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Thermoset nanocomposites using hybrid nano

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Article in Materials Chemistry and Physics · August 2010

DOI: 10.1016/j.matchemphys.2010.02.073

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 Materials Chemistry and Physics 122 (2010) 343–349

Contents lists available at ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Thermoset nanocomposites using hybrid nano TiO2 –SiO2

Abdollah Omrani a,∗ , Saeedeh Afsar b , Mohammad Ali Safarpour b
a
Faculty of Chemistry, University of Mazandaran, P.O. Box 453, Babolsar, Mazandaran, Iran
b
Department of Physical Chemistry, Faculty of Chemistry, Iran University of Science and Technology (IUST), Narmak, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: A systematic approach was considered to study the matrix properties by introducing hybrid nanosize
Received 1 August 2009 TiO2 –SiO2 (50–120 nm, 2.5–10% by weight) filler into an epoxy resin. Ultrasonic mixing process was
Received in revised form 4 February 2010 employed to disperse the particles into the resin system. The thermal, flame retardancy, morphology and
Accepted 28 February 2010
the viscoelastic properties of the nanocomposite and the neat resin were measured using DSC, TGA, DMTA,
and SEM techniques. The curing reaction at four different temperatures was studied for the nanocompos-
Keywords:
ite having 5% nano TiO2 –SiO2 and then the reaction rate and conversions were analyzed. The experimental
Nanostructures
data exhibited an autocatalytic behavior of the reaction that was explained by the model proposed by
Coatings
DSC
Kamal. The dependence of the activation energy on the conversion degree was interpreted by isoconver-
Thermal properties sional method. Morphology studies using SEM showed that the nanoparticles were dispersed into the
entire volume of the resin, homogeneously. From the experimental data, the nanocomposite exhibited
increase in storage modulus, glass transition temperature (Tg ), and decomposition temperature from the
neat epoxy system.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction hyperbranched polymers have the advantage of highly branched

Epoxy resins are handled in a variety of applications due to their
excellent properties such as thermal stability, mechanical response,
electrical, corrosion resistance, and good dimensional stability. The
crucial factors influencing their performances are the molecular
structure, curing conditions, and the resin–hardener ratio. It is well
known that the commonly used epoxy resins are highly rather
brittle when cured with stoichiometric amount of curing agents
due to its highly cross-linked structure. Its poor fracture tough-
ness restricts the use of this resin in structural applications. The
improvement of toughness is then highly desirable to meet their
brittleness. Nowadays, strengthen the epoxy-based thermosets
through the addition of a second phase is an active research area in
composites science and technology. Significant efforts have been
devoted to this issue using different approaches by incorporating
micrometer size liquid rubber [1–3], core–shell rubber particu-
lates [4–7], thermoplastic particles [8–11], and hyperbranched
polymers [12–14] into epoxy resins. Addition of rubber phase to
the epoxy matrix leads to impressive toughening but results in
the deterioration of the modulus, processability, and glass transi-
tion temperature. The introduction of thermoplastic particles will
provide a sensible toughening effect and cannot assurance satisfac-
tory results in handling and processing conditions. Although the
∗ Corresponding author. Tel.: +98 112 5342383; fax: +98 112 5342350.
E-mail address: omrani@umz.ac.ir (A. Omrani).
structure and the large number of functional reactive groups but
unfortunately, they suffer the disadvantage of poorer mechanical
properties compared to their linear analogues. As a result, there is
still a noteworthy need to develop alternative toughening methods
to improve epoxy toughness without compromising other desir-
able properties. Development in the synthesis of nanometer size
particles, as a second phase, has made it possible to improve the
properties of thermosetting polymers as a facile way. Nanoparticles
can fill up the feeble microregions of resins to boost the interac-
tions at the polymer–nanofiller interface. A dramatic increase in
the interfacial area can then improve the polymer properties sig-
nificantly. Organic–inorganic hybrids have paid great attentions in
recent years. It is found that the resin modified using inorganic par-
ticles, such as TiO2 , SiO2 , Al2 O3 , clay, and SiC can improve the resin’s
properties remarkably [15–20]. Titanium dioxide has been used as
the filler to improve the properties of many polymers. Many stud-
ies are devoted for TiO2 filled composites in the area of thermal,
viscoelastic, and mechanical properties as well as photocatalytic
activity [21–24]. Individual titania has poor mechanical properties
and small specific surface area. Its structural and sorptive char-
acteristics are less thermally stable and TiO2 suspensions are less
stable toward coagulations. To enhance the characteristics of TiO2
particles, SiO2 has been incorporated as shell, core or in a dispersed
phase since the component introduced plays a role of controlling
the catalytic activity and refractive indices. It was observed [25,26]
that hybrid TiO2 –SiO2 exhibits higher catalytic activity in compar-
ison to sole TiO2 . Although this hybrid nanoparticles would not

