Journal of Science: Advanced Materials and Devices 1 (2016) 90e97

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Journal of Science: Advanced Materials and Devices

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Original article

Enhancement of polarization property of silane-modified BaTiO3

nanoparticles and its effect in increasing dielectric property of
epoxy/BaTiO3 nanocomposites
Thi Tuyet Mai Phan a, Ngoc Chau Chu a, Van Boi Luu a, Hoan Nguyen Xuan a, *,
re c
Duc Thang Pham b, Isabelle Martin c, Pascal Carrie
a
Faculty of Chemistry, VNU University of Science, Hanoi, Viet Nam
b
Faculty of Engineering Physics and Nanotechnology, VNU University of Engineering and Technology, Hanoi, Viet Nam
c
MAPIEM Laboratory, University of Toulon, La Garde cedex, France

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

Article history: The surface modification of synthesized nano-BaTiO3 particles was carried out using g-aminopropyl tri-
Received 15 April 2016 methoxy silane (g-APS) in an ethanol/water solution. The modified particles were characterized by FTIR,
Accepted 16 April 2016 TGA, surface charge analysis, and by dielectric constant measurement. The silane molecules were attached
Available online 21 April 2016
to the surface of BaTiO3 particles through SieOeBaTiO3 bonds. The g-APS grafted on BaTiO3 made
the dielectric constant of the particles increase at frequencies
0.3 kHz in a wide range of temperature
Keywords:
(25  Ce140  C), due to the presence of eNH2 groups. The dependence of the polarization vs. electrical field
BaTiO3
was measured in order to elucidate the dielectric behavior of the silane treated BaTiO3 in comparison to
Epoxy
Nanocomposite
untreated BaTiO3. The nanocomposite based on epoxy resin containing BaTiO3 nanoparticles untreated and
Surface modification treated with g-APS was also prepared and characterized. The results indicated that the g-APS-modified
Dielectric properties BaTiO3 surfaces significantly enhanced the dielectric property of the nanocomposite.
© 2016 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

1. Introduction (30e90 wt.%) [6e8]. However, the agglomeration of BaTiO3 parti-

In recent years, study on polymer/ceramic composites has
received much attention from academic researchers and industry
because polymers are flexible, inexpensive and easily processed
[1,2]. Although the polymer/ceramic combination may give the
composites some advantages from both sides, the development of
new materials that have good dielectric and mechanical properties
is still challenging [3,4].
Barium titanate (BaTiO3), a perovskite-type electro-ceramic
material, has interesting properties; a high dielectric constant,
along with ferro-, piezo-, and pyro-electric properties. BaTiO3 is
widely applied in the manufacture of multilayer ceramic capacitors
(MLCC), infrared detectors, thermistors, transducers, electro-optic
devices and sensors [5]. Various researchers have studied poly-
mer/BaTiO3 composites with improved dielectric, piezoelectric and
ferroelectric properties, especially those with very high BaTiO3 load
* Corresponding author. Tel.: þ84 4 3826 1854; fax: þ84 4 3824 1140.
E-mail address: hoannx@vnu.edu.vn (H. Nguyen Xuan).
Peer review under responsibility of Vietnam National University, Hanoi.
