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“Grafting to” route to PVDF-HFP-GMA/BaTiO3

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nanocomposites with high dielectric constant and

Cite this: J. Mater. Chem. A, 2014, 2,
5244 high thermal conductivity for energy storage and
thermal management applications†
Liyuan Xie,a Xingyi Huang,*a Ke Yang,a Shengtao Lib and Pingkai Jiangac

The introduction of high dielectric constant ceramic nanoparticles into an insulating polymer is an
important approach to prepare high dielectric constant nanocomposites for electric energy storage
applications. A key to obtaining desirable properties is the homogeneous dispersion of the nanoparticles
in the corresponding polymer. Conventional methods used to improve the nanoparticle dispersion
enhance the physical interaction between the nanoparticle and the polymer matrix via nanoparticle
surface modification. In this work, the covalent bonding between the nanoparticle and the polymer
matrix was utilized to simultaneously enhance the nanoparticle dispersion and nanoparticle/polymer
interaction by functionalizing both the polymer and the nanoparticles. The poly(vinylidene fluoride-co-
hexafluoropropylene) [PVDF-HFP] was functionalized with glycidyl methacrylate (GMA) via atom transfer
radical polymerization. The barium titanate (BaTiO3) nanoparticles were modified by amino-terminated
silane molecules. Then the nanocomposites were prepared by a “grafting to” method. Namely, grafting
GMA functionalized PVDF-HFP to the surfaces of the BaTiO3 nanoparticles. The introduction of GMA
into the PVDF-HFP not only increases the dielectric constant, but also changes the dielectric response of
PVDF-HFP. More importantly, this “grafting to” approach results in core–shell structured BaTiO3@PVDF-
Received 12th December 2013
Accepted 21st January 2014
HFP-GMA and thus a homogeneous dispersion of BaTiO3 nanoparticles in the nanocomposites. The
dielectric constant, electric energy density and thermal conductivity of the nanocomposites are
DOI: 10.1039/c3ta15156e
significantly enhanced with the increase of BaTiO3, while the dielectric loss shows a slight decrease as
www.rsc.org/MaterialsA the nanoparticle loading increases.

way to fabricate high-performance composites with a high

Introduction dielectric constant. So far, many high dielectric constant ceramic
High dielectric constant materials have attracted more and more lled polymer composites have been successfully fabricated.12–18
attention because of their important applications in the electrical When the particle size of the ceramics is in the nanoscale
and electronic industries,1–3 including electric stress control,4,5 range the corresponding polymer nanocomposites can exhibit
high energy storage devices6–8 and embedded capacitors.9,10 Some superiority, in comparison with the polymer composites with
ceramics, such as barium titanate (BT) and lead zirconium tita- microscale ceramic particles.19 However, the homogeneous
nate (PZT), have high dielectric constants, but their breakdown dispersion of nanoparticles in polymers is a great challenge
strength is low and their processability is poor. On the other hand, because of the high surface energy of nanoparticles.20 Moreover,
polymers possess a high breakdown strength and good process- a high volume fraction of ceramic nanoparticles is usually
ability, but their dielectric constant is relatively low.11 Therefore, required in order to obtain a high dielectric constant. In this
combining ceramics and polymers is expected to be an effective case, the uniform dispersion of nanoparticles into the polymer
matrix becomes more difficult. In recent years, many efforts
have been reported to achieve nanocomposites with good
nanoparticle dispersion, including the use of hybrid llers,21
a
Department of Polymer Science and Engineering, Shanghai Key Laboratory of
Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, Shanghai
nanoparticle surface modication by organic molecules such as
200240, People's Republic of China. E-mail: xyhuang@sjtu.edu.cn
b
State Key Lab of Electrical Insulation and Power Equipment, Xi'an Jiaotong University,
silanes,22 phosphonic acid12 and ethylene diamine,8 and nano-
Xi'an, China particle surface initiated in situ polymerization.6,23–26 However,
c
Shanghai Engineering Center for Material Safety of Nuclear Power Equipment, the strategy of functionalizing the polymer matrix has seldom
Shanghai 200240, People's Republic of China been reported for the preparation of nanocomposites with a
† Electronic supplementary information (ESI) available. See DOI: high dielectric constant.
10.1039/c3ta15156e