0254-0584/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2010.02.073
344 A. Omrani et al. / Materials Chemistry and Physics 122 (2010) 343–349

posses the advantages of both TiO2 and SiO2 , but could expand
their applications through the production of active sites owing
to TiO2 and SiO2 interactions. Inserting TiO2 onto SiO2 provides
a facile approach to produce titania surface having high thermal
stability and good mechanical properties [27]. On the other hand
very small research reports have been appeared in the literature on
employing nano TiO2 in combination with other solid nanoparticles
as toughening agent of epoxy resins. According to our knowledge
no study has been made on cure kinetics and final properties of
epoxy resin cured with 4,4 -diaminodiphenyl sulfone (DDS) in the
presence of hybrid nano TiO2 –SiO2 in the literature. In this paper,
attempts were made to develop nanoparticles filled epoxy com-
posites with improved final properties. Mesoporous hybrid nano
TiO2 –SiO2 particles using polyethylene glycol as a pore-forming
agent were synthesized and then directly incorporated into epoxy
matrix without any surface treatment. To evaluate the key factor
of materials processing, i.e., kinetic parameters, isothermal curing
experiments are conducted on the optimum composition. Finally,
the effectiveness of the used procedure in the final viscoelastic,
thermal stability, and morphology was evaluated by means of
DMTA, TGA, and SEM techniques.

2. Experimental

2.1. Materials Fig. 1. TEM image of the synthesized hybrid nano TiO2 –SiO2 .

The matrix material used in the present study was a commercial diglycidyl
ether of bisphenol-A epoxy resin (DGEBA) purchased from Shell chemicals, Epon
828, having an epoxy equivalent weight of 185 g equiv−1 . The epoxy equivalent
weight of the received resin was determined by chemical titration method using
hydrogen bromide and according to ASTM D 1652-97 [28]. The curing agent was 4,4 -
diaminodiphenyl sulfone (DDS) from Merck which is a solid bifunctional aromatic
amine with a molecular weight of 248.3 g mol−1 . The epoxide groups at both ends
of the chain will participate in cross-linking reaction when mixed with the diamine
(DDS) hardener. All the other solvents and reagents were purchased from Fluka. The
SiO2 /TiO2 nanofiller were synthesized to the procedure described in below.
2.2. Synthesis of hybrid nano TiO2 –SiO2
The sol–gel procedure, with hot water treatment described in the literature
[29,30], was used to produce anatase TiO2 -dispersed silica films. A description of
the utilized approach was given as follows: silicon tetraethoxide was hydrolyzed
with hydrochloric acid (3.6%) at room temperature for 30 min; the mole ratio of
water to silicon was 4. The resulted solution was then mixed with titanium tetra-n-
butoxide and stirred for 30 min continuously. The TiO2 –SiO2 mole ratio was 50/50.
Poly(ethyleneglycol), PEG, of an average molecular weight of 600 was added to the
above solution and the resultant composition served as coating slurry. The weight
ratio of PEG added to the TiO2 –SiO2 oxides was fixed to be unity. The produced
TiO2 –SiO2 films were coated on glass substrates and finally dried at 90 ◦ C for 1 h
in a vacuum oven. A transmission electron microscope (TEM) image of the pro-
duced hybrid nanofiller is shown in Fig. 1. According to TEM image, the mean
particle size of TiO2 –SiO2 were estimated to be around 30–70 nanometers (see
Fig. 1).
2.3. Specimen preparation
The synthesized hybrid nano TiO2 –SiO2 was used as the filler to prepare epoxy
nanocomposites. Various amounts of the nanofiller was mixed with the proper
value of epoxy resin and stirred for 16 h. Then a stoichiometric amount of DDS
was added to the composition and stirred for 30 min. The mixture was sonicated
for 1 h using an ultrasound bath by Delta D200H and then poured into a con-
tainer or in a mold. Bulk samples of 1000 mg from freshly produced mixtures were
separated and about 20 mg in size samples used for thermal curing by DSC. The
samples were sealed with an aluminum pan and kept in a refrigerator before intro-
ducing them toward thermal events. Samples for DMTA and SEM analyses were
prepared using a mini test press machine (Toyoseiki model). The samples were
cured isothermally at 150 ◦ C for 90 min at pressure of 25 MPa and then undergo a
postcuring treatment at 180 ◦ C for 45 min at the same pressure to produce nanocom-
posites.
2.4. Characterization techniques
DSC experiments were made at under high purity nitrogen (40 cm3 min−1 ) using
a NETZSCH STA 409 PC thermal analyzer. The samples were heated from −25 to
250 ◦ C at heating rate of 10 ◦ C min−1 to record the heat evolution due to the ther-
mal polymerization and to determine the optimum concentration of the nanofiller.
The cured sample was then cooled to −25 ◦ C at the same heating speed. Finally, the
samples were reheated to 250 ◦ C in order to determine the glass transition tem-
perature (Tg ) and to confirm the absence of any residual curing. For isothermal
measurements, the temperature was raised from 25 ◦ C to the curing tempera-
ture at the maximum heating rate. The isothermal cure temperatures of 145, 150,
155 and 160 ◦ C were selected from the dynamic heating experiments. The effect
of the used procedure on the viscoelastic and mechanical properties of the pro-
duced epoxy nanocomposites were investigated by DMTA tests. These tests were
carried out on a DMA-TRITON model Tritec 2000 DMA. The frequency was 1 Hz
and the samples were heated from 30 to 250 ◦ C at 5 ◦ C min−1 . The samples were
parallelepiped bars (1.5 mm × 12 mm × 35 mm). The produced nanocomposite was
microstructural characterized by SEM to evaluate the effectiveness of the used dis-
persion treatment. A JEOL Scanning Microscope (JEOL JSM-6400) was utilized for
recording SEM micrographs. All samples were sputter-coated with gold prior to SEM
observations. A JEOL TEM model JEM-1230 operating at 200 kV was used to obtain
information about the size of the synthesized hybrid nanofiller. The film of hybrid
nanofiller was microtomed by Ultracut Uct, which possessed 100 nm thickness sizes.
A thermogravimetric analyzer (TGA; Perkin-Elmer, model: TGA 7, USA) was used to
analyze the thermal degradation characteristics of the epoxy and its nanocompos-
ite. The samples were heated from room temperature to 700 ◦ C at heating speed of
10 ◦ C min−1 in air.
3. Results and discussion
3.1. Thermal properties
Table 1 shows some important data dynamically cured samples
for various compositions. The DSC thermograms were recorded
at heating speed of 10 ◦ C min−1 at two times and the Tg and H
reported as average values. The increase in Tg as the nanofiller
content increases is clear. It could be implied that increasing the
value of hybrid nanofiller promotes the interaction between the
resin matrix and the solid inorganic phase. Better final thermal
Table 1
Results obtained from analysis of the DSC curves for various nanocomposites and
the neat epoxy system.
Hybrid nanoparticle (%) Tmax (◦ C) Tg (◦ C) Htotal (J g−1 -epoxy)
0 163.9 57 231.5
2.5 160.5 67.8 215.9
5 162.5 70.2 269.9
7.5 161.7 75.4 258.1
10 161.3 81.1 227.3
 A. Omrani et al. / Materials Chemistry and Physics 122 (2010) 343–349 345

and mechanical properties could be interpreted as a result of such

interaction.
Since the sample mass was different for each DSC measurement,
to do a reliable comparison on the reaction enthalpy, its value was
reported in terms of Joule per gram of epoxy. Indeed, this trend of
action to determine the optimum composition. Accordingly, it was
recognized that the DGEBA/DDS system having 5% of the hybrid
nano TiO2 –SiO2 is the optimum formulation. This was necessary
because all the studies in the next sections have been conducted
using this formulation.