cles in a polymer matrix is considered to have an important effect
on the final dielectric properties. To eliminate the agglomeration, a
few types of surface treatment agents are often used to disperse the
ceramic particles into the polymer matrix [6,9e11]. Recently, silane
coupling agents have been used to modify the surface of nano-
particles in order to improve their dielectric properties in organic-
inorganic nanocomposites [10]. In addition, silane coupling agents
have been applied to inorganic fillers to achieve better hydrophi-
licity, consequently improving compatibility with polymer matri-
cies such as epoxy resin [11,12]. Many studies [6,8e10,13,14] predict
and theoretically discuss the role of silane as a coupling agent with
modified fillers acting in the network of a polymer composite
matrix. There is little experimental data with careful surface char-
acterization to properly relate the dielectric property of modified
fillers with the silane, despite this being a crucial factor to under-
stand the dielectric properties of the final nanocomposite mate-
rials. To clarify these approaches, in this paper, we focus on the use
of g-aminopropyl trimethoxy silane (g-APS) as a coupling agent to
modify the surface of BaTiO3 particles. We experimentally investi-
gate, in detail, the influence of surface treatment on the

http://dx.doi.org/10.1016/j.jsamd.2016.04.005
2468-2179/© 2016 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
 T.T.M. Phan et al. / Journal of Science: Advanced Materials and Devices 1 (2016) 90e97
microstructure, surface properties and dielectric properties of
BaTiO3 powders (with and without silane functionalization), which
is related to an enhancement of the polarization of the nano-
particles. We also show the role of the g-APS coupling agent at the
BaTiO3 surface on the dielectric property enhancement when
incorporated in a polymer network of epoxy with 5 wt.% of BaTiO3.
The choice of a small amount of BaTiO3 to incorporate in the
polymer network is governed by the fact that it can be use in future
applications as an in-situ sensor for monitoring thermosetting
matrix aging.
2. Material and methods
2.1. Materials
Epoxy resin (DGEBA, Epikote 828 Hexion Chemical), 4,40 Dia-
mino diphenyl methane (DDM, Sigma Aldrich), g-aminopropyl
trimethoxy silane (g-APS, Sigma Aldrich), and BaTiO3 nanopowders
were synthesized directly using a hydrothermal method from
BaCl2$2H2O, TiCl3 and KOH (Merck).
2.2. Preparation of BaTiO3 nanoparticles
Barium titanate (BaTiO3) was prepared by hydrothermal
method using BaCl2$2H2O, TiCl3 (initial molar ratio Ba2þ/Ti3þ ¼ 1.6/
1) and KOH as starting materials [15]. The precursor was mixed,
then transferred to a 150 ml Teflon-lined stainless steel autoclave,
non-stirred and sealed. The hydrothermal reaction was then carried
out at 150  C in an oven for 7 h. After the reaction, the autoclave was
naturally cooled down to room temperature. The obtained product
was then washed with distilled water to remove impurity ions.
2.3. Preparation of g-APS modified BaTiO3 particles
The g-APS coupling agent was dissolved in a water/ethanol so-
lution (90:10 v/v) and BaTiO3 particles were added to the solution.
The mixtures were ultrasonicated for 20 min and stirred at 60  C for
1 h [16]. Then, the treated suspension was centrifuged to remove
ethanol and was subsequently washed by ethanol and dried at
50  C in an oven.
2.4. Preparation of BaTiO3/epoxy nanocomposite
The g-APS modified BaTiO3 particles were ultrasonically
dispersed in ethanol for 1 h in order to form a stable suspension.
The suspension of BaTiO3 in ethanol was added to the epoxy resin
and the solution was magnetically stirred for 30 min, then sub-
jected to ultrasonic treatment for 1 h. Afterwards the solution was
heated to 80  C for 4 h to remove the solvent. The heating was
continued to 110  C, then stoichiometric ratios of amine functions
of DDM was added to epoxy functions of DGEBA to form the ho-
mogeneous mixture. This mixture was transferred on a glass
lamellar substrate to make the nanocomposite film using a bar-
coater. Subsequently, a curing process was carried out in three
steps: at 50  C/30 min, at 110  C/30 min and at 180  C/3 h. Finally
the films were cooled down to room temperature. The samples
were stored in desiccators to avoid moisture.