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Ferroelectric poly(vinylidene uoride) [PVDF] and its and the ask was sealed with a rubber plug. The oxygen in the
copolymers, such as poly(vinylidene uoride-co-hexa- ask was carefully removed by evacuating and back-lling with
uoropropylene) (PVDF-HFP) and poly(vinylidene uoride-co- N2 gas three times. 1.733 g PMDETA was added by syringe. This
triuoroethylene)(PVDF-TrFE), have high dielectric constants mixture was stirred at 60  C for 24 h. The products were
because of the presence of highly electronegative uorine and precipitated in methanol, and the mixture was ltered to obtain
the spontaneous alignment of C–F dipoles in the crystalline modied PVDF-HFP (denoted as PVDF-HFP-GMA). The PVDF-
phases.27 These polymers are promising matrixes for HFP-GMA was redissolved in DMF, precipitated in methanol
preparing nanocomposites with a high dielectric constant.28–33 and then was ltered. This cycle was repeated four times to
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In this study, poly(glycidyl methacrylate) was introduced onto obtain pure PVDF-HFP-GMA. The obtained PVDF-HFP-GMA was
the PVDF-HFP chains via in situ atom transfer radical poly- dried under vacuum at 60  C for 12 h.
merization (ATRP) and the as prepared polymer was denoted
as PVDF-HFP-GMA. Then the PVDF-HFP-GMA/BT nano- Preparation of the BT nanocomposites
composites were prepared by grating the PVDF-HFP-GMA to
The PVDF-HFP-GMA/BT nanocomposites were prepared via a
the BT nanoparticle surfaces via covalent bonding. The
solution blending method. Firstly, the required quantity of
dielectric responses, energy storage and thermal conductivity
BT-APS nanoparticles was dispersed into DMF by applying
of the nanocomposites were investigated.
ultrasonic waves for 30 min at room temperature. At the same
time, PVDF-HFP-GMA was dissolved in DMF at 50  C. Then the
Experimental suspension of BT-APS/DMF and the solution of PVDF-HFP-
Materials GMA/DMF were mixed and stirred with an electric stirrer at
80  C for 30 min. The resulting mixture was precipitated in
g-Aminopropyl triethoxysilane (g-APS) was purchased from GE
methanol and was ltered to get the nanocomposites. The
silicones. 2-Bromo-2-methylpropionyl bromide (a-bromoisobu-
obtained PVDF-HFP-GMA/BT nanocomposites were dried under
tyryl bromide) and N,N,N0 ,N00 ,N00 -pentamethyldiethylenetri-
vacuum at 80  C for 12 h. Finally, the dried nanocomposites
amine (PMDETA) were purchased from Acros. An aqueous
were compressed into lms at 180  C under a pressure of about
solution of H2O2 (30 wt%), glycidyl methacrylate (GMA), CuBr,
20 MPa. Nanocomposites containing different BT volume frac-
N,N-dimethyl formamide (DMF), methanol, toluene and other
tions (10%, 20%, 30%, 40% and 50%) were prepared and were
organic reagents or solvents were supplied by Shanghai
denoted by the GMA-BT-volume fraction (GMA-BT-10, GMA-BT-
Reagents Co. Ltd. The GMA was passed through a column lled
20, GMA-BT-30, GMA-BT-40 and GMA-BT-50). For comparison,
