Polymer-Plastics Technology and Engineering

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A Review on Hybrid Fillers in Rubber Composites

Zainathul Akhmar Salim Abdul Salim, Aziz Hassan & Hanafi Ismail

To cite this article: Zainathul Akhmar Salim Abdul Salim, Aziz Hassan & Hanafi Ismail (2018) A
Review on Hybrid Fillers in Rubber Composites, Polymer-Plastics Technology and Engineering,
57:6, 523-539, DOI: 10.1080/03602559.2017.1329432

To link to this article: https://doi.org/10.1080/03602559.2017.1329432

Published online: 27 Dec 2017.

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POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING
2018, VOL. 57, NO. 6, 523–539
https://doi.org/10.1080/03602559.2017.1329432

none defined

A Review on Hybrid Fillers in Rubber Composites

Zainathul Akhmar Salim Abdul Salima,b, Aziz Hassana, and Hanafi Ismailc
a
Faculty of Science, University of Malaya, Kuala Lumpur, Malaysia; bFaculty of Applied Science, Universiti Teknologi MARA, Shah Alam,
Selangor, Malaysia; cSchool of Materials and Mineral Resources Engineering, Universiti Sains Malaysia Engineering Campus, Nibong Tebal,
Penang, Malaysia

ABSTRACT KEYWORDS
This review article is aimed at reporting the recent development of hybrid fillers used in vulcanized Curing; hybrid filler;
rubber. This review will consider the synergistic effect of rubber hybrid composites that consist mechanical properties;
exclusively of conventional fillers; carbon black and/or silica as the primary filler, which are morphology; vulcanized
rubber
combined with secondary fillers from various sources. The discussions are mainly focused on the
analyses and comparisons of the curing characteristics, morphology, and mechanical properties of
the rubber composite-filled hybrid fillers. The compatibility and the existence of synergistic effects
between the different types of fillers show the potential for development and application in rubber
industries.

GRAPHICAL ABSTRACT

A general introduction to hybrids to have multifunctions or new functions that the orig-
inal materials did not possess. Ashby and Bréchet[3]
The word “hybrid” is derived from the Greek–Latin
described hybrid as a combination of two or more
word, which means something that has been mixed with
monolithic materials (Figure 1) in a predetermined
other materials or composition. Recently, this termin-
geometry and scale, optimally serving a specific engin-
ology is used in various scientific fields, mainly in
eering purpose.
materials science and engineering. However, in most
The earliest usage of the word “hybrid” began in the
cases, the definition is not clarified and the actual
1980s when soft-chemistry techniques that are capable
meaning is not clearly understood[1,2].
of producing inorganic materials at low temperature
In general, the term “hybrid” carries various mean-
were developed. During the beginning of the industrial
ings depending on the field of research. Nanko[2]
era, more and more hybrid materials were produced,
defined hybrid materials as a deliberate combination
for instance, inorganic pigments were suspended in
of two or more materials, which complement each other

CONTACT Hanafi Ismail ihanafi@usm.my School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia Engineering Campus, 14300
Nibong Tebal, Penang, Malaysia.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpte.
© 2017 Taylor & Francis
524 Z. A. S. A. SALIM ET AL.
Figure 1. Combination of two (or more) materials to form new
hybrid[3]. Reproduced from Ashby, M. F. and Bréchet, Y. J. M by
permission of Elsevier Science Ltd.
solvents for paints, and mineral clays were mixed with
polymers. Since then, the concept of “hybrid” has pene-
trated many areas of research associated with chemistry,
physics, biomedical, materials science, and engineering.
From the time this concept was first introduced, the
development of new or altered materials with improved
properties became the motivating goal for many
researchers. These hybrid elements or compounds must
retain their original properties, while simultaneously
maintaining their own beneficial aspects. These charac-
teristics have led to the growing popularity of hybrid
materials[4]. Current developments in materials science
are also aimed at merging the physical and/or chemical
characteristics of individual materials to allow the
superposition of their properties. Achieving this stage
would mean possible novel design developments[3].
Fabricating a useful hybrid can be very challenging
and expensive. Part of the difficulties derives from the
multiple choices available: choice of materials, choice
of mixing processes, choice of treatments to ensure
good dispersion and homogeneity, and choice of
internal geometry and morphology of the constitutive
materials. Good decision-making is crucial to ascertain
that the new hybrid materials feasibly and optimally
meet the design requirements[3].
In polymer systems, hybrid composites can be
described either as; (i) components in which one type
of reinforcing material is placed in a mixture of different
matrices or (ii) two or more reinforcing and nonreinfor-
cing fillers mixed in a single matrix. Both approaches
can also be combined. The combination of two or more
materials to form a hybrid can occur at a nanometer
scale or molecular level when orbital interaction occurs.
This will create a new material that possesses
new properties that are not necessarily found in the
individual components. These are the criteria that
show the dissimilarities between hybrid materials and
composites. Hybrid materials must have greater func-
tions or properties compared to those of normal com-
posites. Nevertheless, nanocomposite materials can be
considered as hybrid materials when the nanoparticles
are homogenously dispersed in a polymer matrix[1].
In the case of a polymer with hybrid fillers, the term
“synergy” plays a vital part in describing the interactions
among the components, whose combination produces
a superior effect than the sum of the effects of the indi-
vidual components. In other words, synergy is the joint
action of agents that can each increase the effectiveness
of the other when combined. Most researches in this field
indicated positive synergistic effects and improved overall
properties of the reinforced matrix with hybrid fillers[1].
Fillers in rubber composites
Fillers reinforcement in vulcanized rubber is a very wide
and complex subject among rubber technologists and
researchers. Unfilled rubber, also known as gum vulca-
nizate, is vulcanized rubber that contains ingredients
necessary for the vulcanization or curing process[5].
The use of fillers as the compounding ingredients in
rubber mixes is threefold. First, they are added to the
mix to lower the cost of the final products. Fillers used
in the rubber industry are usually cheaper than the
polymers in which they are used. Second, fillers are
added to the rubber during mixing to modify the
processing performance. Fillers can significantly affect
most aspects of the processing behaviors of rubbers.
Apparently, gum mix rubber compounds show poor
processing characteristics, such as giving high extrudate
swell and high calendar shrinkage[5]. Third, certain
fillers are added to the compound for reinforcing
purposes[6]. The term reinforcement has been exten-
sively used by rubber technologists to denote the
enhancement of strength and strength-related proper-
ties, abrasion resistance, hardness, and modulus[5–7].
Classification and characterization of filler
The classification of fillers for rubbers (Figure 2) varies
considerably according to the nature of the product.
Users of fillers must be aware that no two fillers are
the same. Fillers can be classified as reinforcing,
semireinforcing, and nonreinforcing. All fillers can
increase the hardness, modulus, and stiffness of vulca-
nized rubber whether or not they are reinforcing or
nonreinforcing[5].

