizates were
measured and compared with refe-
rence compounds containing aromatic
oil. This study may provide valuable
data for small producers if any formula-
tion adjustments are required in order
to match the performance previously
obtained by aromatic oils and their
possible preferences.
Substitution von aromatischen
Prozessölen in Kautschukmi-
schungen
Umweltfreundliche Öle · aromatische
Öle · Kautschukmischungen · Vulkani-
sation · mechanische Eigenschaften
Die Auswirkung von sechs umwelt-
freundlichen Ölen und aromatischem
Standardöl auf die Eigenschaften von
NR, SBR, NR/SBR und BIIR/NR Mi-
schungen und Vulkanisaten werden
untersucht. Die Vernetzungscharakteri-
stik der Compounds und die physika-
lisch-mechanischen Eigenschaften der
Vulkanisate wurden gemessen und mit
den Ergebnissen der Referenzsysteme
mit aromatischem Öl verglichen. Diese
Untersuchungen können in kleinen
Betrieben für die Rezepturanpassung
nützlich sein.
Substitution of Aromatic
Processing Oils in Rubber
Compounds
Rubber materials are widely used in human
life. Most common usage is mainly in tires,
automotive supply industry, white goods,
constructions, textiles and biomedical ap-
plications. The main components of rubber
compounds are rubber, reinforcing fillers,
process oils and oil based softeners. Other
additives, like stabilizers, antioxidants, vul-
canization agents are included in less
amount. Mineral oils with different compo-
sitions (paraffinic, naphthenic and aromatic)
have been proven their importance as sof-
teners and extender process oils in rubber
compounds and have been used for more
than 100 years. Rubber compounds exhibit
a very complex behavior during mixing and
curing stages. This behavior depends strict-
ly on the filler loading, the dispersing quali-
ty of fillers and the other additives. One of
the main roles of processing oils is to reduce
the viscosity of filled rubber mixes and im-
prove processability of compounds. Another
quite important contribution of the oils is to
1 Commercial process oils used
Oil Type Commercial name
DAE Aromatic oil (Reference)
MES Vivatec 200
Nytex 832
TDAE Vivatec 500
Nytex 840
NAP Nytex 4700
Octopus N317
replaced with alternative eco-friendly low
polyaromatic hydrocarbon content process
oils [1].
According to the European Parliament and
of the Council Regulation Concerning the
REACH legislation (EC 18/09/2006), highly
aromatic oils containing polycyclic aromatic
hydrocarbons were banned as of January 1 st,
2010. The PAH limits in the process oil must
be less than 3 % by mass as measured accor-
ding to IP346 method [2]. Rubber process oil
manufacturers have offered some alterna-
tive eco-friendly low PAH content process
oils such as TDEA, MES and naphthenic oils
for replacing aromatic ones in rubber com-
pounds. Also, in the tire and technical rub-
ber goods industry, the big companies have
already realized the required receipt modi-
fications as confidentially. However, to the
best knowledge of the authors, a limited
number of studies are published on new
process oils with low content of aromatic
species [3-6].
Supplier Code
Çakır Kimya, Turkey DAE
Hansen&Rosental MES-1
Nynas MES-2
Hansen&Rosental TDAE-1
Nynas TDAE-2
Nynas NAP-1
Petroyağ, Turkey NAP-2

improve the filler dispersion and to increase Authors

Figures and Tables:
By a kind approval of the authors
the quality of rubber compounds. Aromatic
M. Öter, B. Karaağaç*, Veli Deniz,
process oils are widely used in many types Kocaeli, Turkey
of rubber compounds due to their compati-
bility to SBR and other unsaturated polydi- Corresponding author:
enes. They are traditionally used as extender Bağdagül Karaağaç
oils. The relatively low price of this group of Kocaeli University, Engineering Faculty
products contributes to a given extend to Department of Chemical Engineering
Umuttepe Campus
the wide spread application of these recipe
41380, Kocaeli, Turkey
ingredients especially in tire compounds. Tel: +9 0262 3033533
However, aromatic oils have substantially Fax: +90 262 3591262
carcinogenic potential and are tend to be E-mail: bkaraagac@kocaeli.edu.tr

48 KGK · September 2011 www.kgk-rubberpoint.de

2 Properties of process oils
Property Unit DAE MES-1 MES-2 TDAE-1 TDAE-2 NAP-1 NAP-2
3
Density 15° C kg/dm 0.990 0.915 0.925 0.95 0.923 0.94 0.902
2
Viscosity 40° C mm /s 1240 210 226 410 376 700 22
100 °C mm2/s 26 16 13.3 18.8 18.5 28 3.7
Flash point PM °C 200 270 226 272 243 220 174
Pour point °C 40 -6 -24 27 -18 -15 -42
Sulfur content % 6 0.5 0.06 0.8 0.11 0.4 0.02
Aniline point °C 60 97 92 68 96 90 74
Refractive index 20 °C 1.586 1.505 1.507 1.528 1.508 1.546 1.501
Viscosity gravity Constant 0.891 0.844 0.859 0.888 0.853 0.866 0.861
Color >8 8 1.5 8 <2 >8 0.5
Carbon type distribution CA % 20 15 13 25 12 25 11
CN % 41 27 38 30 36 21 42
CP % 39 58 49 45 52 54 47
Appearance 15 °C dark black clear clear dark brown clear dark black clear
DMSO PAH % >3 <2.5 2 <2.5 2 <3 <3

3 Mixing procedure of rubber compounds

In this study, the performance of six new king temperature on the mill did not exceed Step 1. Master batch Time (min)
eco-friendly process oils which are available 80 °C and rotor speed was 20 rpm. Mixing
Charge Rubbers 0.0-4.0
in the market were evaluated and also com- procedure is given in Table 3.
Filler + process additives 4.0-4.5
pared with that of standard aromatic oil in The rheological properties of rubber com-
Discharge mill 16.0-18.5
different types of rubber compounds. 28 pounds were measured by using a moving
Step 2. Final batch
different compounds were prepared by die rheometer (Alpha Technologies
using new eco-friendly oils and aromatic oil MDR2000) at 160 °C for 20 min. Process cha- Master batch 0.0-3.0
in different rubber compositions such as NR, racteristics of uncured compounds were Vulcanization agents 3.0-3.5
SBR, NR/SBR and BIIR/NR blends. The cure determined by means of a Mooney visco- Discharge mill 7.5-9.0
characteristics of the compounds and phy- meter (Alpha Technologies MV2000) at
sico-mechanical properties of the vulcani- 100 °C. The compounds were vulcanized in
zates were investigated and compared with a hydraulic press at 160 °C under 10 MPa the vulcanizates were determined by using
results of the reference compounds contai- pressure for specified times which corre- Zwick Tensile Testing Machine (Model Z010)
ning aromatic oil. spond to their t90. Specimens were prepared according to ASTM D412. Hardness of vulca-
from compression molded sheets (2 mm in nizates where measured by using a Shore A
Experimental thickness) to study the mechanical proper- type durometer according to ASTM D2240.
ties of vulcanizates. Tensile properties of The vulcanized samples were subjected to
Materials
Natural rubber (Standard Indonesian Rub-
ber, SIR20), SBR1502 (Petrohemija HIPREN 4 Typical rubber compounds prepared
1502T) containing 25 % styrene and 75 % N100 Compounds S100 Compounds N50S50 Compounds B60N40 Compounds
butadiene, and Bromobutyl rubber (BIIR, Material phr Material phr Material phr Material phr
Exxon Mobil) were used as rubber matrix. SIR20 100 SBR1502 100 SIR20 50 SIR20 40
Carbon black (N220, N234, N550 and N660) SBR 1502 50 BIIR 60
and silica (Ultrasil VN2) that are commer- N550 28 N234 70 N220 50 N660 60
cially used in rubber and tire industries Silica 16
were used as reinforcing fillers in the com-
Process oila 4 Process oila 6 Process oila 3 Process oila 8
pounds. Six different process oils were used
in compounds. The main properties of these ZnO 5 ZnO 2.5 ZnO 3 ZnO 1
oils are given in Table 1 and Table 2, respec- Stearic acid 1 Stearic acid 1.5 Stearic acid 1 Stearic acid 2
tively. Peptizer 0.1 Wax 1 Peptizer 0.2
Fenolic resin 1.5 MC WAX 1 Fenolic resin 5 Fenolic resin 4
Methods TMQ 1 TMQ 1 Hydrocarbon Resin 1 Hydrocarbon Resin 7
For all compounds, the ingredients were 6PPD 1.5 IPPD 1 TMQ 1
mixed as a master batch by using a labora- Silane 3 6PPD 1.5
tory two-roll mill with 2 liters capacity and Sulfur 2.5 Sulfur 2.5 Sulfur 1.5 Sulfur 0.5
friction factor 1.2. Vulcanizing agents were CBS 1.3 CBS 1.3 CBS 1 MBTS 1.5
then added into the compounds. The wor- a
DAE, MES-1, MES-2, TDAE-1, TDAE-2, NAF-1 and NAF-2, respectively

www.kgk-rubberpoint.de KGK · September 2011 49

 PRÜFEN UND MESSEN
TESTING AND MEASURING

5 Effects of process oil type on the properties of N100 compounds In this study, it has been intended to evalu-
N100 Compounds with… DAE MES-1 MES-2 TDAE-1 TDAE-2 NAP-1 NAP-2 ate the mechanical properties, both before
and after aging, in terms of the relative dif-
ML (dNm) 1.33 1.70 1.56 1.40 1.58 1.55 2.70
ferences in properties of with DAE and with
MH (dNm) 13.40 12.21 11.93 13.73 13.86 13.23 13.84
Rheological
properties

alternative oil compounds. Normally, it can

ts2 (min) 2.72 2.93 2.97 2.83 2.83 3.05 2.70
be expected that NR and especially SBR and
t90 (min) 5.39 5.67 5.72 5.52 5.50 5.61 5.44
Mooney viscosity
NR/SBR blend based compounds may have
ML(1+4)@100 °C 35.7 34.2 33.4 36.4 34.6 34.8 35.3 a higher degree of compatibility with high
aromatic oils than with naphthenic oils due
Physico-mechanical properties

to the similar graded polarities of the oil

Before aging

Hardness (Shore A) 54.0 53.0 55.0 52.0 54.0 52.0 53.0

Tensile strength (MPa) 19.0 20.1 21.1 20.1 20.5 20.3 18.8 constituents and the chain segments of the
Elongation @break (%) 515.0 551.0 510.0 549.0 528.0 546.0 519.0 rubber matrix. For N100 compounds, all al-
300 % Modulus (MPa) 8.7 8.1 9.6 8.1 9.1 8.5 8.6 ternative oils lead to mechanical properties
very similar with the reference. However,
small changes were observed with naph-
After aging

Hardness
(Shore A) 59.0 58.0 60.0 60.0 61.0 58.0 59.0 thenic oils, as contrary to polarity relation-
Tensile strength ship between NR and naphthenic process
(MPa) 13.5 11.9 13.7 12.1 13.3 12.7 12.2
oils. In the case of SBR containing com-
pounds, the results obtained show that
MES-1 is the most suitable oil for the substi-
6 Effects of process oil type on the properties of S100 compounds
tution of DAE. However, NAPs and TDAE-1
S100 Compounds with… DAE MES-1 MES-2 TDAE-1 TDAE-2 NAP-1 NAP-2
can be a secondary alternative for S100 and
ML (dNm) 3.41 3.69 3.43 3.69 3.64 3.45 3.76 N50S50 compounds, respectively. These re-
Rheological

MH (dNm) 18.49 18.52 17.61 18.99 18.51 20.40 19.96 sults can be attributed to their high viscosi-
properties

ts2 (min) 3.42 3.44 3.58 3.27 2.77 3.13 3.15 ty gravity constants (VGC) that represents
t90 (min) 10.76 10.35 10.50 9.94 10.56 10.52 10.37 better compatibility with rubber matrix and
Mooney viscosity so better mechanical properties [7]. For
ML(1+4)@100 °C 47.3 48.0 47.9 49.7 48.4 47.9 49.8
BIIR/NR compounds, MES-1 provides mini-
Physico-mechanical properties

Before aging

Hardness (Shore A) 73.0 73.0 72.0 71.0 74.0 73.0 71.0 mum change in mechanical properties. This
Tensile strength (MPa) 15.2 15.2 13.9 16.7 15.2 14.7 15.6 can be attributed to similar polarity of BIIR
Elongation @break (%) 487.0 507.0 447.0 527.0 434.0 476.0 472.0 and MES.
300 % Modulus (MPa) 6.6 6.1 6.5 6.3 8.7 6.7 7.3 In order to describe the consequences of
thermal aging, it is useful to determine the
changes in tensile strength and hardness of
After aging

Hardness
(Shore A)
Tensile strength
(MPa)
thermal aging using an air-circulating oven.
The aging temperature was selected as
80 °C and duration was 12 hours. The ten-
sile properties and the hardness values of
the aged samples were determined using
the same procedures that were followed for
unaged ones.
Results and discussion
In this study, the effects of process oil type
on four different rubber compounds that
are typically used in tire industry were eva-
luated. The compound receipts are indica-
ted in Table 4. The amount of the selected
process oils (DAE, MES-1, MES-2, TDAE-1,
TDAE-2, NAP-1 and NAP-2) is systematically
varied in all compounds. Rheological and
physico-mechanical properties of N100,
S100, N50S50 and B60N60 compounds
with different process oils are given in Ta-
ble 5-8. Physico-mechanical properties after
thermal aging are also given in these tables.
77.0 75.0 75.0 74.0 76.0 74.0 74.0
13.1 12.0 11.9 15.0 12.0 13.6 14.3
The experimental results showed that rhe-
ological properties of the evaluated rubber
compounds after the substitution of con-
ventionally used aromatic oils have not been
deteriorated significantly. The Mooney vis-
cosities indicate that major processing cha-
racteristics of the compounds remained al-
most unchanged by using the same amount
of the various process oils. The use of eco-
friendly process oils causes small variations
in the curing behavior. These changes can be
attributed to the different content in aro-
matic species in the oils. The variations are
more evident for NAP-2 in NR compounds.
This result can be attributed to poor compa-
tibility of NAP-2 with rubber matrix in mi-
xing stages and its low viscosity (especially
at low temperatures). Briefly, with this data
it is possible to make fine tunings in com-
pound receipts according to the expecta-
tions about curing characteristics of speci-
fied rubber compounds.
vulcanizates and to evaluate from the diffe-
rence the effects of process oil type. The
hardness values of the new alternative
compounds have remained in an acceptable
range. This trend was also valid after ther-
mal aging. Vulcanizates containing aroma-
tic process oil have been found not to be
durable under thermal aging. Deterioration
in tensile strength of the aged vulcanizates
up to 30 % was observed.
If we compare aged N100 compounds in
terms of the difference in mechanical pro-
perties of the compounds with DAE and
with alternative oils, we can say that NAPs
do not cause a significant change in hard-
ness and tensile strength of NR based vulca-
nizates. Due to the well known fact that NR
compounds are generally not resistant to
thermal aging. It is an important finding
that naphthenic oils can be used for re-
placement of aromatic oils when mechani-
cal properties have great importance after
aging. For S100 compounds, the changes in
main characteristics after aging do not de-
pend on the oil type, significantly. However,
it can be said MES and TDAE provide more
similar aging behavior to DAE. On the other

50 KGK · September 2011 www.kgk-rubberpoint.de

hand, it is showed that those alternative 7 Effects of process oil type on the properties of N50S50 compounds
oils improved the aging resistance of NR/ N50S50 Compounds with… DAE MES-1 MES-2 TDAE-1 TDAE-2 NAP-1 NAP-2
SBR and BIIR/NR based vulcanizates.
ML (dNm) 2.22 2.66 2.84 2.37 2.69 1.93 2.80

Rheological
MH (dNm) 14.08 13.87 14.67 13.91 14.43 14.14 14.47

properties
Conclusion ts2 (min) 7.99 7.90 7.87 7.51 7.83 8.00 7.56
In this study, various basic rubber receipts
t90 (min) 18.34 19.46 18.91 18.98 19.06 19.75 18.68
which contain NR, SBR, NR/SBR and BIIR/NR Mooney viscosity
blends as rubber matrix were prepared by ML(1+4)@100 °C 36.2 36.6 35.8 36.9 36.7 35.6 37.0
using aromatic oil and six new low PAH con-