with basic alumina prior to use. The pure PVDF-HFP with 15%
the untreated PVDF-HFP/BT nanocomposites were also
HFP was supplied from Solvay Plastics. The BT nanoparticles,
prepared via the same blending method and were denoted as
with an average diameter of 100 nm, were provided by the
BT-10, BT-20, BT-30, BT-40 and BT-50.
Shandong Sinocera Functional Material Company, China. The
specic surface area of the nanoparticles was 10.55 m2 g1.
Characterization
Unless otherwise specied, all the chemicals were used as
received. Fourier-transform infrared (FTIR) was conducted with a Perkin-
Elmer Paragon 1000 instrument over the range of 4000–450 cm1.
Functionalization of the BT nanoparticles Nuclear magnetic resonance (1H NMR) spectra were recorded with
a Varian Mercury plus-400 spectrometer in DMSO-d6, using TMS
The treatment of the original BT nanoparticles was according to
as the standard. Thermogravimetric analysis (TGA) was conducted
our previous report.24 Briey, 100 g BT nanoparticles were
using a NETZSCH TG209 F3 instrument with a heating rate of
added into a 500 ml aqueous solution of H2O2 (30 wt%) in a
20  C min1 in an air ow (20 ml min1). Transmission electron
round-bottomed ask. The mixture was sonicated for 30 min
microscopy (TEM) images were obtained from a JEOL JEM-2100
and was then reuxed at 105  C for 4 h. The nanoparticles were
instrument operated at an accelerating voltage at 160 kV. Samples
recovered by centrifugation at 9000 rpm for 5 min. The obtained
were prepared by dropping the sample solutions onto carbon-
BT nanoparticles were washed with deionized water two times
coated copper grids and air-drying before measurement. Contact
and then were dried under vacuum at 80  C for 12 h. 40 g BT
angle measurements were performed using the sessile drop
nanoparticles, treated by H2O2 aqueous solution, were added
method on a Contact Angle System OCA 20 (Data Physics
into 300 ml toluene in a round-bottomed ask and sonicated for
Instruments GmbH, Germany) in air. Scanning electron micros-
30 min. 20 g g-APS was then added and the mixture was heated
copy (SEM) images were recorded using a JEOL JEM 7401F eld
to 80  C for 24 h under an N2 atmosphere. The nanoparticles
emission scanning electron microscope. All samples were
were recovered by centrifugation at 9000 rpm for 5 min. The
prepared by fracturing the composites at room temperature and
obtained BT nanoparticles were washed with toluene two times
then sputter-coating with a homogeneous gold layer to avoid
and were dried under vacuum at 80  C for 12 h.
accumulation of charges. The broadband dielectric properties of
the nanocomposites were measured using an impedance analyzer
Functionalization of PVDF-HFP (Aglient 4294A) in the frequency range 100 to 107 Hz at various
20 g PVDF-HFP was dissolved in 300 ml DMF in a round- temperatures. All of the samples had a layer of gold evaporated on
bottomed ask at 50  C. 20 g GMA and 1.435 g CuBr were added both surfaces to serve as electrodes. The DC breakdown strength