Figure 2. Classification of fillers[5].
The main characteristics of fillers that will influence
the properties of vulcanized rubber are particle size,
particle surface area, particle shape, and surface activity.
The reinforcing effect of the filler in rubber compound
would increase, if the filler has a small particle size
range. The sizes of the filler particle can be categorized
as follows:
a) >10,000 nm (10 µm): Degradants
b) 1000–10,000 nm (1–10 µm) : Diluents
c) 100–1,000 nm (0.1–1 µm) : Semireinforcing
d) 10–100 nm (0.01–0.1 µm) : Reinforcing
Presumably, the surface area of the filler particles
would be higher, if the particle size is smaller. This
situation can improve the interactions between the
rubber and the filler particles. If the filler particle is
bigger than the distance of the polymer interchain, an
area of localized stress would be formed, which could
lead to elastomer chain rupture on stretching and
flexing. A filler must have intimate strong contact with
the rubber chains, if it is going to reinforce the rubber–
filler compound. Fillers with larger surface areas will
have more contact areas available, and consequently, will
have a higher potential to reinforce the rubber chains.
The particle shape can also play a significant role in
its ability to divert stress applied to the elastomer. The
basic particle shapes of mineral fillers are shown in
Figure 3, along with their typical aspect ratios (the
measure of their anisometry).
For needle- and fiber-shaped fillers, the aspect ratio is
the ratio of the length to the diameter, while for other
platy fillers, it is the ratio of the diameter of a circle
(which is the face of the plate) to the thickness of the
plate. In general, anisometric particles (those having a
significant difference in length versus width) are more
effective as reinforcements than isometric particles
(those with similar length and width). Particles with a
planar shape have more surfaces available for contact
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 525
with the rubber matrix than isotropic particles with an
equivalent particle diameter.
A filler can have a high aspect ratio, high surface
area, and small particle size, but still provide poor
reinforcement, if it has low specific surface activity.
Surface activity denotes the ability of the filler’s surface
to bond with the rubber matrix. Nonpolar fillers are best
suited to nonpolar elastomers, while polar fillers work
best in polar elastomers. Beyond this general chemical
compatibility is the potential for reaction between the
elastomer and the active sites on the filler surface.
Among various fillers available, carbon black promotes
an intimate contact with elastomers due to the presence
of carboxyl and other functional groups in its particles.
The nonblack fillers generally offer less affinity and less
surface activity toward the common elastomers. This
can be compensated to a greater or lesser extent using
certain surface treatments[8].
Common fillers used in rubber
Carbon black
Carbon black (CB) is the most extensively used and the
oldest reinforcing filler. It can improve strength-related
properties, such as tensile and tear strength, modulus,
Figure 3. Basic particle shapes of filler[8].
526 Z. A. S. A. SALIM ET AL.
hardness, abrasion, and wear characteristics. Approxi-
mately 90% of the CB production worldwide is used
in the tyre industry[9,10].
CB is essentially an elemental carbon in the form of
fine amorphous particles. It is manufactured using
various processing methods, which include furnace,
thermal, channel, and lampblack. For CB-filled vulca-
nized rubber composites, the reinforcement is mostly
influenced by the nanoscale particle size, larger surface
area, and high specific surface activity that promote
extensive rubber–CB interactions[10].
The addition of CB in the rubber compound imparts
a monotonous black color to the finished products[11].
As the source of CB is petroleum, the preparation and
processing of CB is quite hazardous[9]. Therefore,
considerable research efforts are being performed to
develop alternative fillers that would be able to reinforce
specific elastomers as good as CB.
Silica
Silica (SiO2) is an excellent nonblack filler that is widely
used to produce colored rubber products. It is specifi-
cally used in green tyre treads due to its low-heat
build-up. It also yields a lower rolling resistance at equal
wear resistance and wet grip compared to CB[7].
SiO2 can be obtained in various forms. Precipitated
silica is an amorphous particle made by precipitating
sodium silicate solution, while fumed silica is from the
pyrogenic process, and in-situ silica is obtained from
the sol–gel process, as well as silica from natural
sources, such as rice husk ash[8,11,12]. Apart from these
varieties, precipitated silica and pyrogenic (fumed) silica
are often used for elastomer reinforcement[13].
A major issue with silica-reinforced natural rubber is
the incompatibility between the hydrophilic silica and
the hydrophobic natural rubber, which causes the
formation of a strong silica-silica network due to the
low rubber-filler and high filler–filler interaction. An
established method for improving the reinforcement
effect in rubber composites is to treat the silica surface
with silane-coupling agents to promote interactions
between silica and rubber chains[12].
Clay
Clay minerals are abundantly available in nature. They
have been used quite extensively in various agricultural
and industrial applications, mostly as cheapening
filler[14]. However, a few decades ago, researchers dis-
covered that a small amount of clay added as filler could
bring additional benefits to the polymeric matrices.
Layered silicates, such as montmorillonite (MMT),
hectorite, halloysite, and muscovite have been used
to improve polymer properties because of their
potentially high aspect ratios. In fact, their small sizes
(typically < 1 mm) with large surface areas allow clay
minerals to come in close contact with the polymeric
matrices for better polymer–filler interaction.
Among these infinite families of layered silicates,
MMT is a well-known reinforcing filler for polymer
nanocomposites due to its availability, and it is also
environmentally friendly, at a relatively low cost. In
addition, its intercalation chemistry is fairly well under-
stood. However, surface treatment and modification of
clay silicates are compulsory to improve the compati-
bility between the hydrophilic surface of the clay and
the hydrophobic polymer matrix. The compatibility
and interaction between the clay interface and the
polymeric matrices, although intensively studied, are
yet to be fully understood.
Natural fiber and biomass fillers
The search for nonpetroleum-based fillers, which are
environmental friendly, cheap, abundant, and renew-
able, has accelerated into natural fibers and biobased
fillers from biomass. In recent years, natural fibers, such
as jute fiber, kenaf fiber, bamboo fiber, cellulose fiber,
coir fiber, and sisal fiber have been broadly used in
natural rubber (NR) composites. However, natural
fibers possess some disadvantages, such as quality
variations, moisture absorbing, and poor compatibility
with hydrophobic polymer matrix that have limited
their usage[12]. Meanwhile, in some cases, biobased
nanocomposites show unique advantages over tra-
ditional inorganic nanoparticles. Commonly used bio-
based fillers in NR include cellulose whiskers,
chitosan, and nanocrystals of starch. The studies on
these fillers are aimed at developing competitive
production cost with equivalent properties as other pet-
roleum-based fillers. In addition, the biocompatibility
and biodegradability of the biobased fillers are hoped
to be retained after dispersion in the NR matrix[11].
An overview of hybrid fillers in rubber
composites
Among the various types of reinforcing fillers available
in the market, carbon black (CB) and silica are the
two most commonly used fillers in rubber industries.
Undoubtedly, the incorporation of either CB or silica
during compounding will increase strength-related
properties of the compounded rubber to a certain
extent. However, both fillers have their own limitations,
which have prompted scientists and researchers to
develop new alternative fillers, either to replace or to
partially replace these conventional fillers, and reduce
the interdependency toward them. Nonetheless, the