2.5. Analysis and measurements
Powder X-ray diffraction (XRD) patterns were measured on a
Bruker D8 Advance X-ray diffractometer with CuKa radiation
(l ¼ 1.5418 Å, 2q steps ¼ 0.03 /step). The particle size distribution of
the BaTiO3 powders was recorded on a laser diffraction particle size
analyzer (SHIMADZU SALD-2101). The BaTiO3 particles untreated
91
and treated with g-APS were characterized by Fourier transform
infrared spectroscopy (FT-IR) using a Perkin Elmer GX spectropho-
tometer (wavenumber range of 4000e400 cm1). The amount of
organic silane compounds grafted on the BaTiO3 particle surfaces
was determined by thermogravimetric analysis (TGA) using a TA
instruments Q-600 (rate 10  C/min, under a dry nitrogen gas flow
rate of 100 ml/min). The surface charge distribution of BaTiO3 par-
ticles modified and unmodified with g-APS were examined using a
Zeta phoremeter IV (CAD Instrumentation) under the following
conditions: temperature of 25  C and pH ¼ 5.5, where a KCl solution
was used to set the ionic strength. The morphology of the nano-
BaTiO3 powders and composites was studied using scanning elec-
tron microscopy (SEM, HITACHI S4800) and transmission electron
microscopy (TEM, JEOL-JEM-1010). The dielectric constant was
measured directly on a non-sintered BaTiO3 pellet. The pellet
preparation is defined as follows: 0.5 g of BaTiO3 powders untreated
and/or treated with the silane were shaped with a 5-ton hydraulic
press. The pellet diameter (d ¼ 13 mm) and pellet thickness
(e ~ 1 mm) was kept constant to ensure that the pellet of BaTiO3
powders untreated with the silane are identical with treated one.
BaTiO3/epoxy nanocomposite films were measured in a tempera-
ture range from 25  C to 120  C with double gold electrodes over a
frequency range of 10 Hz to 1 MHz using an RCL Master M3553
analyzer and a Dielectric analyzer (DEA, TA Instruments). Polariza-
tion hysteresis curves of BaTiO3 powder samples were analyzed
using a Radiant Precision LC 10 (Radiant Technologies: Hysteresis
Version 4.2.7) with double copper electrodes (S ¼ 0.25 cm2) at 25  C,
under an external voltage of 500 V and frequency of 1 kHz.
3. Results and discussions
3.1. Characterization of BaTiO3 particles and BaTiO3 particles
grafted g-APS silane
Fig. 1a shows the XRD pattern in the 2q region of 20 e70 for
BaTiO3 powders. The Bragg reflections were identified as the cubic
BaTiO3 phase (Pm-3m, a ¼ 4.027(7) Å) [15,17]. The XRD pattern of
the BaTiO3 demonstrated cubic structure by the following charac-
teristic peaks: (100), (110), (111), (200), (210), (211) and (220). The
particles size distribution (Fig. 1b) shows the BaTiO3 powders
consisted of narrow-dispersed particles with homogeneous mor-
phologies. The grain sizes determined at 10.0% D, 50.0% D and 90.0%
D were equal to 64, 93 and 138 nm, respectively.
Fig. 2 shows the FT-IR spectrum of the untreated (a) and treated
BaTiO3 nanoparticles with g-APS silane (b). For untreated BaTiO3,
there were bands at 3432 cm1, which corresponded to the
stretching mode of OeH groups, and a peak at 1626 cm1, which is
characteristic for the bending mode of HeOeH resulting from the
physically adsorbed water on BaTiO3 nanoparticles. While the peak
at 1428 cm1 is related to the stretching vibration of CeO in eCO2 3
due to the trace of BaCO3 phase (less than 2.0 wt.%), the broad
bands between 570 and 597 cm1 were due to TieO stretching
mode of BaTiO3 [8,12].
It is clear from Fig. 2b that the decrease in intensity of the peak
corresponding to eOH groups at 3432 cm1 indicate the occurrence
of the reaction between silanol groups of the coupling agent and
the eOH groups of BaTiO3 particles. The band at 2926 cm1 was
assigned as the stretching vibration of CeH bands of propyl groups.