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was measured by a dielectric strength tester with a ball-to-ball

stainless electrode (DH, Shanghai Lanpotronics Co., China) at
room temperature. Electric displacement–electric eld (D–E)
loops were measured by a Precision Premier II ferroelectric
polarization tester (Radiant, Inc.) at room temperature and 10 Hz
using the same samples prepared for dielectric properties testing.
The thermal conductivity was measured on disc samples by the
laser ash method (Netzsch LFA447, Germany) at various
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temperatures. The thickness of the samples for the measurements

of dielectric properties, breakdown strength and thermal
conductivity was about 200 mm. The thickness of the samples for
the test of the electric displacement–electric eld (D–E) loops was
about 50 mm.

Results and discussion

Preparation and characterization of PVDF-HFP-GMA Fig. 1 FT-IR spectra of PVDF-HFP and PVDF-HFP-GMA.
Scheme 1 illustrates the preparation process of the PVDF-HFP-
GMA/BT nanocomposites. In ATRP, chlorine and bromine
atoms are usually used as initiators. In this study, we used the signicant difference of wettability between GMA and PVDF-
uorine atom of the PVDF-HFP to initiate the ATRP of the GMA HFP. Fig. 3 shows the images of 1 ml water droplets on the
monomers, which introduced many active epoxy groups to the PVDF-HFP and PVDF-HFP-GMA membrane. The contact angle
PVDF-HFP. It has been proven that, although its activity is low, of PVDF-HFP is 90.1  1.7 , similar to the result reported else-
the uorine atom from the PVDF can initiate the ATRP of where.34 However the contact angle of PVDF-HFP-GMA is 85.5 
hydrophilic monomers.34 In our ATRP experiment, various feed 1.5 , smaller than that of PVDF-HFP. The change of contact
ratios of GMA monomer to PVDF-HFP were used and the angle also provides evidence for the successful fabrication of
dielectric constants of the fabricated PVDF-HFP-GMA are shown PVDF-HFP-GMA.
in Fig. S1 and Table S1† (in the ESI). It can be observed that the
dielectric constants of PVDF-HFP-GMA are associated with the
Morphology of PVDF-HFP-GMA/BT and PVDF-HFP/BT
feed ratios and reach a maximum when the feed ratio is 1.0. In
this optimal case, the fraction of GMA corresponds to 0.2 wt%. In order to gra the PVDF-HFP-GMA chains to the BT nano-
Therefore, PVDF-HFP with 0.2% GMA was used as the polymer particle surface, the nanoparticles were functionalized with
matrix. aminopropyl triethoxysilane (Scheme 1), and the characteriza-
Fig. 1 shows the FT-IR spectra of PVDF-HFP and PVDF-HFP- tion of the functionalized nanoparticles has been described in
GMA. A peak for PVDF-HFP-GMA is clearly seen at 1673 cm1, our previous work.24 It is expected that the epoxy groups from
which is due to C]O stretching vibrations. However, no peak GMA graed onto PVDF-HFP could react with the amino groups
can be observed for PVDF-HFP at 1673 cm1. This result indi- on the surface of BT nanoparticles.35 To prove the successful
cates that the GMA is successfully graed to the PVDF-HFP. graing of polymer chains to the nanoparticles, the as prepared
Fig. 2 shows the 1H NMR spectra in DMSO-d6 of PVDF-HFP- PVDF-HFP-GMA/BT nanocomposites were re-dissolved in DMF
GMA. The H in the PVDF exhibits two peaks due to head-to-tail and the BT nanoparticles were washed several times to remove
(ht) and head-to head (hh) addition. The appearance of char- the free polymer chains. Fig. 4 shows TEM images of the washed
acteristic peaks of GMA conrms the successful introduction of nanoparticles. It can be clearly observed that the BT nano-
GMA to the PVDF-HFP. particles were coated by a polymer layer, indicating the
It is expected that the introduction of GMA to PVDF-HFP successful graing of PVDF-HFP-GMA onto the BT nanoparticle
would change the wettability of PVDF-HFP because of the surface.

Scheme 1 Schematic illustration of the preparation process for the

1
PVDF-HFP-GMA/BT nanocomposites. Fig. 2 H NMR spectra of the PVDF-HFP-GMA in DMSO-d6.

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Fig. 3 Images of 1 ml water droplets on (a) the PVDF-HFP and (b) the
Fig. 5 SEM images of the fractured surface of the PVDF-HFP-GMA (a)
PVDF-HFP-GMA membranes.
and PVDF-HFP (b) nanocomposites with 20 vol% BT nanoparticles.