Physico-mechanical properties

Before aging
tent process oils. Using eco-friendly process Hardness (Shore A) 63.0 64.0 65.0 63.0 66.0 62.0 65.0
oils, rheological, physical and mechanical Tensile strength (MPa) 18.5 17.2 19.3 19.2 19.5 16.9 18.3
properties changed only in a narrow range Elongation @break (%) 560.0 562.8 612.0 578.0 686.0 576.0 617.0
for un-aged vulcanizates. For various rubber 300 % Modulus (MPa) 8.3 6.8 7.2 6.4 6.5 6.7 6.5
compounds, it seems possible to adjust
their receipts to have very similar properties
After aging
Hardness
with traditional aromatic oil containing (Shore A) 67.0 69.0 68.0 69.0 68.0 66.0 68.0
compounds. Furthermore, some improve- Tensile strength
(MPa) 15.6 16.6 18.2 18.7 18.8 15.2 18.0
ment can also be achieved in tensile
strength for aged vulcanizates prepared
with these eco-friendly oils. 8 Effects of process oil type on the properties of B60N40 compounds
This study may light the attempts on to eli- B60N40 Compounds with… DAE MES-1 MES-2 TDAE-1 TDAE-2 NAP-1 NAP-2
minate aromatic oils and to replace them
ML (dNm) 0.97 1.05 1.06 1.08 1.02 1.03 0.96
with new generation low PAH content pro-
Rheological

MH (dNm) 8.73 9.06 9.45 9.06 8.72 8.49 7.74

properties

cess oils without significant changes of pro-

ts2 (min) 0.65 0.64 0.63 0.66 0.68 0.68 0.72
perties in rubber based products. This
t90 (min) 1.38 1.36 1.35 1.40 1.42 1.40 1.44
knowledge may also be useful for rubber
Mooney viscosity
industry, especially for small and medium ML(1+4)@100 °C 20.7 21.0 23.7 22.7 22.6 21.7 21.3
sized enterprises.
Physico-mechanical properties

Before aging

Hardness (Shore A) 59.0 60.0 60.0 61.0 59.0 62.0 61.0

Acknowledgements Tensile strength (MPa) 12.5 12.2 12.8 13.0 10.9 11.3 12.6
The authors are grateful to the Kocaeli Uni- Elongation @break (%) 715.0 682.0 625.0 676.0 638.0 634.0 706.0
versity Scientific Research Support Pro- 300 % Modulus (MPa) 3.4 3.5 3.8 3.6 3.3 3.6 3.4
gram for financial support (Grant Nr
2010/045).
After aging

Hardness
(Shore A) 62.0 61.0 63.0 63.0 63.0 63.0 62.0
References Tensile strength
(MPa) 9.5 10.0 12.4 12.2 10.7 10.5 11.7
[1] S., Peters, G., Talaska, A. G., Jonsson Bo, H., Krom-
hout, R., Vermeulen, Cancer Epidemiol. Biomar-
kers Prev. 17 (2008) 77. [4] S., Dasgupta, L., Agrawal, S., Bandyopadhyay, [6] A., Kuta, Z., Hrdlicka, J., Voldanova, J., Brejcha,
[2] “Regulation (EC) No 1907/2006 of the European R., S., Chakraborty, R., Mukhopadhyay, R. K., Mal- J., Praha, J., Pokorni, J. P., Pardubice. Kautschuk
Parliament End of the Council”, Official Journal kani, S. C., Ameta, Polymer Testing 26(2007) 489. and Gummi Kuntstoffe 4 (2010) 120.
of European Union (2006), 439. [5] S., Dasgupta, L., Agrawal, S., Bandyopadhyay, [7] J., Preto, J., Oravec, J., Hronkovic. Chemicke Listy
[3] S., Dasgupta, L., Agrawal, S., Bandyopadhyay, R., S., Chakraborty, R., Mukhopadhyay, R. K., Mal- 105 (2011) 369.
R., Mukhopadhyay, R. K., Malkani, S. C., Ameta, kani, S. C., Ameta, Polymer Testing 27(2008) 277.
Polymer Testing 28 (2009) 251.

www.kgk-rubberpoint.de KGK · September 2011 51