The peaks at 1567 and 1332 cm1 can be attributed to eNH2 and
CeH deformation mode of amino-groups of the coupling agent,
respectively [1,18]. The appearance of the bands at 1143 and
1024 cm1 was indicative of the formation of SieOeBaTiO3 and
SieOeSi bands, respectively, resulting from the condensation of
silanol groups with hydroxyl groups of BaTiO3 particles and other
silanol groups [10,16]. The appearance of the new peaks proved that
92 T.T.M. Phan et al. / Journal of Science: Advanced Materials and Devices 1 (2016) 90e97
Fig. 1. XRD patterns of hydrothermal synthesized BaTiO3 powders (a) and the particles
size distribution of BaTiO3 particles (b).
the g-APS was grafted efficiently onto the surface of BaTiO3 parti-
cles. A schematic illustration of the reaction mechanism of silane
coupling agent with hydroxyl groups on the particle surface was
partially described by [11,19,20] and assumed that the alkoxy
groups (OR) of the silane were first hydrolyzed with water to form
silanol (SieOH) groups and then the silanol groups were condensed
with the hydroxyl groups on the particles.
Fig. 3 shows the TGA curves for BaTiO3 powders untreated and
treated with g-APS. The amount of g-APS grafted onto the BaTiO3
surface was determined to be about 3.0 wt.% with respect to BaTiO3
particles. The weight curve of BaTiO3 powders treated with g-APS
showed three well-defined degradations. By correlation with FT-IR
Fig. 2. FT-IR spectra of BaTiO3 nanoparticles (a) and BaTiO3 powders modified with the
silane (b).
Fig. 3. TGA curves of BaTiO3 powders (a) and BaTiO3 powders modified with the silane
(b). The derivative of weight shows respectively in curves (c) and (d).
results (Fig. 2), the physically adsorbed water is removed at lower
temperatures (50  Ce150  C). The degradation step between 150  C
and 450  C indicate that chemically bound eOH free groups and/or
silane molecules remain on the surface of BaTiO3. Then the pyrol-
ysis of surface silanols was observed at about 570  C [16,19].
Fig. 4 shows the surface charge distribution of the g-APS treated
and untreated BaTiO3. The average values of the surface charge of
the nano-BaTiO3 particles, z(avg.), was roughly 33.7 mV, which
means that the nano-BaTiO3 particles can be stable in the disper-
sion solution (Fig. 4a). The negative charge on the surface of par-
ticles was a result of the presence of hydroxyl groups (OH)
attached to the nano-BaTiO3 surface, as interpreted in the TGA
curves. The surface charge distribution shifted from the negative to
the positive region when the nano-BaTiO3 particles were treated
with g-APS; z(avg.) ¼ þ6.2 mV (Fig. 4b). This result confirms that
the silane molecules were grafted efficiently onto the surface of
BaTiO3 particles following the formation of the SieOeBaTiO3 bonds
(insert in Fig. 4b).
TEM images of BaTiO3 powders untreated and treated with
silane are shown in Fig. 5. It can be seen that the particle size
remained unchanged after grafting with the silane.
Most researchers have studied the dielectric properties of
ceramic BaTiO3 in bulk forms after sintered at temperatures higher
Fig. 4. Surface charge distribution of the g-APS unmodified (a) and modified BaTiO3
(b).
 T.T.M. Phan et al. / Journal of Science: Advanced Materials and Devices 1 (2016) 90e97 93

Fig. 5. TEM images of BaTiO3 unmodified (a) and modified with g-APS (b).

than 1100  C [15,21,22]. No systematic study has been published to
date on the dielectric properties of fresh BaTiO3 nanopowders. To
understand the effects of silane modification on the dielectric
property of BaTiO3 powder, the dielectric constant characterization
was conducted directly on fresh unmodified and modified silane/
BaTiO3 pellets, without sintering, to ensure that the silane mole-
cules were not destroyed at the BaTiO3 surface. Fig. 6a, b shows the
dielectric constant and the dielectric loss as a function of frequency
of the unmodified and silane-modified BaTiO3 nanopowders in the
temperature range of 30  Ce140  C.
In the case of untreated BaTiO3 particles, at fixed frequency, the
dielectric constant decreased as the temperature increased and
sample exhibited low dielectric loss (Fig. 6a, c). Contrary to the
untreated BaTiO3 nanoparticles, the dielectric constant of the g-APS
modified BaTiO3 nanoparticles increased as the temperature
increased (Fig. 6b, d).