3.2. Kinetic analysis

Cross-linking of epoxy prepolymer with amine-based curing

agents could be described according to the mechanism proposed by
Smith and Horie [31]. It proposes primarily two ways (catalytic and
non-catalytic) of ring opening epoxy polymerization. The activation
of the ring opening epoxy is achieved by proton donors such as the
generated hydroxyl groups during the course of reaction. Both of
primary amine and hydroxyl groups can catalyze the reaction as
well. Homopolymerization or etherification is another important
reaction that should be considered at high curing temperatures.
This reaction can be catalyzed by the presence of tertiary amine Fig. 3. Degree of cure versus time profiles for the DGEBA/DDS/nano TiO2 –SiO2 (5%)
and when the epoxy prepolymer is in excess value. The impor- nanocomposite at different temperatures.
tance of the etherification reaction depends also on the basicity
of the used cross-linking agent. For cross-linking temperature near
data used to calculate the degree of cure at various temperatures
to Tg , the sample vitrifies and the curing process is controlled by
and the corresponding profiles are shown in Fig. 3.
the diffusion [32], owing to the reduced mobility of reactants in
Fig. 3 exhibits that the curing degree varies with the curing
the reaction system. But when the isothermal curing temperature
temperature and time. At a given temperature, the curing degree
(cross-linking temperature) is about 30 ◦ C higher than the Tg , the
increased fast during the initial reaction stage, then increased grad-
effect of the diffusion on the polymerization mechanism can be
ually, and finally tended to a certain value. This was attributed to
omitted. Until now, there are no general kinetic schemes that could
the sequence reactions of chain extension, branching and self cross-
be universally accepted to interpret cross-linking mechanism of
linking of epoxy resin during the polymerization. These reactions
epoxy-amine reaction. In the case of aromatic amines, the substi-
were reduced the mobility of the reacting molecules. To calculate
tution effect postpones the cross-linking and the formation the gel
the reaction rate, it is proposed that the heat flow is proportional
because the produced secondary amines are less reactive than pri-
to the reaction rate. Therefore, the raw data from DSC profiles were
mary amine groups. In order to study isothermal curing reaction,
used to calculate the rate of reaction according to the following
the first stage was to choose the appropriate curing temperatures.
equation:
Using the data from dynamic DSC four isothermal temperatures
of 145, 150, 155, and 160 ◦ C were selected. Fig. 2 displays the DSC d˛ dQ 1
Reaction rate = = × (1)
curves of the cured nanocomposite having 5 Phr of the nanofiller. dt dt Ht
Expectably, the maximum rate of the cure peak was increased
with increasing isothermal temperature, while the time to reach where ˛ is the cure degree, dQ/dt is the heat flow, and Ht is the
the apex decreased with increasing temperature. The original DSC total reaction heat. The reaction rate at various isothermal temper-
atures was calculated and the result is shown in Fig. 4.
The methods used to study the curing kinetics could be classi-
fied in mechanistic [33] or phenomenological [34,35] approaches.
Mechanistic models were made from the balance of chemical
species involved in the chemical reaction. Since the epoxy cure is
very complex due to the contact between the chemical kinetics
and changes in their physical properties, thus, it is difficult to take
a mechanistic model as a suitable tool to obtain the reliable kinetic
parameters. Phenomenological or empirical models were preferred
to study the curing kinetics of these polymers. Most recently, the
phenomenological approach proposed by Kamal [36] was used to
analysis the curing reaction of epoxy nanocomposites. For the ther-
mosetting polymers, the reaction rate is usually expressed as:

d˛
 −E 
a
= A exp f (˛) (2)
dt RT

where A is the frequency factor, Ea is the activation energy, f(˛)

Fig. 2. Isothermal DSC profiles of DGEBA/DDS/nano TiO2 –SiO2 (5%) nanocomposite
obtained at different temperatures.
is a function of the cure degree (˛), R is the gas constant, and T is
the absolute temperature. When a reaction could be catalyzed by a
proton donor that presented or produced during the curing process,
the reaction mechanism is considered to be autocatalytic. Normally,
the following equation can be refereed as the Kamal autocatalytic
346 A. Omrani et al. / Materials Chemistry and Physics 122 (2010) 343–349

Fig. 4. Reaction rate versus conversion profiles at different temperatures.

