Dang 2005
Dang 2005
Dang 2005
Received: March 1, 2005; Revised: April 28, 2005; Accepted: May 13, 2005; DOI: 10.1002/marc.200500137
Keywords: dielectric properties; morphology; nanocomposites; TEM; X-ray
Macromol. Rapid Commun. 2005, 26, 1185–1189 DOI: 10.1002/marc.200500137 ß 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1186 Z.-M. Dang, H.-Y. Wang, Y.-H. Zhang, J.-Q. Qi
nanosized one. Nevertheless, the thermal stability and Results and Discussion
mechanical properties of the composites will be improved
when the inorganic nano-filler replaces the micro-filler Figure 1(A) and (B) show typical morphologies of the dried
in the polymer composites. They are evaluated as the alter- BT/PVDF mixtures with BT volume fractions of 0.20 and
native materials for embedded microcapacitors in future. 0.40, respectively. It can be seen that the nanosized BT
It is well know that the dielectric properties of compo- particles do not show obvious agglomerations. It can also be
sites strongly depend on the dispersion of different phases. seen that a great deal of the BT nanoparticles are inclined
Frequently, the nanoparticles impart some particular pro- to absorb on the surface of the PVDF particles to form a
perties to the composite only when the particles are special structure as shown in Figure 1(A) and (B). This is
homogenously dispersed in the polymer matrix. The poly- because an interstitial hydrogen ion may exist in the BaTiO3
mer composites with electroactive ceramic nanoparticles lattice when nanoparticles are synthesized from a water
were prepared with the ball-milling techniques and a sol-gel solution.[14] Moreover ethanol is an organic polar solvent,
process.[11–13] In this communication, BaTiO3/polyvinyli- which makes it possible to disperse BT nanoparticles and
dene fluoride (BT/PVDF) nanocomposites were prepared PVDF. It can be seen that the size of the PVDF particles is
via a natural adsorption action, which occurred between the about five times bigger than the size of the BT nanoparti-
nanosized BT and PVDF particles and, subsequently, a hot- cles. In this case, the smaller particles have an inclination to
press technology. The BT/PVDF nanocomposites without adsorb onto the surface of the bigger particles. In addition, it
obvious BT agglomerations give us hope of the application is also known that the specific surface area increases with a
of the BT/PVDF nanocomposites as an alternative dielec- decrease in the particle size of the BT powders, the powders
tric to embedded microcapacitors as a result of this simple with smaller size have such a big specific surface and total
and convenient technology. surface energy that they have more adsorption centers.
Therefore, it is easy to make BT nanoparticles absorb onto
the surface of the PVDF particles. In fact, the nanoparticles
Experimental Part also lean towards mutual attraction, to reduce the surface
energy. The optimum dispersion of mixtures would be
Preparation of BT/PVDF Nanocomposites
achieved by virtue of the co-instantaneous effect of two
Our nanocomposites composed of a laboratory synthesized adsorption actions. The circle structure of the BT coating on
nanosized BaTiO3 and PVDF polymer were prepared via a PVDF in the dry mixtures with BT ¼ 40 vol.-% is more
physical mixing process in absolute ethanol (A.R.). The regular than the one with BT ¼ 20 vol.-% via the same pro-
preparation procedure of the nanosized BT particles of 30– cess condition, as shown in Figure 1(A) and (B). Maybe this
60 nm diameter is given elsewhere.[14] The nanosized BT is because the number of BT nanoparticles increases
particles were dispersed into the suspension solution in abso-
dramatically while the number of PVDF particles decreases
lute ethanol via a high energy ultrasonic treatment for 10 min.
The BT suspension was then mixed together with the sus- in the mixtures, which results in an increase of the chance of
pension of PVDF. The mixture was further stirred by employ- collision between the BT nanoparticles and PVDF particles.
ing ultrasonic action for 20 min. Afterwards, the mixture was The result shows that the mixtures with a suitable BT/PVDF
poured onto a glass plate and dried at 50 8C for 3 h to ensure the volume fraction ratio could make the nanosized BT
complete evaporation of ethanol. Finally, the dry mixture particles adsorb around the surface of the PVDF.
powders were then molded by hot-pressing at about 200 8C and The morphology of the BT/PVDF 0–3 nanocomposites
10 MPa. The final samples with a disc-shape are 12 mm in with a BT volume fraction 0.20 and 0.40 are shown in
diameter and 1mm in thickness. BT/PVDF nanocomposites Figure 1(C) and (D), respectively. It can be seen that there are
with a BT volume fraction ranging from 0 to 0.50 were no obvious agglomerations of BT throughout the com-
fabricated. posites. However, the dispersion in the composite with
20 vol.-% is not homogenous. It is believed that the volume
Measurements fraction of PVDF in the composite is so high that some PVDF
particles have not been absorbed, resulting in the inhomo-
In order to characterize the dry BT/PVDF mixtures and com- geneous dispersion of BT nanoparticles in the composite.
posites, their morphologies were analyzed by employing Therefore, it might be concluded that the homogenous BT/
transmission electron microscopy (TEM, JEOL JEM- PVDF nanocomposites could be prepared by the natural
1200EX). The phase structure of the BT/PVDF nanocompo-
adsorption effects occurring between the BTand PVDF when
sites, as well as the nanosized BT powers and PVDF polymer,
there is a suitable BT/PVDF volume ratio in the composite.
were analyzed using an X-ray diffractometer (XRD, Japan).