Fig. 6. Dielectric constant and dielectric loss vs. frequency and vs. temperature of BaTiO3 powders unmodified (a, c) and modified with g-APS (b, d).
94 T.T.M. Phan et al. / Journal of Science: Advanced Materials and Devices 1 (2016) 90e97
At a frequency of 0.3 kHz and greater, the values of dielectric
constant of the silane-modified BaTiO3 sample are higher than that
of untreated BaTiO3 sample in all ranges of measured temperature.
However, at frequencies lower than 0.3 kHz, the reverse phenom-
ena were observed. For example, at 0.01 kHz and 30  C, the
dielectric constant was about 250 and dielectric loss was about 2.2
for untreated BaTiO3, while the dielectric constant was about 110
and the dielectric loss was about 0.25 for treated BaTiO3. These
observations have been difficult to explain. Nevertheless, we note
that the dielectric constant in materials is primarily caused by the
dipolar polarization effect induced by the permanent dipoles
existing in the particles. In the case of BaTiO3, the permanent di-
poles result from the uneven distribution of the charge-density
between O, Ba and Ti atoms [24]. In BaTiO3 treated with the g-
APS, the silane molecules grafted at the surface of BaTiO3 particles
introduces additional permanent dipoles due to the presence of
eNH2 groups. The consequence is an increase in the dielectric
constant (at frequency higher than 0.3 kHz) and a decrease in the
dielectric loss of the silane treated BaTiO3 particles in comparison
to the untreated BaTiO3 particles. Indeed, the decreased dielectric
loss tangent can be understood by the following explanation:
BaTiO3 nanoparticles are coated by stable and dense aminosilanes,
resulting in an insulating layer outside of the dielectric cores that
restricts the migration and accumulation of the space charge within
the pellets.
In order to elucidate the differences in the dielectric behavior
between the untreated BaTiO3 and silane-treated BaTiO3 samples,
owing in part to this complementary ionic polarization, a set of
polarization measurements on the two pressed BaTiO3 pellets were
performed. Fig. 7 shows the polarization (P) vs. electrical field (E)
plots of non-sintered BaTiO3 pellets treated with silane and un-
treated. The untreated BaTiO3 sample shows a minor polarization
hysteresis loop because the applied field did not reach its saturation
value [25]. At 5.0 kV/cm, the sample showed a small remanent
polarization (Pr) of 0.055 mC/cm2, saturation polarization (Ps) of
0.28 mC/cm2 and a low coercive electric field (Ec) of 0.45 kV/cm. The
minor ferroelectric polarization loop obtained for the non-sintered,
untreated BaTiO3 sample can be explained by a slightly distorted
cubic phase of the BaTiO3 nanoparticles due to the small, local Ti
distortions [23] or TiO6 octahedral distortion in the BaTiO3 crystal
structure. The cell parameters a z c, so it was difficult to correctly
identify and separate the (200) peak from XRD pattern as previ-
ously mentioned (Fig. 1a), in which the sample exhibited a typical
ferroelectric polarization loop. On the other hand, the silane-
Fig. 7. Hysteresis loops of BaTiO3 sample unmodified and modified with g-APS at 25  C
and frequency of 1 kHz.
treated BaTiO3 sample introduced additional dipoles due to the
presence of eNH2 groups. The polarization value were observed to
be larger than those of the untreated BaTiO3 sample at any given
electrical field (E) in the range 0e5.0 kV/cm for the first quadrant,
and 5.0 to 0 kV/cm for the third quadrant.
The electric displacement notably increases with the silane
graft, which should be attributed to the increase of the dielectric
constant of the nanoparticles. Fig. 7 also presents the increase of the
electric displacement of the nanoparticles at various applied elec-
tric fields; indicating that it is reasonable to obtain a larger electric
displacement at a higher electric field. These results demonstrate
that the significant increase of the dielectric displacement should
be related not only to the ferroelectric BaTiO3, but also to the
interface areas in the pellet. As a typical ferroelectric, the BaTiO3
particles in the pellet exhibit large polarization under the applied
electric field. Besides, as the dielectric constant of BaTiO3 is much
larger than BaTiO3 grafted with g-APS, the distribution of electric
field is distorted, leading to higher electric fields in the organic
interface and larger polarization of the g-APS.