Fig. 5. Dependence of the global activation energy to degree of cure.

model:
d˛
= (k1 + k2 ˛m )(1 − ˛)n
dt
where k1 and k2 are the rate constants and m and n are reac-
tion orders of the autocatalytic and n-order reactions, respectively.
From Fig. 4, the conversion rate had a maximum value at time non-
zero typically in the cure degree range of ˛ = 0.15–0.3 indicating
that the nanocomposite cure obeyed autocatalytic mechanism. So,
the Kamal autocatalytic model was used to estimate the kinetic
parameters. Several methods have been proposed to obtain the
parameters in Eq. (3) [37,38]. In the present study, we applied
the graphical method that described in our last publication [39]
to obtain the kinetic parameters. The results of the kinetic analysis
are listed in Table 2.
As the curing temperature increases the both rate constants
were increased. We did not consider the effects of diffusion into
the Kamal equation because the selected isothermal temperatures
were enough higher than the glass transition temperatures. Since
the epoxy-based nanocomposites cure is a multistep process a
newly discipline, namely isoconversional kinetic analysis, has been
developed recently [40,41] to better interpret the curing reaction by
probing the change of the global activation energy with cure degree.
The fundamental assumption of the isoconversional method is that
the reaction model is not dependent on heating rate in temperature
scan curing or temperature in isothermal curing. We attempt here
to employ the method used before in the literature [42,43] to con-
struct the Ea versus cure degree (conversion) profile. Fig. 5 shows
the result of isoconversional analysis. Clearly, the curing process
was under control of a same phenomenon in the conversion range
0.1–0.7 since the changes in activation energy in this range was
not high. As the cure degree increases from 0.7 to higher values,
the corresponding value of activation energy was increased due
to being importance another phenomenon in the curing process.
This could be attributed to increase in the cross-link density which
reduces the mobility of the active components in the reaction
(3) media.
3.3. Dynamic mechanical thermal analysis (DMTA)
The effect of the synthesized hybrid nanofiller on the dynamic
mechanical properties and the Tg of the produced nanocompos-
ite and the neat epoxy polymer were observed by DMTA analyzer
at three-point bending mode. The dissipation factor (tan ı) is the
ratio of the loss modulus and the stored modulus. Its value at peak
maximum shows the glass transition temperature. Fig. 6 shows the
storage modulus and tan ı profiles versus temperatures for the both
systems. The Tg was shifted toward higher temperature, about 33 ◦ C
due to the addition of the nanofiller. It might be implied that the
used nanofiller increases the glass transition temperature of the
soft-phase by restricting segmental chain motion and generating
an interphase region.
These restriction effects result in broadening the tan ı peak,
decrease in intensity (height) of this peak, and reduction of the
damping capacity. At the same time, the storage modulus of the
epoxy increased after adding the nanofiller in the whole tempera-
ture range (see Fig. 6). The modulus of epoxy/DDS/nano TiO2 –SiO2
nanocomposite and the temperature at which the modulus begins
to decrease are much higher than those of the neat epoxy system
demonstrating the strong confinement of nano-dispersed particles
on the nanocomposite. The increase in the storage modulus value
was significant for the both glassy and rubbery regions. This obser-
vation is most likely related to the interaction between the hydroxyl
groups of epoxy and the hydroxyl groups in the hybrid nanopar-
ticles at surface. The increase in Tg , also suggests that degree of
interaction between the polymer chains and the surface of the pro-
duced hybrid nanoparticles is increased.
3.4. Surface morphology of the synthesized nanocomposite