continued demand for newer inexpensive, lower weight,
readily available, and environmental friendly reinfor-
cing fillers have become a big challenge to researchers.
Recently, the concept of hybrid fillers, especially with
the inclusion of nanoscale filler particles, has attracted
the attention of many researchers. It was revealed that
the multiphase hybrid filler was able to preserve the
superior properties of all fillers, as well as showed pro-
cessing synergistic effect in polymers and elastomers
due to the compatibility and co-operative interactions
at the nanoscale level[15].
In this review, the synergistic effect of conventional
fillers, namely CB, silica, and calcium carbonate, with
other potential fillers from mineral clays, natural fibers,
and industrial wastes in rubber composites will be dis-
cussed. As for the various hybrid composites that have
different combinations of fillers in rubber matrices, it
is necessary to compare their properties with compo-
sites that contain only one type of filler. The compari-
sons can be related to their curing characteristics,
morphology, and mechanical properties.
Hybrid of conventional fillers
In most cases, CB-reinforced rubber possesses a higher
modulus than silica-reinforced rubber. However, silica
offers an extraordinary combination of abrasion resist-
ance, tear strength, and ageing resistance. Since CB
and silica have different advantages, a combination of
both may give superior properties to the rubber com-
pound. A hybrid filler that consists of CB and silica
can be utilized in many commercial applications, such
as tyre treads, hoses, and engine mounts[7].
Rattanasom et al. have proven that the optimum
loading of CB/silica hybrid filler can give better overall
mechanical properties to the vulcanized rubber[7]. In
this study, the rubber compounds were prepared
through melt mixing. All ingredients, except for the
curatives, were mixed with rubber in a lab size internal
Figure 4. Scorch time and cure time for NR-filled CB/silica hybrid composites[7]. Reproduced from N. Rattanasom, T. Saowapark, and
C. Deeprasertkul by permission of Elsevier Science Ltd.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 527
mixer. Then, curatives were added to the rubber mix on
a two roll mill. Various ratios of silica and CB were
added, but the total amount of hybrid filler was kept
constant at 50 phr. Figure 4 shows the scorch time
(ts2) and optimum cure time (t90) of the NR-filled CB/
silica hybrid composites.
Scorch time indicates the time during which a rubber
compound can be worked at a given temperature before
curing begins, while optimum cure time is an estimation
of the overall curing rate of the compound. In this
study, the scorch time and the optimum cure time of
the compounds were steadily increased up to 30 phr
of silica content. Then, the scorch time and optimum
cure time were slightly reduced, although the silica con-
tent was further increased. It was believed that due to
the higher amount of silica added, the use of coupling
agent may not be sufficiently enough to reduce the
adsorption of the accelerator on the silica surface.
Furthermore, when the silica content exceeded 30 phr,
the compound viscosities were increased, which led to
high shear heating during mixing. This led to the
premature vulcanization of the rubber, which correlate
with the gradual decrease in scorch time and cure time
values. Higher values of minimum torque, ML were
indicated by higher viscosities of compounds that have
high silica contents. In this study, the authors related
most of the mechanical properties to the compatibility
and rubber–filler interactions. A slight increase of
modulus was recorded at 10 phr silica content, while
the crack growth resistance exhibited greater improve-
ment at 30 phr silica content. However, when the silica
loading was increased, the modulus values depicted a
slump trend for both unaged and aged compounds,
which was also seen in abrasion resistance. Silica is
known to have strong filler–filler interaction. When
the silica loading is high, silica–silica interaction became
stronger than filler–rubber interaction. This situation
can lead to poor silica dispersion in the vulcanized
rubber. Thus, based on the results, the authors concluded
528 Z. A. S. A. SALIM ET AL.

that the optimum loading of silica/CB hybrid fillers was

at 20/30 phr. This combination can boost up the overall
properties of the vulcanized rubber, as well as being
more practical during mixing and compounding.
The synergistic effects of CB and silica were not only
tested in vulcanized natural rubber. Noriman and
Ismail[16] reported remarkable results for hybrid CB/
silica in styrene butadiene rubber/recycled acrylonitrile
butadiene rubber (SBR/NBRr) blends. The SBR/NBRr
blends at a ratio of 85/15 were reinforced with different
loadings of CB/silica (50/0, 40/10, 30/20, 20/30, 40/10,
0/50 phr). These hybrid fillers were incorporated in
the rubber blends either with or without silane-coupling
agent, Si69. Rubber blends that were mixed with 30/
20 phr of CB/silica hybrid filler gave the highest value
of fatigue life. However, rubber compounds that were
filled with Si69 gave higher fatigue life values compared Figure 5. Structures of polymer clay nanocomposites;
to those without Si69 at similar filler ratios. This proved (a) conventional composites, (b) intercalated nanocomposites,
that the addition of Si69 has successfully suppressed the and (c) exfoliated nanocomposites[18]. Reproduced from R.
filler–filler interaction of silica, which led to an Sengupta, S. Chakraborty, S. Bandyopadhyay, S. Dasgupta, R.
Mukhopadhyay, K. Auddy, and A.S. Deuri by permission of John
improved rubber–filler interaction, thus consequently
Wiley and Sons.
extending the fatigue life of the compound. Nonetheless,
the incorporation of more silica in the rubber blends
(>20 phr) was found to gradually reduce the fatigue life aggregated, and partially exfoliated structures of the
values. This was due to the increased filler–filler interac- rubber–clay nanocomposites. Figure 6a and b shows
tion of silica, which consequently reduced the rubber– TEM images of rubber nanocomposites that contain 7
filler interaction[7]. Additionally, due to the acidic and 30 phr of organically modified MMT (OMt),
surface of silica, hydrogen bonds were formed with respectively. The study that was conducted by
basic materials, which was responsible for the formation Galimberti et al. found that at lower OMt loading, the
of agglomeration of silica[16]. filler was well distributed and homogeneously dispersed
within the rubber matrix. At higher OMt loading (30
phr), the TEM image clearly shows the highly exfoliated
Hybrid of conventional fillers with mineral clays
structure of the filler with both sequestered and stacked
Other than silica, various types of mineral clay fillers, layers were surrounded by the rubber matrix[20].
such as kaolin, montmorillonite, sepiolite, and barite In the case of vulcanized rubber, it is crucial to
have been extensively developed to partially replace understand the effect of the organomodified clay on
CB. The development of hybrid organic–inorganic the vulcanization reaction. Vulcanization is a critical
nanocomposites consisting of polymer matrix and a
layered silicate have opened up a range of potential
uses[17]. Figure 5 shows the structures of polymer matrix
and clay with layered silicate forming the
nanocomposites[18].
Most researchers realize that the intercalation of
polymer chains is essential. It promotes clay exfoliation
to ensure the ultimate clay dispersion that favors the
improvement of polymer properties[19]. However, the
inorganic nature of clay layers hinders their compati-
bility with the polymer matrix. To overcome this, the
silicate layer surfaces need to be modified to render
Figure 6. TEM images of rubber nanocomposites filled with:
them organophilic, so that the organically modified
(a) OMt – 7 phr, and (b) OMt – 30 phr[20]. Reproduced from
nanofillers can significantly disperse within the rubber Maurizio Galimberti, Michele Coombs, Valeria Cipolletti, Pierluigi
matrices[9]. Transmission electron microscopy (TEM) Riccio, Theonis Riccò, Stefano Pandini, and Lucia Conzatti by
was used to observe the presence of intercalated, permission of Elsevier Science Ltd.

