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Proceedings of the Polymer Processing Society 28th Annual Meeting ~ PPS-28 ~ December 11-15, 2012, Pattaya (Thailand)



M. Nillawong
, C. Sirisinha
Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol
University, Bangkok 10400, Thailand manuchet.1@gmail.com
Research and Development Centre for Thai Rubber Industry (RDCTRI), Faculty of Science,
Mahidol University, Salaya Campus, Salaya, Nakhon Pathom 73170, Thailand chakrit.sir@mahidol.ac.th

Hydrogenated nitrile butadiene rubber (HNBR) filled with precipitated silica (PSi) was prepared under various mixing
conditions, i.e., normal conditions (discharge temperature =80C, mixing time =15 minutes) and extreme conditions
(discharge temperature =140C, mixing time =30 minutes). Silane coupling agent, TESPT or the so-called Si-69,
was also incorporated at various loadings. It is found that increases in mixing time and temperature could significantly
enhance bound rubber content (BRC) of HNBR compounds, indicating an improvement in rubber-filler interaction. The
BRC is highest at mixing temperature and time of 140C and 30 minutes, respectively. In this work, the peroxide was
employed as crosslinking agent. Unlike conventional sulfur vulcanization, the peroxide curing reveals a cure retardation
behavior with the addition of Si-69, and the retardation magnitude could be aleviated by increases in mixing
temperature and time. Rheological properties as measured by Rubber Process Analyzer (RPA) exhibit elastic
contribution of HNBR compounds and vulcanizates with increasing BRC. Moreover, tensile and dynamic properties are
enhanced with increasing magnitude of rubber-filler interaction. Results obtained imply the importance of proper
mixing conditions of PSi/Si-69 with rubber matrix for achiving good reinforcing and cure efficiencies.

Keywords: Hydrogenated nitrile butadiene rubber, Silica, Silane coupling agent, Bound rubber, Mixing conditions

Nowadays, Hydrogenated nitrile rubber (HNBR) is
used in high performance applications, such as engine
seals, timing belts, gaskets, and paper mill rolls.
Usually, reinforcing fillers are introduced in rubber in
order to enhance properties of rubber products [1].
Precipitated silica (PSi) is well known as a non-black
reinforcing filler. Compared with carbon black (CB),
PSi gives higher tensile strength, abrasion resistance,
and rolling resistance in cured rubbers [2]. However,
due to strong interaction between PSi particles through
silanol groups (Si-OH) on PSi surfaces, the difficulty
in dispersion of PSi into rubber matrix is resulted. In
order to tackle this problem, an introduction of silane
coupling agent (SCA) is commonly used. Apart from
the enahancement in mixing efficiency, the SCAs are
known to improve filler dispersion and rubber-filler
interaction [3]. Typically, a mercapto silane is usually
used in sulfur curing system for the purpose of
enhanced cure efficiency. Furthermore, it has been
found that the in-situ coupling reaction under various
mixing conditions leads to improvements in ruber-filler
interaction and mechanical properties [4]. In order to
quantify the magnitude of rubber-filler interaction, a
measurement of bound rubber content (BRC) via
solubility method is usually carried out [5]. However,
not so many works focus mainly on a correlation of
BRC, viscoelasic behavior, and mechanical properties
of PSi filled elastomer. The main objective of this work
is to study the influences of mixing conditions for
maximizing the coupling efficiency of Si-69 in HNBR
filled with PSi. As a highlight of this work, the
peroxide was employed instead of conventional sulfur
curing system to examine its influence on cure and
silane coupling efficiencies. In addition, the
correlations of BRC, viscoelastic behavior, and
mechanical properties are established.

Hydrogenated nitrile rubber (HNBR) with 85%
hydrogenation and 36% acrylonitrile content was used
in this work. Precipitated silica (PSi) was introduced as
reinforcing filler. The Si-69 silane was used as
coupling agent with varied concentrations of 2, 4, 6, 8,
and 10 wt% of PSi. Other chemicals used in this work
are shown in Table 1.

Proceedings of the Polymer Processing Society 28th Annual Meeting ~ PPS-28 ~ December 11-15, 2012, Pattaya (Thailand)
Table 1 Materials used in the present study
Materials Amount (phr)
Hydrogenated nitrile rubber
Precipitated silica (PSi) 40
(TESPT or Si-69)
2, 2, 4-Trimethyl-1, 2-
hydroquinoline (TMQ)
Stearic acid 1
Zinc oxide (ZnO) 5
Tri-2-ethylhexyl trimellitate
trimethacrylate (TRIM)
Zinc diacrylate (ZDA) 6
Dicumyl peroxide (DCP) 2

HNBR compound was prepared under normal
(discharge temperature = 80C, mixing time = 15
minutes) and extreme conditions (discharge
temperature =140C, mixing time =30 minutes) using
a laboratory-sized internal mixer (Haake Rheomix 90,
Germany). Mixing was performed under rotor speed
and fill factor of 40 rpm and 0.85, respectively. The
compounding ingredients excluding TRIM, ZDA, and
DCP were incorporated in the first mixing step.
Thereafter, the rubber compound was mixed with co-
agents and DCP via the use of Haake Rheomix 90
again at rotor speed and temperature of 40 rpm and
40C, respectively. Cured HNBR specimens for
mechanical tests were prepared by a hydraulic hot-
press (Chai Suriya Rubber Factory, Thailand).