For dielectric measurement, electrodes were painted on the Figure 2 shows the X-ray diffraction (XRD) patterns of
sides of the samples using conductive silver paste. The alter- nanosized BaTiO3 powders (a), pure PVDF (e), and the BT/
nating current (AC) electrical properties of the samples were PVDF composites with 0.1 (b), 0.3 (c), and 0.5 (d) volume
measured using a HP4191A impedance analyzer over the fractions. The single crystal BT powder has a pure
frequency ranges of 100 Hz to 40 MHz at room temperature. perovskite phase, as shown in Figure 2(a). When it comes
Macromol. Rapid Commun. 2005, 26, 1185–1189 www.mrc-journal.de ß 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Morphology and Dielectric Property of Homogenous BaTiO3/PVDF Nanocomposites . . . 1187
Figure 1. TEM micrographs of the dry BT/PVDF mixtures with a (A) 0.20 and (B) 0.40 volume
fraction of nanosized BT particles; TEM micrographs of the BT/PVDF nanocomposites with a (C) 0.20
and (D) 0.40 volume fraction of nanosized BT particles.
to their patterns, some changes can be seen. As shown in However, a change in phase for the PVDF is more ob-
Table 1, S-01, S-02, S-03, and S-04 are in order of BT vious, as shown in Figure 2. The pure PVDF shows the
volume fractions ranging 100, 10, 30, and 50%. It was found strongest peak around 2y 19.58, but the diffraction peaks
that there are some changes in the dhkl values of BT in the of PVDF in the composites are negligible with an increase
composites, especially that of {110} and {100}. It is mainly of the BT concentration. Maybe this is because the BT
due to the ion transfer within the crystal lattice, which nanoparticles dispersed in the PVDF might have an impor-
results from the heat polarization in the course of the hot- tant effect on the crystallization of the PVDF polymer.[15]
pressing process. It is true that the change of relative As a result, the amorphous regions of the PVDF polymer are
intensity (I/I1) is clear with the change of BT content. A enlarged. According to this viewpoint, the damage to the
cubic structure can be distinguished from a tetragonal PVDF crystallization becomes more and more serious with
structure with {200} around 45. However, Figure 2 reveals the increase of nanosized BT volume fraction. The results
that the intensity of {200} decreases dramatically at 50 vol.- show that the crystallization of the polymer plays an impor-
%. This is because the number of agglomerates significantly tant effect on the morphology of the BT/PVDF nanocom-
increases in the composite. posites.
Macromol. Rapid Commun. 2005, 26, 1185–1189 www.mrc-journal.de ß 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1188 Z.-M. Dang, H.-Y. Wang, Y.-H. Zhang, J.-Q. Qi
60 50
0.30
Maxwell Garnett
Dielectric constant
(e)
Dielectric constant
40 Experimental
50
30
0.25
Loss tangent
(d) 20
40
Intensity
10
20 1 kHz
(b) 0.15
10 MHz 10 MHz
10
110
112
111
200
100
100
(a) 0.10
0.0 0.1 0.2 0.3 0.4 0.5
fBaTiO
20 40 60 3
Figure 3 shows dielectric permittivity (a) and loss (b) of Figure 4. It can be seen that the dielectric permittivity of
the BT/PVDF nanocomposites with different volume pure PVDF and all composites decreases with frequency.
fractions of BT at 1 KHz and 10 MHz, respectively. As The dielectric permittivity of the composites at low fre-
expected, the dielectric permittivity of the BT/PVDF quency (1 KHz) is higher than that at high frequency
nanocomposites increases with the content of the nanosized (10 MHz). However, the dielectric permittivity decreases
BT. The dielectric permittivity at 1 KHz is 40.74 in the very slowly when the frequency is less than 1 MHz. The
composite with a 0.50 volume fraction of BT. It can be dielectric losses increase with frequency over a frequency
found that the dielectric permittivity measured at 1 KHz is range of 10 kHz to 5 MHz. A clear peak of dielectric loss
greater than the one at 10 MHz. Dielectric loss decreases could be seen at about 5 MHz. This is an obvious relaxation
with an increase of BT concentration at 10 MHz, at which loss process related to the PVDF polymer. The relaxation
the value of dielectric loss is limited from 0.11 to 0.23. But loss makes the dielectric permittivity reduce significantly at
the dielectric losses of the nanocomposites are less than this frequency, as shown in Figure 4a. In general, in this
0.05 at 1 KHz. For illustration and comparison, the inset in study, the dielectric properties the BT/PVDF nanocompo-
Figure 3 also shows the calculations from the well-known sites are very desirable, which may lead to potential applica-
Maxwell–Garnett approximation.[6,15,16] The approxima- tions in the electronic industry.
tion is known to be reasonable for polymer-based compo-
sites consisting of a continuum matrix with embedded
inclusions. In contrast with our past result,[6] it can be seen
Conclusion
that the experimental data is in quite good agreement with
the values predicted by the Maxwell–Garnett theory. This BaTiO3/PVDF nanocomposites can be prepared via a
could be attributed to the formation of homogenous BT/ natural adsorption action occurring between the nanosized
PVDF nanocomposites. BT and PVDF particles in absolute ethanol and subsequent
The dependence of dielectric permittivity and loss of hot-press technology. It was discovered that the BT/PVDF
pure PVDF and composites on frequency are presented in mixtures with a suitable BT/PVDF volume fraction ratio
Macromol. Rapid Commun. 2005, 26, 1185–1189 www.mrc-journal.de ß 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Morphology and Dielectric Property of Homogenous BaTiO3/PVDF Nanocomposites . . . 1189
60
fBaTiO =0
dielectric properties, indicating a potential application in
Dielectric permittivity
(a) 3
10
0
0.30
[1] Y. Bai, Z. Y. Cheng, V. Bharti, H. S. Xu, Q. M. Zhang, Appl.
(b)
0.25 Phys. Lett. 2000, 76, 3804.
Loss tangent
Macromol. Rapid Commun. 2005, 26, 1185–1189 www.mrc-journal.de ß 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim