Characterization and Properties of Activated
Nanosilica/Polypropylene Composites
With Coupling Agents
Ong Hui Lin, Hazizan Md Akil, Z.A. Mohd Ishak
School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal,
Penang, Malaysia
In this work, nanosilica/polypropylene composites con-
taining 1 wt% of silica nanoparticles were prepared by
melt mixing in a Thermo Haake internal mixer. Prior
compounding, nanosilica was subjected to surface
activation using sodium hydroxide (NaOH) solution.
The effectiveness of the activation process was eval-
uated by measuring the amount of hydroxyl groups

OH) on the surface of nanosilica via titration method
(

and supported by FTIR analysis. Two coupling agents
namely 3-aminopropyl triethoxysilane (APTES) and neo-
pentyl (diallyl)oxy,tri(dioctyl) phosphate titanate (Lica
12) were used for surface treatment after activation
process. The mechanical properties of polypropylene
matrix reinforced with silica nanoparticles were deter-
mined by tensile and impact test. Hydroxyl groups on
the nanosilica surface played an important role in
enhancing the treatment with silane coupling agents.
To increase the amount of hydroxyl groups on the
nanosilica surface, the optimum concentration of
NaOH is 1 mol%. Tensile strength, tensile modulus,
and impact strength of nanosilica/PP composites
improved with activation process. As the coupling
agent is concerned, APTES coupling agent is more
pronounced in enhancing the mechanical properties of
the composites when compared with Lica 12 coupling
agent. POLYM. COMPOS., 30:1693–1700, 2009. ª 2008 Soci-
ety of Plastics Engineers
INTRODUCTION
Polymeric nanocomposites are materials that are cre-
ated by introducing inorganic nanoparticles (often refer to
as filler) into organic polymer matrix and are finely dis-
persed within the matrices [1]. In comparison with neat
polymers and microparticulate composites, nanocompo-
sites have been reported to exhibit markedly improved
properties, such physical, modulus, strength, flame resist-
ance, gas barrier performance, better dimensional stability,
Correspondence to: Hazizan Md Akil; e-mail: hazizan@eng.usm.my
Contract grant sponsor: Universiti Sains Malaysia, Penang.
DOI 10.1002/pc.20744
Published online in Wiley InterScience (www.interscience.wiley.com).
V
C 2008 Society of Plastics Engineers
POLYMER COMPOSITES—-2009
solvent resistance, and optical transparency. Furthermore,
these improvements are usually achieved at low concen-
tration of inorganic filler (1–10 wt%). This is strongly
contrasted with conventional filled polymers (microparti-
culate) which generally require high filler loading, typi-
cally 25–40 wt%. In this context, the nanocomposites are
much lighter in weight and can be processed more easily
as compared to microcomposites. Therefore, it has
attracted by various applications such as in automotive,
packaging, electrical, electronic, appliances, and equip-
ment industries [2–4].
Semicrystalline isotactic polypropylene (i-PP) has
become the most interesting commodity thermoplastic,
because of its higher isotacticity, enhanced mechanical
properties, and narrow molecular weight distribution and
good clarity. Therefore, its worldwide production grew up
very fast and there is a tendency to replace some of the
traditional polymers in many of their applications. Me-
chanical properties of this polymer can be easily
improved by introducing nanoparticles with high surface
area that could act as reinforcement particles [5]. Nano-
particles have the ability to create a great amount of inter-
phase in a composite that could enhance the intermolecu-
lar interaction of the matrix because of the incredibly
high surface area to volume ratio [6]. As we know that,
nanocomposites with excellent properties must produce
well-distributed nanoparticles over the polymer matrix
without unwanted agglomerates. So, this will be the major
task for all the researchers who work in this area.
From the practical point of view, dispersive mixing in
preparing polymer-based particulate composites has an
important technical meaning. However, a homogenous
dispersion of nanoparticles in a polymer is often difficult
to achieve with the existing compounding techniques
because of the strong tendency of the particles to agglom-
erate and generate high melt viscosity during processing.
In many cases, the so called nanoparticle-filled polymers
contain a number of loosen cluster of nanoparticles, as
demonstrated by the work of Jana and Jain [7] which
deals with untreated nanosilica/polyethersulphone compo-
 TABLE 1. Details of the coupling agents for the surface treatment.
Coupling agent
3-Aminopropyl-triethoxysilane
(APTES)
Neopentyl (diallyl)oxy, tri(dioctyl)
phosphato titanate (Lica 12)
sites. They observed that when the composites are sub-
jected to force, loosen cluster of nanoparticles initiate pre-
mature failure because of stress contact region.
There are at least three ways to overcome this dilemma
and to give full advantages of nanoparticles to ensure
strong adhesion between the nanoparticles and polymer
matrix. The first is to treat the surface of nanoparticles,
the second is to modify the surface properties of polymer,
and the last is to develop a new mixing technology by the
addition of an interfacial modifier or a compatibilizer to
the composites. Rong et al. were developed both irradia-
tion grafting polymerization and chemical grafting reac-
tions on the nano-SiO2 surface [2–4, 6]. They summarized
that the ultrafine phase dimension played a major role in
influencing the characteristic of the polymer nanocompo-
sites, and the properties of the composites were strongly
dependent on the nature of the filler–matrix interface.
Both isothermal and nonisothermal crystallization behav-
ior of PP/nano-SiO2 was studied [5]. The authors reported
that the surface treatment of nanoparticles is an effective
way to improve the interface between nanoparticles and
PP matrix. The improvement of the adhesion between PP
and SiO2 and modification of the PP surface properties by
chemical grafting, plasma treatment, or plasma polymer-
ization had been carried out in order to change the nonpo-
lar PP to a polar one [8, 9]. PP-g-MA copolymer was
employed by Bikiaris et al. as compatibilizer which can
be utilized as a boundary layer material. On the basis of
the theory of filler toughening of the polymer matrix, the
formation of a boundary layer between the filler and ma-
trix was predicted [10]. The most recent work has been
done by Zhou et al. to produce nanosilica/PP composites
by introducing a bifunctional monomer glycidyl methac-
rylate (GMA) onto the nanoparticles surface by chemical
graft polymerization and melt blended with aminated PP
[11]. They found out that the reinforcing and toughening
effects were controlled by flexibility of the grafted poly-
mer as well as processing method.
In general, fumed silica is a synthetic amorphous sili-
con dioxide manufactured by hydrolysis of silicon tetra-
1694 POLYMER COMPOSITES—-2009
Chemical formula Producer
Fluka Chemie
Kenrich
chloride in an oxygen-hydrogen gas flame at high temper-
ature. In contrast to crystalline silica which is carcino-
genic, fumed silica is considered as nontoxic and
nonirritating due to its completely amorphous state. Due
to the high temperature involved during production of
fumed silica, concentration of hydroxyl group on its sur-
face which could trigger the coupling mechanism is low
[12]. Therefore, activation process is proposed to generate
higher concentration of hydroxyl group prior to coupling
treatment. The use of fumed silica as fillers in thermo-
plastics has been documented by some researchers [13–
16]. They claimed that fumed nanosilica generated a rein-
forcing effect when introduced into thermoplastic matrix.
In this work, 1 wt% of fumed silica was subjected to
surface activation process prior to coupling treatment
using either 3-aminopropyl-triethoxysilane (APTES) or
neopentyl (diallyl)oxy,tri(dioctyl)phosphate titanate (Lica
12). The concentration of hydroxyl group on the surface
of silica was quantified. FTIR analysis was performed to
study the chemical changes and coupling mechanism.
EXPERIMENTAL DETAILS
Materials
Polypropylene homopolymer (TITANPRO PM-255)
was supplied by Titan PP polymers (M) with a melt flow
index of 1.6 g/10 min (at 2308C). The density of the poly-
mer is 0.9 g/cm3. Quartz fumed silica with an average
primary particle size of 7 nm and a specific surface area
of 390 m2/g was obtained from Sigma-Aldrich. 3-Amino-
propyl-triethoxysilane (APTES) and a commercial grade
of titanate Lica 12 (neopentyl(diallyl)oxy,tri(dioctyl)phos-
phate titanate) supplied by Fluka Chemie and Kenrich
Petrochemicals, respectively, was used as coupling agents
in this compounding. The chemical composition of the
two coupling agents can be found in Table 1. Sodium hy-
droxide (NaOH) was used as received in the surface acti-
vation process.
DOI 10.1002/pc
Surface Activation of Fumed Silica
Three different molar ratios between fumed silica and
NaOH such as 1:0.01, 1:0.05, and 1:0.1 were used to
study the effectiveness of the surface activation process
on fumed silica. NaOH was diluted in 100 ml distilled
water and placed into a round-bottom flask. About 4.00 g
of fumed silica was added and the mixture was stirred
using a mechanical stirrer in a water bath at the tempera-
ture of 60–708C for 24 h. Then the mixture was cooled
down to room temperature prior to neutralization using
acetic acid. Activated silica powder was separated from
the solution under centrifugal forces. The powder was
then washed with methanol for three times and placed
into the oven for drying at 1208C for 24 h.
Titration Method to Quantify the

OH Groups on the
Fumed Silica Surface After Activation Process
The number of hydroxyl group (

OH) on the surface
of nanosilica is estimated by using titration method as
described in [17]. Two grams (W) of nonactivated and
activated silica particles were weighed and charged into
an Erlenmeyer flask (100 ml), where 80 ml of 0.05 N
aqueous solution of NaOH was added. The flask was
capped and stirred by using magnetic stirrer for 24 h at
ambient temperature. The mixture was then separated by
centrifugation process and 10 ml of the solution was
sampled. Prior to titration process, 0.5 g of phenolphthal-
ein was added into a mixture of 50 ml ethanol and 50 ml
distilled water. Three drops of phenolphthalein solution as
an indicator was added into the solution and further
titrated until neutralization (color changes from purple to
transparent) with a 0.05 N aqueous solution of HCl (A
ml). The above procedures were repeated with a blank so-
lution (0.05 N NaOH without silica sample). The amount
of the solution of HCl for neutralization is B ml
ðB
AÞ 3 0:05 3 8
X¼ ð1Þ
W dried in a vacuum oven for 24 h at 808C, prior to the melt
where X is the amount of the surface

OH groups per
unit weight of the silica particles (mM/g).
Filler Treatment Using 3-Aminopropyl-Triethoxysilane
Activated fumed silica (1 mol% of NaOH) was used
for surface modification with coupling agents. About 4.0 g
of activated and nonactivated silica were functionalized
with 2 wt% (2 g) of 3-aminopropyl-triethoxysilane
(APTES) according to solvent content in 100 ml ethanol
under continuous stirring for 24 h at room temperature.
The amino silane content was chosen based on the
research work done by Takahashi and Paul [18]. The mix-
ture was then separated under centrifugal forces, washed
again with ethanol to drive off excessive silane, and dried
in an oven at 808C for 24 h.
DOI 10.1002/pc
FIG. 1. Concentration of

OH group on the activated fumed silica sur-
face with different concentration (mol%) of NaOH solution.
Filler Treatment Using Titanate Lica 12
(Neopentyl(diallyl)oxy,tri(dioctyl) phosphate titanate)
The amount of Lica 12 to be incorporated does not
depend on the surface area of the fillers. According to the
reference manual supplied together with Lica 12 [19], the
recommended dosage of Lica 12 is either 0.5 wt% of total
filler or 0.2 wt% of resin, whichever provides the greater
absolute amount of titanate. Toluene was used as a sol-
vent to reduce the viscosity of the titanate. The 100 ml
toluene (solvent) was added into an Erlenmeyer flask and
the titanate was stirred mechanically into the solvent for
30 min. The filler (4.0 g) was then added into the flask
and the slurry was mixed for 3 h at room temperature
until good dispersion was achieved. The slurry was then
under centrifugation, washed again with toluene to drive
off excess titanate, and dried in an oven at 808C for 24 h.
Composites Preparation and Characterization
Modified fumed silica particles were grind in mortar
and pestle followed by sieving (62 lm) to obtain fine and
uniform particle size. After that the silica particles were
processing. All composites were prepared using melt blend-
ing technique in a Thermo Haake Polydrive Internal Mixer
fitted with cam blades at a rotor speed of 60 rpm Mixing
time and temperature were held constant at 8 min and
1808C, respectively. For system with silica filled compos-
ite, silica particles were added after 4 min of compounding
time. The compounded materials were sheeted by two roll
mill before hot compression. All composite samples were
compression molded (using frame mould) at 1808C into a
plaque of 1.0 mm and 4.0 mm thick for tensile and Izod
impact testing, respectively. Prior to the 2 min compression
process, preheating was carried out for 8 min. The mould
was immediately transferred to a cold press for 8 min.
Measurements of the mechanical properties, such as
tensile strength, modulus, yield strength, and elongation at
break were performed on an Instron 5533 dynamometer,
in accordance with ASTM-D638 using a crosshead speed
POLYMER COMPOSITES—-2009 1695
 FIG. 2. Enlarged FTIR spectra changes of four major peaks which are silanol, siloxane, H2O molecule, and
geminol after surface activation with different concentration of NaOH solution (mol%). (SiO2–pure silica, and
SiNA-1, SiNA-5, SiNA-10 are referring to 1, 5, and 10 mol% of NaOH, respectively).

of 50 mm/min and gauge length of 50 mm. Prior to meas-
urements the moulded specimens were cut into a dumb-
bell shape and conditioned at room temperature for at
least 24 h. The un-notched Izod impact experiment was
performed using an impact pendulum tester (Zwick Model
5101) with 7.5 J heater according to the ASTM-D256. All
mechanical tests were conducted at room temperature.
Five measurements were conducted for each specimen
and the results were averaged to obtain a mean value.
red Spectrophotometer (FTIR) with 4 cm21 resolution to
identify surface functional groups. Particles were mixed
with dried powdery potassium bromide (KBr), palletized
under pressure and then scanned for 32 times. The scan-
ning of the FTIR spectrophotometer was carried out in
the range of wavelength of 4,000–400 cm21. Sample
plates were directly put on the holder to collect spectra.
RESULTS AND DISCUSSION

Infrared Spectroscopy Surface Activation on Fumed Silica

The FTIR spectrums of nontreated and treated silica The purpose of surface activation process is to increase
were recorded on a Perkin-Elmer Fourier Transform Infra- the concentration of

OH group on the surface of fumed

1696 POLYMER COMPOSITES—-2009 DOI 10.1002/pc

 TABLE 2. IR vibration bands of fumed silica [9]. substitution. From the figure, it can be observed that
21 fumed silica activated by 1 mol% and 10 mol% of NaOH
Wavenumber (cm ) Peak assignment
provided higher amount of

OH group which are
3,400
OH vibration (stretching)
Si
1.09 mM/g and 1.11 mM/g, respectively (about 150%
1,630


OH bending (molecular H2O) higher than that of nonactivated fumed silica). Approxi-
1,250–1,020
O

Si

Si asymmetric stretching vibration mately 1 mol% of NaOH (in the range of this study) is an
960–975
O (H . . . . . . . H2O) bending
Si
optimum amount of NaOH that used for the activation pro-
800 In-plane bending (geminol)
cess to take place efficiently. The above results showed that
silica surface has been successfully activated by NaOH.
silica. The fumed silica which usually synthesized through This can be further examined by using FTIR technique.
high temperature hydrolysis (about 1,400 K) of SiCl4 in A series of spectrums recorded FTIR on various silica
the O2/H2 flame [12] has limited amount of hydroxyl (SiO2) particles is given in Fig. 2, there is a strong ab-
group presents on its surface as compared to natural sorbance at 1,100 cm21 attributed to the Si

O

Si (si-
silica. In this study, the concentration of the hydroxyl loxane) groups and a broad peak with a maximum at
group on the surface of silica (before and after activation 3,440 cm21 attributed to the surface hydroxyl groups.
process) was calculated using Eq. 1. The summary of the Assignments of IR bands of fumed silica are also given in
result is given in Fig. 1. The surface of silica was modi- Table 2 [20]. On the other hand, the absorbance of
fied by substituting silanol group with other functional Si

O

Si peak became weaker for the spectrum of silica
group from coupling agent via intercharging the degree of activated by 1 mol% (SiNA-1) and 10 mol% of NaOH

FIG. 3. Proposed bonding mechanism of APTES to the surface of silica particle.

DOI 10.1002/pc POLYMER COMPOSITES—-2009 1697

 FIG. 4. The reaction of a monoalkoxy or neoalkoxy triorganofunctional titanate coupling agents with the
surface of inorganic filler resulting in the formation of an organic titanium monomolecular layer on the inor-
ganic particle surface.

(SiNA-10) but spectrum for silica activated by 5 mol% ganic interphase, giving rise to the formation of organic
NaOH (SiNA-5) remain unchanged. This may be due to monomolecular layers on the surface of the substrate (see
the breaking of the siloxane groups after activation pro- Fig. 4). These layers are compatible and/or react with the
cess. Furthermore, the silanol band at 3,400 cm21 for organic phase via alcoholysis mechanism which can be
SiNA-1 and SiNA-10 become broader and deeper after represented by the following [21]:
surface activation as compared to raw nanosilica. It can
be concluded that the 1mol% of NaOH is enough to acti- MOH þ R0 O

TiðO

X

R00

YÞm
vate the silica surface by introducing more

OH group ! MO

TiðO

X

R00

YÞm þ R0 ðOHÞ ð2Þ
onto the silica surface (proved by titration).
where M, substrate; H, surface proton; m, 3,titanate trior-
ganofunctional.
Surface Modification on Fumed Silica The effectiveness of modification by silane and tita-
nates coupling agents on nanosilica surface was studied
Chemical surface modification may be defined as the by using FTIR analysis. Series of FTIR spectrums of vari-
chemical bonding of molecules or molecule fragments to
a surface in order to change its chemical or physical prop-
erties in a controlled way [20]. Organofunctional silane
APTES have an advantage over comparable organic com-
pounds in that the silane has potential for bonding
through several mechanism. Electrokinetic forces can be
used to attract or repel at relative great distances. At
closer approach, Van Der Waals forces, hydrogen bond-
ing, and covelent bonding are possible through silanol
groups. By combining all of these possibilities in a single
molecule, the silane is uniquely capable of competing
with water for hydroxylated surfaces [20].
Reaction mechanism of silane coupling agent on silica
surface is believed to occur in three steps as illustrated in
Fig. 3. First, the alkoxy group in the coupling agent will
undergo a hydrolysis process. Water for the hydrolysis
may come from the surface humidity of the filler (in the
case of silane treatment). Next, the hydrolyzed silane reacts
with the hydroxyl from the filler surface by hydrogen bond
formation. Then, Si