Table 2 SEM images of the fracture surfaces of the neat epoxy resin and
Results obtained from the kinetic analysis using the Kamal equation by applying the epoxy/hybrid nanofiller nanocomposite (5 wt.%) after three-point
graphical procedure.
bending tests are shown in Fig. 7. The fracture surfaces of the neat
T (◦ C) k1 (min−1 ) k2 (min−1 ) m n m+n r epoxy resin in Fig. 7a shows river lines which are the characteristics
145 0.000296 0.531 0.37 0.42 0.79 0.9922 of brittle fracture behavior. The fracture surface between the river
150 0.000411 0.573 0.43 0.39 0.82 0.9826 lines is relatively smooth. The fracture surfaces of the epoxy/nano
155 0.000498 0.594 0.75 0.45 1.2 0.9769 TiO2 –SiO2 nanocomposite (Fig. 7b), however, shows substantial
160 0.000695 0.683 0.87 0.81 1.68 0.9888
increase in the surface roughness exhibiting the reinforcement
 A. Omrani et al. / Materials Chemistry and Physics 122 (2010) 343–349
Fig. 6. DMTA profiles of storage modulus and tan ı changes with temperature for the epoxy nanocomposite (A) and pure system (B).
of the hybrid nanofiller in the epoxy matrix. Fig. 7c reveals that
the nanocomposite is curled and entangled which indicates reli-
able dispersibility and interfacial bonding between the organic
and inorganic phases. As it was shown in the magnified images
(Fig. 7d), the hybrid nanoparticles were embedded and tightly held
by the resin matrix and they were broken instead of being pulled
out during the flexural test. This verifies the existence of strong
interfacial bonding between the two phases. From the nanocom-
posite images it was concluded that good interfacial bonding
and flexural properties were achieved as the result of reliable
dispersion.
However, some micrometric nano TiO2 –SiO2 agglomerations
were observed on the surfaces of micrograph. These aggregates
may act as stress concentrators which are responsible for increasing
surface toughness.
3.5. Evaluation of thermal stability
Fig. 8 shows TGA curves of the neat epoxy and its nanocom-
posite. In order to do a better comparison, we attempt that the
temperature at 5% loss in mass (Td,5% ) be the initial thermal degra-
347
dation temperature. It was found that the Td,5% of the neat epoxy
is 315 ◦ C. Adding the hybrid nano TiO2 –SiO2 into epoxy resin at
5% increased the Td,5% value up to 331 ◦ C, which was actually 16 ◦ C
higher than that of the neat epoxy. Clearly, this phenomenon was
due to the addition of the nanofiller. This could be interpreted in
terms of its capability to catalyze the curing reaction and/or its role
as thermal stabilizer. The contribution of the catalytic effect could
be evaluated by defining a simple criterion namely relative curing
level (RCL). It is possible to calculate the RCL quantity using the val-
ues of reaction enthalpy in Table 1. The RCL value was determined
by dividing the value of reaction enthalpy for nanocomposite to
that value of the neat epoxy system. Therefore, the amount of RCL
is found to be 1.2. Obviously, with increasing the curing level in
the presence of nano TiO2 –SiO2 , the Td,5% value was dramatically
increased as well. On the other hand, the interaction/s between the
polymer chains and the inorganic nanoparticles may have another
contribution against thermal degradation. At 600 ◦ C, the char yield
of the neat epoxy and its nanocomposite were found to be 0% and
25%, respectively. The high value of reside for the nanocompos-
ite may again attributed to one or more numbers of the above
mentioned reasons.
348 A. Omrani et al. / Materials Chemistry and Physics 122 (2010) 343–349

Fig. 7. SEM photographs on fracture surface of the neat epoxy (a) and its nanocomposite (b–d).

4. Conclusion

The influence of the dispersion of hybrid nano TiO2 –SiO2 on the

thermo-physical properties of the epoxy nanocomposite was inves-
tigated. The results showed that the addition of 5% hybrid nanofiller
into epoxy matrix can improve the thermal stability and viscoelas-
tic properties considerably. Results from DSC experiments exhibit
that a proportional increase in the Tg was observed with increased
the nanofiller content. The curing analysis was followed by DSC
and the kinetic analysis was done by an autocatalytic model. As
the reaction proceeds, the enthalpy of reaction increases for the
nanocomposite. In order to obtain a desirable dispersion of nano
TiO2 –SiO2 in the resin matrix, an ultrasonic treatment was used.
Images from SEM measurements revealed that the used dispersion
method was reliable. At all temperatures below 100 ◦ C, the loss
modulus of the nanocomposite was higher than that of the neat
epoxy system as could be seen from DMTA curves. The increase in
loss modulus at 30 ◦ C was about 35%. The TGA thermogram showed
that the nanocomposite was still thermally stable up to 331 ◦ C.

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