3.2. Effect of g-APS coupling agent on the dielectric properties of
BaTiO3/epoxy nanocomposite
Fig. 8 shows the fractured surfaces of the epoxy nanocomposite
containing BaTiO3 particles unmodified and modified with the
silane as characterized by SEM. It can be seen that the BaTiO3
particles with g-APS were almost uniformly distributed throughout
the epoxy matrix and there exists nearly no aggregation of BaTiO3
particles. Consequently, the g-APS coupling agent is beneficial to
improve the compatibility between the BaTiO3 particles and the
epoxy matrix without adding any dispersant as is usually done in
these systems [14].
Fig. 9 shows the dielectric constant and dielectric loss curves of
the neat epoxy resins and the epoxy nanocomposites containing
5 wt.% of BaTiO3 unmodified and modified with the silane. It can be
seen that the dielectric constant of all samples slightly decreases
when frequency increases over the entire frequency range.
The dielectric constant of the nanocomposites reinforced with
BaTiO3 particles, both modified and unmodified with g-APS, were
higher than that of epoxy resin contrary to the dielectric loss. Thus,
the nanocomposites containing modified BaTiO3 nanoparticles had
a higher dielectric constant and lower dielectric loss compared to
that containing the unmodified one across the entire frequency
range. As compared to the BaTiO3/epoxy nanocomposite, the
interface areas should be the key to the large dielectric displace-
ment of the BaTiO3 grafted g-APS/epoxy composite.
It is likely that silane acts as molecular bridges between the
polymer and the ceramic filler, resulting in the formation of cova-
lent chemical bonds across the interfaces, which also improves the
dielectric properties [8]. First, the silane coupling agent acts as an
effective passivation layer, reducing the concentration of the polar
groups (ionizable hydroxyl) on the BaTiO3 surface while mini-
mizing the amount and mobility of the charge carriers usually
associated with the surface [26,27]. This should ultimately decrease
the dielectric loss at high loading but it still remains constant in
these nanocomposites as shown in Fig. 9(b). Secondly, these phe-
nomena could be interpreted by the fact that the silane acts as a
molecular bridge between the polymer and the BaTiO3 particle,
improving the interface adhesion between epoxy resin and BaTiO3
particles. Thus, the BaTiO3 particles grafted with g-APS can increase
the 0e3 connectivity in the epoxy resin network as illustrated in
Fig. 10. Obviously, this prevents the movement of the polymer
network, which also improves the dielectric properties assuring an
even distribution of higher permittivity particles because of the
excellent microstructure obtained in these composites [28]. The
 T.T.M. Phan et al. / Journal of Science: Advanced Materials and Devices 1 (2016) 90e97
Fig. 8. SEM images of fractured surfaces at different magnitude of the composite epoxy/BaTiO3 (a, b); composite epoxy/BaTiO3 modified with the silane (c, d).
Fig. 9. Dielectric constant (a) and dielectric loss (b) vs. frequency of epoxy resin,
nanocomposite epoxy/BaTiO3 powders unmodified and modified with g-APS.
95
dielectric constant of the nanocomposites (εc) was calculated based
on the LichteneckereRother logarithmic law of mixing applicable
to chaotic or statistical mixtures [29]:
ln εc ¼ y1 ln ε1 þ y2 ln ε2 (1)
where y1 and y2 are the volume fractions of the two components
having relative permittivity ε1 and ε2, respectively (Table 1). Epoxy
nanocomposites containing modified BaTiO3 particles had a larger ε
value than predicted by the logarithmic law of mixing (6.96
experimentally versus 3.57 theoretically), whereas the dielectric
constant of the nanocomposites containing unmodified BaTiO3
particles matched well with the predicted value (3.55 versus 4.01),
indicating the strong effect of the connection molecules between
the filler and matrix on the dielectric constant. For a particulate-
filled polymer composite with a given filler loading, the dielectric
constant and dielectric loss are not only related to the composite
microstructure but also associated with the dielectric constant of
polymer matrix and interfacial polarization as the polymer/filler
interaction can change the dielectric response of the polymer ma-
trix and results in a variation of dielectric constant of the polymer
matrix.
Here, we focus on the dielectric property differences between
BaTiO3/epoxy and BaTiO3 grafted g-APS/epoxy. Regarding the effect
of composite microstructures on the dielectric property of the
nanocomposites, it is believed that the good dispersion of the
BaTiO3 nanoparticles and average interfacial adhesion between the
nanoparticles and the epoxy matrix is an important factor resulting
in dielectric constant. This is because the good nanoparticle
dispersion and average interfacial adhesion between the surface
OH of BaTiO3 and epoxy might reduce pores and voids usually
observed in the nanocomposites in particular at high nanoparticle
loading [6].
In the case of unmodified BaTiO3 particles, the presence of
BaTiO3 in the epoxy network acted mainly as an additive. In addi-
tion, the intrinsic dielectric constant of BaTiO3 grafted g-APS was
not sufficiently higher than raw BaTiO3 to be responsible for the
96 T.T.M. Phan et al. / Journal of Science: Advanced Materials and Devices 1 (2016) 90e97
Fig. 10. Reaction scheme for BaTiO3 particles (a) and silanized BaTiO3 particles (b) with epoxy/DDM resin.
Table 1
The comparison of ε measured values of the nanocomposite samples and the ε estimated values by the LichteneckereRother logarithmic law of mixing at 30  C and 10 kHz.
ε ε nanocomposite calculated
BaTiO3 62.3
BaTiO3 grafted g-APS 66.2
Epoxy 3.05
higher dielectric constant of the BaTiO3 grafted g-APS/epoxy
nanocomposites. Therefore, the dielectric performance of the
BaTiO3 grafted g-APS/epoxy composite was enhanced by the effect
of the interfacial polarization of the epoxy matrix to reach a rela-
tively high dielectric constant and very low dielectric loss.
4. Conclusions
Barium titanate nanopowders were synthesized by the hydro-
thermal method with “cubic” crystalline structure and an average
particle size in the range of 93 nm. This study has also demon-
strated and confirmed the important role of g-APS in modifying the
BaTiO3 surface particles on their dielectric and polarization prop-
erties. At 5.0 kV, the untreated BaTiO3 sample shows a small
remanent polarization (Pr) of 0.055 mC/cm2, saturation polarization
(Ps) of 0.28 mC/cm2, and a low coercive electric field (Ec) of 0.45 kV/
cm; whereas the silane-treated BaTiO3 particles show
Pr ¼ 0.402 mC/cm2, Ps ¼ 1.04 mC/cm2 and Ec ¼ 1.25 kV/cm. The
presence of silane at the surface of BaTiO3 particles (~3.0 wt.% of the
silane respect to BaTiO3 particles) leads to a shift of the surface
charge distribution of the modified particles to the positive charge
region. Finally, we show that the g-APS coupling agent was bene-
ficial to the compatibility between the BaTiO3 particles and the
epoxy matrix and enhanced significantly the dielectric property of
the nanocomposite. At frequency of 10 kHz, the dielectric constant
of modified silane-BaTiO3/epoxy composite was increased by
approximately 2 times (ε ¼ 6.96) compared to the unmodified
silane-BaTiO3/epoxy composite (ε ¼ 4.01) and to pure cured epoxy
resin (ε ¼ 3.05).
These preliminary results show that it would be of interest to
study grafted BaTiO3 at various small loading in an epoxy resin
(between 5 and 20 wt.%) to establish the relationships between the
controlled BaTiO3 interface and the induced mobility of the
ε nanocomposite measured
3.55 4.01
3.57 6.96
e e
interphase on the nanocomposite's dielectric properties to
approach further applications.
Acknowledgments
This work was supported by the Vietnam National Foundation
for Science and Technology Development under Grant number
104.03-2012.62.
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