O crosslinks are formed between the
filler surface and the adjacent functional groups in a con-
densation reaction with the elimination water [7].
Lica 12 is a tetrafunctional compound derived from ti- FIG. 5. FTIR spectra of silica treated by different coupling agents: (a)
tanium, which reacts with the free protons in the inor- silica as received, (b) silica treated APTES, and (c) silica treated Lica 12.

1698 POLYMER COMPOSITES—-2009 DOI 10.1002/pc

 FIG. 6. Tensile properties of nanosilica filled polypropylene as a function of coupling agents at 1 wt% filler con-
tent: (a) tensile strength, (b) Young’s modulus, (c) elongation at break, and (d) un-notched Izod impact strength.

ous silica nanoparticles are presented in Fig. 5. Activated
and nonactivated silica were further modified using
APTES and Lica 12, respectively. For spectra of activated
silica modified by APTES and Lica 12, absorption bands
in the region of 2,800–3,000 cm21 are observed due to
CH-stretching vibrations of CH2 and CH3 groups [20].
But, no significant peak of NH2 (typically at 3,373 cm21;
3,310 cm21; 1,597 cm21) groups were seem in spectrum
of silica treated with APTES [20]. It may be due to the
small amount of APTES used in this system. In the case

DOI 10.1002/pc POLYMER COMPOSITES—-2009 1699

of activated silica with 1 mol% of NaOH was chosen for
further investigation.
Tensile Properties
In this section, comparison of tensile properties
between activated (NaOH) fumed silica and nonactivated
fumed silica treated by APTS and Lica 12 at 1 wt% filler
content is discussed. The tensile properties of nanosilica
filled polypropylene composites as a function of coupling
agents are displayed in Fig. 6. From Fig. 6a, it is clear
that activation process shows its effectiveness in the
amino silane coupling system in order to increase the ten-
sile strength. For other system, activation process has
given negative result on this property (tensile strength val-
ues even lower than that the neat PP). It is due to the
increasing of

OH group on the silica surface after acti-
vation process which more applicable for the amino silane
coupling agent to take place in the reaction compared to
the Lica 12. On the other hand, Lica 12 titanate coupling
agent is useful for the treatment on filler surface which
has low concentration of

OH group such as calcium
carbonate (CaCO3) [22].
In the case of Young’s modulus, activation process has
improved the toughness of the composites as shown in Fig.
6b. Surprisingly, composite with silica treated by APTES
under activation process provide the highest value among
the systems. The capability of the composite interface to
transfer elastic deformation was greatly depended on the
interfacial stiffness and static adhesion strength [6]. A high
interfacial stiffness corresponds to a high composite modu-
lus. The increase of modulus in this composite system is
due to the modulus matching of the filler and the matrix.
Failure strain in tensile testing can be correlated to the
rupture behavior of composites materials. In general, the
incorporation of particulate filler usually deteriorates the
level of strain at failure [6]. Failure strain of various com-
posites studied is summarized in Fig. 6c. It is obvious to
note that a greater increase at elongation at break is
observed for composite with 1 wt% of pure nanosilica
without activation process, reaching up to 320% com-
pared to neat PP. Nanosilica filler has introduce additional
crazing and perhaps act as stoppers to crack growth at the
same time [23]. But, the activation process has reduced
the elongation at break for all the systems. The activation
process inhibits the strain hardening during matrix orien-
tation when the load was applied.
From the un-notched impact strength (Fig. 6d), it can be
seen that none of the specimens considered has the impact
energy value lower than that of neat PP. The activation
process on both APTES and Lica 12 coupling systems are
not so pronounced as the impact strength is concerned.
CONCLUSIONS
Activation process has been successfully applied on
nanosilica surface. Activated nanosilica treated by amino
1700 POLYMER COMPOSITES—-2009
silane coupling agent showed better tensile strength and
Young’s modulus (at 1 wt% filler content) as compared to
Lica 12 coupling agent. The optimum concentration of
NaOH solution to activate the nanosilica surface was
1 mol%.
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DOI 10.1002/pc