industrial process to obtain useful rubber products, such
as tyres, tubes, and hoses from raw rubbers. It increases
the elasticity, while decreasing the plasticity of the
elastomer, to form a three-dimensional molecular
cross-linked network structure, with stability that highly
dependent on temperature and time. Regardless of the
nature and polarity of the rubber, the organoclay exerts
two effects on the rubber curing stage. First, the organo-
clay acts as a catalyst and speed up the vulcanization
reaction; and second, it increases the delta torque
(torque difference; MH – ML) value, thus indicating a
strong impact of organoclay on the cross-linking density
of the rubber compound. These effects are observed
even at low organoclay concentration in the rubber
composite, which are significantly lower than those used
with conventional fillers, such as CB and silica[17].
Considering the fact that the addition of organoclay
can accelerate the curing process, and simultaneously
boost up the critical performance of the rubber com-
pound, Galimberti et al. reported the synergistic
reinforcement of CB and modified nanoclay (NC) in
natural rubber[20]. It was discovered that NR with the
hybrid filler promoted superior mechanical properties
over that of NR with CB as a single-phase filler. In this
research, MMT clay was modified with di(hydrogenated
tallow)-dimethylammonium as the organophilic cation
to yield organoclay. NR, with the addition of 0 to
11 phr of organically modified MMT (OMt) and
60 phr of CB, were mixed with other compounding
ingredients in an internal mixer at 80°C. Figure 7 shows
the scorch time (ts1) and the optimum cure time (tc90) of
the NR-filled CB–OMt hybrid composites.
This study found that the scorch time and the
optimum cure time for these compounds were simul-
taneously decreased with the addition of CB at 60 phr
and continuously decreased as the loading of OMt
Figure 7. Scorch time and cure time of NR-filled CB–OMt
hybrid composites[20]. Reproduced from Maurizio Galimberti,
Michele Coombs, Valeria Cipolletti, Pierluigi Riccio, Theonis
Riccò, Stefano Pandini, and Lucia Conzatti by permission of
Elsevier Science Ltd.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 529
increased. A low scorch safety may relate to processing
problem, however a fast curing speed can be considered
as an advantage. In addition, the delta torque of the
compounds filled with CB–OMt was reasonably
increased, which infers to the increase in the cross-link-
ing density due to the presence of OMt in the rubber
compound. In addition, it was also observed that the
CB–OMt hybrid fillers were able to enhance the proper-
ties of the rubber composites. The highest modulus and
material stiffness values recorded by these CB–OMt
hybrid composites were mostly due to the compatibility
of both fillers with the rubber matrix. The intercalation
of the rubber chains into the layered silicate galleries
had significantly improved the interaction between the
rubber matrix and the organoclay as previously
indicated in TEM images in Figure 6.
The outstanding properties imparted by rubber–clay
nanocomposites have opened up new challenges in
developing CB/NC hybrid fillers to reinforce various
kinds of rubber matrices for numerous applications.
Praveen et al. chose styrene butadiene rubber (SBR) as
the matrix to study the synergistic effect of CB and
modified MMT organoclay fillers, because SBR has a
very low gum strength. Hence, the reinforcement effect
of the hybrid fillers to the rubber matrix can be easily
understood[9]. As previous discussed in this review,
the SBR nanocomposites were prepared by melt
blending in an open mill. There were two sets of SBR
nanocomposites prepared; one set was only added with
NC, while the other set was the combination of 20 phr
CB with various amounts of NC.
Figure 8a shows the morphology of SBR filled with
10 phr NC without CB. The existence of exfoliated
and intercalated clay layers are clearly seen in this
micrograph. With the addition of 20 phr CB, the clay
layers exhibited more complex intercalated structures
with CB and the rubber matrix. It was observed that
there was a tendency for CB particles to associate
around the NC layers, as shown in Figure 8b and c.
The authors concluded that the optimum loading
ratio for the NC/CB hybrid filler was 10/20 phr. The
presence of CB in the SBR matrix favored the disper-
sion, intercalation, and exfoliation of NC with the
optimum loading. The dispersion of NC in the rubber
matrix was controlled by two main factors; the
matrix–CB–NC interaction and the CB–NC–filler inter-
action. These factors led to achieving the reinforced
intercalated structure.
In relation to mechanical performance, further
increment of the NC content contributed to a gradual
increase in the percentage of elongation at break and
modulus. However, NC, as a single-phase filler, showed
lower properties than NC/CB hybrid reinforcing filler.
530 Z. A. S. A. SALIM ET AL.
Figure 8. TEM images of: (a) SBR with 10 phr NC without CB at
10 kx magnification; 1. Cylindrical ZnO particle; 2. Exfoliated clay
layers; 3. Intercalated clay layers; 4. Aggregate; (b) SBR with
10 phr NC with CB at 10 kx magnification; 1. An assembly of clay
platelet and CB network; 2. One CB microstructure inserted
between two clay platelets (nanounit); 3. Aggregate of CB and
clay; and (c) SBR with 10 phr NC with CB at 25kx magnification;
1. CB network attached with clay intercalate; 2. Immobilized
intercalated structure[9]. Reproduced from S. Praveen, P.K.
Chattopadhyay, P. Albert, V.G. Dalvi, B.C. Chakraborty, and S.
Chattopadhyay by permission of Elsevier Science Ltd. Notes:
SBR, styrene butadiene rubber.
This binary system suggested a synergistic effect that led
to the remarkable improvement of mechanical proper-
ties, as indicated in Figure 9.
The higher strength of the SBR-filled NC/CB hybrid
compound can possibly be attributed to the structure of
both fillers. The layered arrangement of NC allowed the
chain slippage that prevented the breakage of molecules,
even at higher strains. Meanwhile, the strong affinity
and interaction between the rubber matrix and CB con-
tributed to the modulus of the compound.
Synergistic effect was also reported by Zhao et al. in a
study of nanobarite (NB) and CB hybrid fillers in NR
matrix[10]. Barite is a mineral filler consisting of barium
sulfate, which is commonly used in polymer industries.
In this study, the CB content was fixed at 45 phr, and
was added in all compounds, while the content of the
modified NB was varied. Both important elements in
curing characteristics; the scorch time and the optimum
cure time were decreased with increasing NB content,
which proved that the incorporation of modified NB
in the rubber compound had accelerated the curing
reaction. However, the torque values were increased
when the NB content was increased caused by the
mobility restriction of the NR chains during the curing
Figure 9. Mechanical properties of SBR-filled CB/NC hybrid
composites: (a) Elongation at break and (b) Tensile strength[9].
Reproduced from S. Praveen, P.K. Chattopadhyay, P. Albert,
V.G. Dalvi, B.C. Chakraborty, and S. Chattopadhyay by permission
of Elsevier Science Ltd. Notes: SBR, styrene butadiene rubber.
process due to higher polymer–filler interactions. Other
mechanical properties, such as tensile strength, tear
strength, and abrasion resistance were also influenced
with the incorporation of modified NB. The authors
concluded that the optimum ratio of CB/NB was 45/2.
This ratio indicated a balanced compatibility between
CB and modified NB in reinforcing NR.
Senthivel et al.[15] have demonstrated reasonable
properties improvement in rubber-filled CB and halloy-
site nanotube (HNT) hybrid composites. HNT is a
naturally occurring aluminosilicate that is used as a
potential reinforcing filler in various types of elastomers
to improve the mechanical and thermal properties of
the composites[15]. In this study, acrylonitrile butadiene
rubber (NBR) was chosen as the matrix. CB loading was
kept constant at 60 phr, while the HNT loading was
varied from 0 to 10 phr. In this study, the curing
characteristics; scorch time and optimum cure time of
NBR hybrid composites had increased with increasing
HNT loading. This finding had contradicted reports
from other studies. They claimed that the adsorption
of curatives onto the HNT surface and into its lumen
had delayed the cure time of the compounds, which
means longer processing safety with longer cross-link
formation[21]. Similar results were obtained by Ismail
et al.[21,22], where an increased amount of CB, as a
replacement for HNT, had sped up the curing process.
Both the minimum and maximum torques of the NBR

hybrid composites had also increased when the HNT
content was increased up to 6 phr. As reported earlier,
the increase in torque value was due to the rubber–filler
interactions, in this case the NBR–CB–HNT interac-
tions. When the HNT content was increased, the
mobility of the rubber chains was reduced by the
presence of both fillers.
As shown in Figure 10, both tensile strength and
elongation at break of the hybrid composites had
steadily increased when the HNT loading was increased
up to 6 phr. This confirms the “nano” effect of HNT,
whereby the filler was well dispersed in the rubber com-
posites, and had reinforced the rubber at low loadings,
as suggested by Varghese et al.[23]. Ismail et al.[22] also
reported that the addition of 5 phr of HNT in a rubber
matrix was able to improve the tensile properties. How-
ever, in another study conducted by Ismail et al.[21], the
tensile values had dropped at 10 phr of HNT loading.
This indicated that at low filler loading (less than
10 phr), the high surface area of the filler’s nanoplatelets
was enabling the maximum contact points with the
rubber molecules, thus promoting maximum interac-
tions with the matrix. Strong interactions between the
rubber and the hybrid fillers may allow more efficient
load transfers, thereby leading to better mechanical
properties as reported. However, as described by
Senthivel et al.[15], due to aggregation of the HNT fillers,
the tensile strength was reduced after 6 phr loading. The
increase of the elongation at break values was due to the
unique structure of the tubular HNT, which can
improve the stiffness and ductility of the composites.
Based on these results, the authors have agreed that
the optimum ratio of CB/HNT hybrid fillers was
60/6 phr[15]. This optimum ratio had obviously given
superior overall performance to the rubber composites.
Most of the reported hybrid fillers were based on a
combination of CB as the primary filler, and supported
Figure 10. Mechanical properties of NBR-filled CB/HNT hybrid
composites[15]. Reproduced from K. Senthivel, K. Manikandan,
and B. Prabu by permission of Elsevier Science Ltd. Notes:
NBR, acrylonitrile butadiene rubber; HNT, halloysite nanotube.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 531
by secondary fillers from numerous sources. Recently,
there has been heightened interest in developing hybrid
fillers from nonpetroleum-based sources, such as silica
and calcium carbonate (CaCO3) as the main filler,
which are safe to handle, environmental friendly
materials[24].
Nik Ismail et al. studied the synergistic effect of
hybrid reinforcement based on precipitated silica (PS)
and montmorillonite (MMT) nanofillers on the
mechanical properties of a silicone rubber (SR). No
current work has been reported on the effect of hybrid
fillers on the properties of SR. SR is a specialty rubber
with good resistance to chemicals and radiation, and
possesses excellent electrical properties[25]. However,
the major limitation of this elastomer is its poor mech-
anical strength. In this study, the amount of MMT was
kept constant at 6 phr, while the amount of silica was
varied at 0, 2.5, 6, and 10 phr.
The results showed that the optimum cure time was
increased, while the scorch time and rate of cure were
decreased with increasing PS content, as shown in
Table 1. As reported earlier, coupling agents, which
are known to reduce the adsorption of accelerator on
the PS surface, may not be sufficient at high filler
loading. Therefore, the increasing amount of PS had
inhibited them from reacting with the rubber chains
to form cross-links during curing, thus delaying the
curing process. Additionally, the Δtorque values, which
are related to the cross-link density of the SR/PS/MMT
nanocomposites, rose gradually when the PS loading
was increased. This might be due to the formation
of physical bonds that strengthen the rubber–filler inter-
actions between the rubber chains and PS[25]. Moreover,
at the optimum loading of the hybrid filler (SR/MMT/
PS: 100/6/10 phr), the authors reported improvements
in the overall properties of the SR/PS/MMT compared
with those of the control rubber. Enhancements were
recorded in tensile strength, modulus at 100 and
300%, elongation at break, Young’s modulus, stored
energy density at break and hardness.
In addition to SR, ethylene–propylene–diene mono-
mer (EPDM) rubber is one of the synthetic rubbers that
have captured the interest of researchers. EPDM rubber
is suitable for outdoor applications since it possesses a
Table 1. Cure characteristics of SR/MMT/PS composites[24].
Cure rate
Cure time Scorch time index Δtorque
Compound (min.) (min.) (min 1) (dNm)
Control SR 7.24 3.13 24.3 21.29
SR/MMT (6 phr) 7.23 3.32 25.6 23.40
SR/MMT/PS (2.5 phr) 11.41 3.38 12.5 24.49
SR/MMT/PS (6 phr) 10.26 3.11 14.0 27.92
SR/MMT/PS (10 phr) 13.42 2.45 9.1 30.36
532 Z. A. S. A. SALIM ET AL.
high saturated backbone that results in high resistance
to aging, heat, and oxidation, while offering dynamic
mechanical and electrical properties. Considering the
remarkable properties of EPDM, Ismail and
Mathialagan[26] chose EPDM rubber as the matrix to
study the effect of partial replacement of silica and
CaCO3 by bentonite clay. Bentonite (Bt) is a soft rock
clay, which originated from smectite materials. Bt is
formed by layers that are about 1-nm thick, which are
stacked together by weak forces. This characteristic
makes bentonite easily penetrable by smaller molecules,
which results in a good rubber–clay interaction[26].
Five different compositions of EPDM/silica/Bt and
EPDM/CaCO3/Bt (i.e., 100/30/0, 100/25/5, 100/15/15,
100/5/25, and 100/0/30 phr) were prepared using two
roll mill. From the results, the scorch time and the cure
time of both EPDM composites that contained silica/Bt
and CaCO3/Bt were gradually decreased when Bt load-
ing was increased. At high silica or CaCO3 loading, the
curing process of the rubber composites was retarded.
Silica surface contains acidic silanol groups, which are
chemically reactive. They tend to react with the amine
group that is present in most accelerators used in sulfur
curing system. Consequently, the amount of active sul-
furating agents would be reduced, thus resulting in
longer scorch and optimum cure time[26]. However,
due to the larger surface area of silica compared to
CaCO3, as listed in Table 2, the cure time for EPDM
that contained CaCO3/Bt hybrid filler was faster than
for the EPDM/silica/Bt composites at similar loading.
Ismail et al. found that the smaller specific area of
CaCO3 provided less reaction with accelerators, thus
speeding up the vulcanization reaction with the pres-
ence of more sulfurating agents[26].
Figure 11 shows the tensile strength properties and
elongation at break of the EPDM composites. Both
the tensile strength and elongation at break of the
CaCO3/Bt-filled EPDM had increased consistently with
higher loading of Bt. As mentioned earlier, CaCO3
possesses a smaller surface area compared to Bt, which
leads to better dispersion of Bt in the EPDM matrix. On
the other hand, the mechanical properties of EPDM
composites with silica/Bt hybrid fillers had gradually
increased up to 15 phr of loading ratio for both fillers,
which then continuously dropped with further
Table 2. Physical characteristics of bentonite, silica, and
calcium carbonate[26].
Silica
Physical characteristics Bentonite (Bt) (Vulcasil C)
Average particle size (µm) 0.82 4.00
Surface area (m2/g) 2.6766 1.1380
Figure 11. Mechanical properties of EPDM-filled silica or
CaCO3/Bt hybrid composites[26]. Reproduced from H. Ismail,
and M. Mathialagan by permission of Elsevier Science Ltd. Notes:
EPDM, ethylene propylene diene monomer.
increment of Bt. The authors noted that at 15 phr, the
hybrid fillers have achieved the synergistic effect that
had improved the mechanical properties of the
composite materials. Furthermore, at 15 phr, the smaller
particle size of Bt was able to penetrate between the
silica and the rubber chain, and become well dispersed
within the matrix. This condition has enhanced most
of the strength-related properties of the EPDM rubber
composites.
Hybrid of conventional fillers with industrial
wastes and natural fibers
For decades, the “Reduce, Reuse and Recycle (3R)”
awareness campaign is touted to ensure that the
environment stays clean, safe, and healthy. Due to the
government’s 3R policy, rubber technologists have been
urged to develop new fillers from renewable sources
and waste materials. Due to their high resistance to
atmospheric and biological agents, which had generated
some degradable issues[27], several efforts are being
done to reuse and recycle waste tyres and polyethylene
terephthalate (PET) that are mostly used for bottling
beverages, into secondary fillers in rubber compound.
Additionally, solid wastes, such as palm ash and paper
sludge also have the potential to be developed as fillers
because these wastes are abundantly available at no cost.
Although it was reported that the incorporation of these
solid wastes into various polymer matrices had led to a
slight decrease in the mechanical performances of the
polymer composites, their efficiencies as secondary
fillers in hybrid systems with conventional fillers like
Calcium CB and silica have yet to be proven.
carbonate
(CaCO3) As the largest producer of palm oil in the world, the
5.84 disposal of solid ash from the combustion of oil palm
0.8961 fibers and shells in palm oil mill factories have become

a major environmental issue in Malaysia[28]. In
addition, by-products from paper industries, namely
paper sludge, are believed to offer a new kind of filler
in polymer since it is mainly composed of short cellu-
lose fibers and inorganic materials[29]. Ismail and Haw
studied the effect of hybrid palm ash/silica filler in natu-
ral rubber[28]. The authors found that the addition of
palm ash had accelerated the curing process, while the
optimum cure time was delayed when silica was added
to the rubber compound. This study showed that
palm ash is better than silica in speeding up the curing
process of the rubber vulcanizate. The same results were
obtained when hybrid paper sludge/silica filler was
incorporated into the rubber matrix[29]. Silica has high
porosity, thus it can absorb certain rubber ingredients,
such as stearic acid and accelerators. This would decrease
the number of curatives, and delay the scorch and cure
times of the composites. Silica can also react with zinc
oxide, which consequently will reduce zinc reactivity,
thus slowing the sulfur reaction. Therefore, when paper
sludge or palm ash is replaced by silica, the vulcanization
reaction will be decelerated. This is because the increased
silica loading will decrease the amount of curatives avail-
able for the vulcanization process.
Other than that, partial replacement of palm ash by
silica had resulted in higher tensile strength and tensile
Figure 12. SEM micrographs of tensile fracture surface of hybrid NR composites; (a) 30 phr paper sludge-filled NR composite without
CB or silica at 200� mag.: (b) 10 phr paper sludge and 20 phr CB-filled NR composite at 203� mag.: and (c) 10 phr paper sludge and
20 phr silica-filled NR composite at 203� mag.[29].
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 533
modulus. The increased silica loading had increased
both properties tremendously. The particle size of silica
(0.02–0.025 mm), which is smaller than the particle size
of palm ash (75 mm) was able to provide a larger surface
area, thus creating greater interaction between the silica
and the rubber matrix. The strong interaction could
have effectively disperse the stress from the rubber
matrix to the particles of the fillers and therefore,
improved the tensile strength and modulus of this
composites. Ismail et al.[29] have also studied the effect
of the partial replacement of paper sludge by CB and
silica on natural rubber composites. SEM micrographs
of tensile fracture surface at 30 phr of paper sludge,
without the incorporation of CB and silica, have exhib-
ited many agglomerates and filler pull-out, as shown in
Figure 12a. In contrast, SEM micrographs for paper
sludge/CB (10/20 phr) and paper sludge/silica (10/20
phr) showed no such failures, as indicated in
Figure 12b, and c, respectively. This was in line with
the higher tensile strength obtained for composites with
full replacement of CB. The more uniformed and
smooth surface indicated that these composites had
experienced less failure.
Ismail and Haw also reported that the stiffness of the
hybrid palm ash/silica composites were increased with
increasing silica loading[28]. Most of these findings
534 Z. A. S. A. SALIM ET AL.
confirmed that incorporating higher loading of reinfor-
cing fillers would produce stiffer and harder rubber
composites. The incorporation of silica had also
improved the fatigue life of the composites. The silica
was well dispersed and wetted efficiently by natural
rubber as compared to palm ash. Meanwhile, the
unwetted filler surface became a stress concentration fac-
tor that led to fatigue failure of the rubber composites.
Nabil, Ismail, and Rashid have conducted a study on
the properties of natural rubber composites filled with
commercial fillers, namely CB, HNT, and silica, with
recycled polyethylene terephthalate (R-PET)[27]. Five
different compositions of the hybrid fillers (CB/R-
PET, HNT/R-PET, and Silica/R-PET) were prepared
using two-roll mill at 20/0, 15/5, 10/10, 5/15, and
0/20. Figure 13 shows the curing characteristics of these
composites. Both the scorch time (ts2) and the optimum
cure time (tc90) for NR composites filled with CB/R-PET
had increased with higher R-PET loading, while the
scorch and optimum cure times for rubber composites
filled with HNT/R-PET, and Silica/R-PET, had
gradually dropped.
Based on the vulcanization studies conducted by Da
Costa et al.[30], the course and large surface area of CB
(where the rubber and curatives can interact), and its
high surface reactivity (that can vigorously form cross-
links), had accelerated the curing process of rubber
composites filled with high CB loading. The decreasing
patterns of ts2 and tc90 values of HNT and silica with
increased loading of R-PET may be due to the weak
Figure 13. Curing characteristics of NR filled with CB/R-PET, HNT/R-PET, and Silica/R-PET composites[27]. Reproduced from
Hayeemasae Nabil, Hanafi Ismail, and Azura Abdul Rashid by permission of John Wiley and Sons. Notes: R-PET, recycled polyethylene
terephthalate; HNT, halloysite nanotube.
interactions between HNT and silica with the curatives.
The more R-PET added to replace HNT and silica, the
faster the curing rate observed. Figure 13c shows the
torque differences of the rubber composites. All hybrid
composites showed gradual decrease in torque differ-
ence with increasing R-PET, which can be indirectly
related to the decreasing cross-link density of the
composites. Among these three hybrid composites,
composites with CB/R-PET had shown the highest
torque difference values. It is inferred that the higher
surface area and the higher surface activity of CB, in
comparison with HNT and silica, had improved the
interaction between the rubber and the filler. The
molecular chain of the rubber may have become
trapped in the CB aggregates due to its high surface
structure, which had increased the viscosity during
mixing, thus giving higher torque difference values at
high loading of CB. These values had dropped with
the increase of R-PET loading[27].
As reported by Nabil et al.[27], the tensile strength
values for all hybrid composites had decreased with
increasing R-PET loading. The authors suggested that
the bigger particle size of R-PET resulted in a low
surface area, which had minimized the interactions
between the R-PET flakes with the conventional fillers.
This in turn, affected the dispersion of the filler during
the mixing process. The weak interaction led to the
initial failure in transferring stress from the rubber
matrix to R-PET. Among all hybrid fillers, CB/R-PET
recorded the highest value of tensile strength. Even