The BRC measurement was carried out by dissolving
uncured compounds in acetone for 7 days, and then
weighing the insoluble part. Rheological properties
were monitored by Rubber Process Analyzer
(RPA2000, USA) under strain sweep test at test
frequency and temperature of 1 rad/s and 100C,
respectively. Swelling test was conducted to assess the
magnitude of crosslink density in cured HNBR with
the use of acetone as solvent. Tensile properties were
measured according to ASTM D 412 using the
universal tensile tester (Instron, USA). Heat build up of
cured specimens was measured as per ASTM D 623
Test Method A by the use of BF Goodrich Flexometer
(Model II, USA).

Results and Discussion
Bound rubber content

Fig.1 represents the BRC results of uncured HNBR
compounds, in which the mixing HNBR with PSi/Si-69
under extreme conditions leads to a rise in BRC at any
given Si-69 loadings. The results imply a development
of rubber-interaction through high mixing temperature
and long time. However, the HNBR compound with
2% Si-69 shows very low magnitude of BRC despite
being prepared under extreme mixing conditions. This
is due to insufficient amount of Si-69, leading to
incomplete surface coverage on PSi particles.

Figure 1 BRC of HNBR compounds prepared with
different mixing conditions

Figure 2 Crosslink density of cured HNBR specimens
prepared from (a) normal (b) extreme conditions

Fig. 2 reveals crosslink density of cured HNBR
specimens as measured by a swelling method. It is
evident that the crosslink density decreases
progressively with increasing amount of Si-69, due to a
cure retardation behavior caused by released sulfur
from Si-69 in peroxide curing system [6].
Nevertheless, the cured HNBR specimens prepared
from the extreme conditions exhibit greater crosslink
density. This implies a development in cure efficiency
attributed to the smaller amount of released sulfur
Proceedings of the Polymer Processing Society 28th Annual Meeting ~ PPS-28 ~ December 11-15, 2012, Pattaya (Thailand)
molecules available for retarding the crosslink reaction.
Moreover, the magnitude of crosslink density
measured by swelling test depends not only on
chemical crosslink, but also on rubber-filler interaction
in cured rubber [7]. The strong rubber-filler interaction
leads to the tightly bound rubber and thus the low
swelling ratio, i.e., high value of reported crosslink

Figure 3 Tan delta as a function of strain of cured
HNBR specimens prepared from different mixing
conditions: normal condition (a); extreme condition (b)

Rheological behavior in terms of tan delta is
demonstrated in Fig. 3. As evidenced in Fig. 3 (a), tan
delta of specimens with Si-69 is significantly lower
than those without Si-69. This is due to the formation
of rubber-filler through coupling reaction among
silanol groups, silane and HNBR molecules leading to
the increase in elastic response. Moreover, it is evident
that the mixing performed under extreme conditions
offer low tan delta indicating the enhancement in
elastic contribution through improved cure efficiency
in conjunction with strong rubber-filler interaction.

Figure 4 Tensile properties of cured HNBR specimens
as a function of silane loading: (a) tensile strength; (b)
elongation at break; (c) modulus at 100% elongation

Fig. 4 reveals tensile properties of cured HNBR
specimens. With increasing Si-69, tensile strength and
elongation at break increase, but modulus decreases.
By the use of extreme mixing conditions, the
occurrence of tightly bound rubber and enhanced cured
efficiency contribute to the significant increase in
modulus with the expense of elongation at break.
Combined effects of enhanced rubber-filler interaction
and cure retardation is probably responsible for the
Proceedings of the Polymer Processing Society 28th Annual Meeting ~ PPS-28 ~ December 11-15, 2012, Pattaya (Thailand)

Figure 5 Dynamic mechanical properties of cured
HNBR as a function of silane loading: (a) temperature
rise; (b) dynamic set

Dynamic mechanical properties of cured HNBR
specimens are shown in Fig. 5. The increase in Si-69
loading gives rise to the increase in temperature rise
and dynamic set, implying a decrease in elasticity via
the cure retardation behavior as discussed previously.
However, the use of extreme mixing condition is
capable of alleviating the undesirable cure retardation
as a result of strong rubber-filler interaction together
with improved cure efficiency. This leads to lower
molecular mobility which is a major cause of energy
dissipation via heat [8].

In this work, two different mixing conditions were
used: normal and extreme conditions. As determined
by BRC, the rubber-filler interaction is developed more
efficiently under extreme mixing conditions, i.e.,
performing the mixing at high temperature and long
time. Rheological properties of cured HNBR
specimens are in good agreement with BRC results.
The higher the BRC, the lower the tan delta, and thus
the greater the elastic contribution. The crosslink
density as measured by swelling method exhibits
enhancements in cure efficiency and rubber-filler
interaction caused by extreme mixing conditions as
evidenced by results of tensile properties and dynamic
mechanical behaviors.

Financial supports from Center of Excellent for
Innovation in Chemistry (PERCH-CIC) and the
Thailand Research Fund through the Royal Golden
J ubilee Ph.D. Program are acknowledged.


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