though the HNTs have a unique structure that is
capable of forming three-dimensional orientations in
the rubber compound, the strong interaction between
CB and the rubber matrix remain undefeated by other
fillers. As mentioned previously, the low tensile strength
of silica/R-PET was due to the high silica–silica
interactions[27]. It was also found that by increasing
the R-PET loading, the elongation at break for rubber
composites filled with CB/R-PET was increased at a
constant rate, whereas the elongation at break for other
composites were gradually decreased. By replacing CB
with R-PET, the rigidity of the rubber was reduced
due to the low structure of R-PET. On the contrary,
the decreasing patterns of elongation at break were
recorded for both composites with HNT/R-PET and
silica/R-PET hybrid fillers. With the increased R-PET
loading, the reduction of crack propagation resistance
was suggested to be the main reason for the lower
elongation before failure[27].
In another study, Nabil and Ismail had performed a
fatigue life test on hybrid commercial fillers/R-PET-
filled NR composites[31]. It was clearly described that
the fatigue life had improved with the addition of more
commercial fillers. These results are strongly supported
by the fact that the commercial fillers have smaller
particle sizes compared to R-PET. Consequently, more
interactions and interfacial adhesions had formed
between the fillers and the rubber matrix, which
improved the stress transfer during cyclic deformation
test, and reduction of stress concentration points.
According to these results, the fatigue life can be
arranged in the following sequence: NR/CB/R-PET >
NR/HNT/R-PET > NR/Silica/R-PET composites.
Obviously, the incorporation of CB in the rubber matrix
has improved the stress transfer efficiently, and conse-
quently, lessened the damage progression of the compo-
sites compared to with the other two hybrid fillers. Poor
dispersion of silica in the rubber matrix due to high
silica–silica interaction could have been the main reason
Figure 14. SEM images of fractured surfaces; (a) NR/CB/R-PET, (b) NR/HNT/R-PET, and (c) NR/Silica/R-PET composites at a loading
ratio of 10/10 (phr/phr)[31]. Notes: R-PET, recycled polyethylene terephthalate; HNT, halloysite nanotube.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 535
for the lowest fatigue life recorded. Remarkably, the
fatigue life of NR/HNT/R-PET composites was higher
than the NR/Silica/R-PET composites. As previously
mentioned, the unique structure and the high aspect
ratio (L/D) of the HNT had encouraged a strong rub-
ber–filler interaction. This interaction had enhanced
the interfacial adhesion, hence limiting the chain scis-
sion that finally improved the fatigue life under repeated
cyclic deformation. This was proven by looking at the
condition of the fractured surfaces of the composites
in Figure 14a–c. These SEM images show the
morphology of the fractured surfaces of CB/R-PET,
HNT/R-PET, and Silica/R-PET-filled NR composites
at a loading ratio of 10/10 (phr/phr). It was clearly
observed that R-PET detachments had occurred in all
composites. However, Figure 14c shows the presence
of numerous voids, which had literally led to the forma-
tion of stress concentration that was responsible for the
poor fatigue life of the NR/Silica/R-PET composites.
Apart from R-PET, waste tyres are one of the major
solid wastes in the world. The high demand for trans-
portation vehicles around the world has increased the
production of tyres, which will subsequently become
wastes. The uncontrolled dumping of waste tyres has
encouraged scientists and researchers to reutilize it into
something beneficial. One of the efforts is to develop
waste tyres into secondary fillers in rubber composites.
Ismail, Omar, and Othman have initiated a study on
the curing characteristics and mechanical properties of
hybrid fillers of waste tyre dust (WTD) and CB in NR
composites[32]. Five different compositions of WTD/
CB hybrid fillers were prepared using two-roll mill at
30/0, 20/10, 15/15, 10/20, and 0/30 phr. Ismail et al.[32]
reported that the optimum cure time had increased with
the increment of CB loading. The authors suggested that
the delayed cure time at higher CB loadings was due to
the unreacted accelerator that remained in the WTD.
FTIR analysis showed where several bonds, namely,
N-H, C-N, and ‒CH2 were detected in the IR spectrums,
536 Z. A. S. A. SALIM ET AL.
as seen in Figure 15. These were believed to be the
bonds that existed in the unreacted accelerator within
WTD[32].
The tensile strength of the rubber composites had
also increased with increasing CB loading. The weak
interfacial adhesion between WTD and NR matrix
contributed to the lowest value of the tensile strength,
recorded at 30 phr of WTD-filled NR composites. The
rubber molecules might have retained most of its physi-
cal properties, even after being transformed into dusts.
This could have complicated the adhesion between
WTD and NR matrix due to the strength of the cross-
link bonds between them[32]. CB could have adhered
well with the rubber matrix due to its porous surface
structure. Rubber matrix tends to fill the pores on CB
surface, and forms a strong adhesion between them.
This condition could have led to the improved
reinforcement and the boost in tensile strength values.
The elongation at break of the composites had
decreased with increasing CB. The slump trend of the
elongation at break values, right after the incorporation
of CB, was again related to the surface porosity of CB.
When the rubber matrix filled the pores on the CB
surface, the deformation and elongation of the com-
pounds were hindered. As a result, the elongation at
break was decreased, while the reinforcement of the
NR composites was increased with the increment of
CB loading. This may have contributed to the enhance-
ment of fatigue life with higher CB loadings.
Apart from studying the properties of NR filled with
hybrid commercial fillers and solid wastes, Ismail et al.
Figure 15. IR spectrum of WTD[32]. Reproduced from H. Ismail, N. F. Omar, and N. Othman by permission of John Wiley and Sons.
Notes: WTD, waste tyre dust.
had also analyzed the effect of hybrid WTD fillers with
kenaf fibers in NR composites[33]. Like other naturally
available fibers, kenaf is known for its reinforcing effect
that is valued in various applications, such as in the
building and construction sectors, as well as in the pro-
duct manufacturing industries. Similar to their previous
study, five different compositions at a constant ratio of
30 phr of filler loading were prepared using two-roll
mill. Rapid cure times were observed at higher loadings
of WTD, and with the addition of more kenaf fibers in
the NR composites, longer curing time was obtained. As
previously discussed, the existence of unreacted cura-
tives in WTD (see Figure 15) could have accelerated
the curing process of the NR composites. These bonds
(N-H, C-N, and ‒CH2) usually exist in accelerators,
such as N-Cyelohexy1-2-benzothiazole sulfonamide
(CBS). CBS contains sulfur elements that can react with
rubber molecules to initiate curing. As a result, higher
loading of WTD would give shorter curing time that
can benefit the production in terms of saving time
and cutting down on energy consumption[33].
The weak interfacial adhesion between kenaf fibers
and rubber matrix can affect the tensile strength of
the NR composites. NR is a nonpolar elastomer. The
incompatibility of NR matrix and kenaf fibers was due
to the presence of hydroxyl polar groups in the natural
fibers, which had contributed toward the lower tensile
strength values. This has also affected the fatigue life
of the composites. With the addition of 10 phr of kenaf
fibers, the value of fatigue life had dropped steeply.
These results proved that the adhesion between kenaf

fibers and NR matrix was weaker than the adhesion
between WTD and NR matrix[33]. In addition, with
the increment of kenaf fiber loading, the elongation at
break was decreased. The stiff property of kenaf fibers
that comes from lignin, cellulose, and hemicellulose[34]
is responsible for the slump trend of the elongation at
break values. The more kenaf fibers are added, the stif-
fer the NR composites will be.
Other plant sources, apart from kenaf, can also be
utilized as secondary fillers in rubber composites. The
utilization of agro-wastes not only benefits the environ-
ment but also provides renewable resources of fillers at
low cost. Various studies have analyzed the potential of
these natural sources as fillers in rubber composites,
either in fiber or in powder form. Rice husk and rattan
are among the natural sources that have been analyzed
as partial replacements for commercial fillers in NR
composites.
Attharangsan et al.[35] have conducted a study on the
properties of NR composites filled with CB and rice
husk powder (RHP) hybrid fillers at various filler ratios
(0/30, 5/25, 10/20, 20/10, and 30/0). Both the scorch
time and the cure time had decreased with increasing
CB loading. Muniandy et al.[36] also reported similar
results in their research on the partial replacement of
rattan powder (RP) with commercial fillers; CB, mica,
and calcium carbonate (CaCO3). During compounding,
a high amount of CB was able to generate heat from the
shearing force due to its higher viscosity[35]. The forma-
tion of hydrogen sulfide, and the breakage of S‒N
linkage when heated with accelerator (sulfonamides)
during mixing, had directly accelerated the curing
process[36]. However, the opposite results were obtained
with the incorporation of mica and CaCO3 in the NR
composites. As reported by Pasbakhsh et al.[37], the
delay in cure time was due to the ability of both mica
and CaCO3 to interact with accelerators, which led to
the reduction of the number of active sulfurating agents,
thus consequently, retarding the curing process.
As expected, the overall mechanical performance of
NR composites filled with CB/RHP had improved with
the incorporation of more CB. The strength-related
properties, such as tensile strength, modulus, and
fatigue life of NR composites were mostly influenced
by the particle size, particle surface area, and particle
shape of the fillers used. The authors reported that the
bigger particle size had contributed to the lower surface
area of RHP, which was responsible for its weak interac-
tion with the NR matrix. The irregular shape of RHP,
as compared to CB, had also made the interaction
more complicated. RHP failed to support the stress
transferred from the rubber matrix, which led to the
lowest tensile strength values at 30 phr loading of
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 537
RHP. Furthermore, the hydrophilic RHP and the
hydrophobic nature of NR had also caused lower inter-
action and adhesion between them[35]. Consequently,
poor dispersion of RHP within the NR matrix would
have occurred, thus creating lower composite proper-
ties. Similar results were attained in NR composites
filled with RP with commercial fillers. Increased mech-
anical properties were obtained from NR composites
filled with CB/RP, followed by mica/RP, and last,
CaCO3/RP hybrid fillers. The lowest tensile strength
value for NR/CaCO3/RP can be related to the bigger size
of CaCO3 particles as compared to the particle sizes of
mica and CB. This condition has resulted in a weaker
interaction with the rubber matrix. The weak interfacial
adhesion of CaCO3 within the matrix hindered the
transfer of stress from the matrix to the filler system,
which resulted in failure upon tensile loading.
Conclusion
Even though the development of hybrid fillers in rubber
composites is still in the preliminary stage, recent work
in this area suggests that improvements in the overall
rubber composites properties can be achieved. The main
aim for studying the various combinations of hybrid
fillers is to discover new alternative fillers. These
new fillers can either replace or partially replace two
conventional fillers; CB and silica, in line with the
continued demand for newer inexpensive, low weight,
readily available, and environmentally friendly reinfor-
cing fillers. It is believed that the synergistic improve-
ment of hybrid fillers is well beyond the improvement
obtained when using a single filler. The rubber
composite-filled hybrid fillers had mostly displayed
improvements in cure characteristics, which favor the
processing condition. Apart from that, at the optimum
loading of the hybrid fillers, superior tensile strength
and modulus have been recorded. The enhancement
in the critical performance of rubber composites was
strongly related to the processing parameters, the type
of fillers, the interactions between these fillers as well
as the interaction between the fillers and the rubber
matrix. The behavior and the physical properties of
the filler particles play huge roles in achieving good
filler–filler, and filler–rubber interactions. Certain types
of fillers need to be treated to improve their compati-
bility with the rubber matrix. Other than that, filler
particles in the nanoscale with high surface areas were
also proven to disperse well compared to fillers in
microscale structures. Therefore, comprehensive and
thorough investigations need to be done in obtaining
uniformed morphology of the hybrid-filled nanocom-
posites. In conclusion, a larger scope exists in the
538 Z. A. S. A. SALIM ET AL.
development of novel rubber products using hybrid
fillers. It is believed that with continuous effort from
researchers and scientists, these hybrid fillers will have
widespread applications in the near future.
Acknowledgments
The authors wish to gratefully acknowledge Universiti
Teknologi MARA (UiTM) and Ministry of Education
(MOE) for the UiTM/SLAI scholarship to the Author 1.
The authors express the gratitude to UiTM, UM, and USM
for all research facilities and technical supports provided.
Funding
The authors would like to thank Universiti Malaya (UM) for
the research grant (PG160-2015A).
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