Fig. 5a shows SEM images of the fractured surfaces of the reported elsewhere.15 Fig. 6c shows the frequency dependence
PVDF-HFP-GMA/BT and PVDF-HFP/BT nanocomposites. The of electrical conductivity for the PVDF-HFP-GMA/BT nano-
enlarged SEM images are shown in Fig. S2† (in the ESI). One can composites. One can see that the introduction of BT nano-
see that the BT nanoparticles were well dispersed in the PVDF- particles slightly increases the electrical conductivity of the
HFP-GMA matrix and most of the nanoparticles are buried in nanocomposites. Since the dielectric loss at the frequencies
the matrix (Fig. 5a). In contrast, the BT nanoparticles in pure larger than kilohertz mainly originates from the electrical
PVDF-HFP matrix forms obvious aggregations and some air conduction and dipolar polarization, this result indicates that
pores can be observed (Fig. 5b). The homogeneous dispersion of the decrease of dielectric loss in the nanocomposites should be
the BT nanoparticles should be attributed to the covalent mainly attributed to the highly restricted polymer chain motion.
bonding between the PVDF-HFP-GMA and the nanoparticle The frequency dependence of the dielectric properties of
surface, which results in homogeneous encapsulation of the PVDF-HFP/BT nanocomposites has been provided in Fig. S3†
polymer on the nanoparticle surfaces. In this case, the (in the ESI). One can see that the frequency dependence of the
compatibility between the nanoparticles and polymer matrix is dielectric properties of the PVDF-HFP/BT nanocomposites
signicantly enhanced and thus the nanoparticle dispersion is shows similar behavior to the PVDF-HFP-GMA/BT nano-
much improved. composites. Namely, the dielectric constant increases with the
increase of BT loading and the dielectric loss decreases with the
increase of BT loading. The comparison of the dielectric prop-
Dielectric response of the nanocomposites erties between the PVDF-HFP-GMA/BT and PVDF-HFP/BT
The frequency dependence of the dielectric properties of the nanocomposites of 1 MHz was carried out and the results are
PVDF-HFP-GMA/BT nanocomposites was measured at various shown in Fig. 6d. It can be observed that only a slight difference
temperatures. Fig. 6 shows the frequency dependent dielectric of dielectric constant and dielectric loss was observed in the two
properties of the PVDF-HFP-GMA/BT nanocomposites at room types of nanocomposites. Considering that the nanocomposites
temperature. Compared with the pure PVDF-HFP, the intro- with high dielectric constant are more attractive for practical
duction of GMA increases the dielectric constant of the PVDF- application, the slightly lower dielectric loss of the PVDF-HFP-
HFP-GMA, which may be due to the introduction of polar GMA nanocomposites with high BT concentrations show the
functional groups.36 It can be observed in Fig. 6a that the superiority of the “graing to” method. The origin of the slightly
dielectric constant of the PVDF-HFP-GMA/BT nanocomposites lower dielectric loss may result from the enhanced restriction of
increases with the loading of BT nanoparticles. For example, the the polymer chains in the PVDF-HFP-GMA nanocomposites,
dielectric constant of GMA-BT-50 is 34.8 at 1 MHz, about which is consistent with the aforementioned analysis on the
3.9 times that of the polymer matrix (Fig. 6d). However the nanoparticle concentration dependence of dielectric loss in the
dielectric loss decreases with the increase of BT loading. The PVDF-HFP-GMA nanocomposites.
dielectric loss of GMA-BT-50 is 0.128 at 1 MHz, only 61% of that In order to obtain further information about the interface
of the polymer matrix (Fig. 6d). Similar results have been between the nanoparticles and polymer matrix, Fig. 7 shows the
frequency dependent dielectric properties of the PVDF-HFP-
GMA/BT nanocomposites, the PVDF-HFP-GMA and the PVDF-
HFP at various temperatures. One can see from Fig. 7 that,
compared with PVDF-HFP, the PVDF-HFP-GMA shows a strong
temperature-dependent dielectric response, particularly at low
frequencies. Interestingly, the introduction of the BT-APS
nanoparticles results in a much weaker temperature-dependent
dielectric response of the nanocomposites. This result can be
understood by the fact that covalent bonding exists between the
nanoparticles and PVDF-HFP-GMA matrix. Unlike the
Fig. 4 TEM images of the washed PVDF-HFP-GMA grafted BT PVDF-HFP, the PVDF-HFP-GMA shows a dielectric response
nanoparticles. typical of strongly polar polymers such as polyamide, namely

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Fig. 6 Frequency dependence of the dielectric properties for the PVDF-HFP-GMA/BT nanocomposites at room temperature: (a) dielectric
constant, (b) dielectric loss tangent and (c) electrical conductivity; (d) comparison of the dielectric properties for the PVDF-HFP-GMA/BT and
PVDF-HFP/BT nanocomposites at 1 M Hz.

the dielectric apparatus exhibits a strong dependence on dependence of dielectric response, low dielectric loss and low
temperature.37 The strong temperature-dependent dielectric conductivity at high temperatures and low frequencies, when
response mainly originates from the electrical conduction compared with PVDF-HFP-GMA.
effect, which is conrmed by the temperature-dependent elec- One of the important applications of the high dielectric
trical conductivity of the three samples. Compared with the constant materials is its use as a dielectric material in energy
PVDF-HFP and the PVDF-HFP-GMA/BT nanocomposites, as storage devices. The energy storage density of PVDF-HFP-GMA/
shown in Fig. 7c, the PVDF-HFP-GMA shows not only much BT nanocomposites can be calculated from the electric
higher, but also nearly frequency-independent electrical displacement-electric eld curves by the following equation:39,40
conductivity at high temperatures and low frequencies. The Ð
ATRP of GMA from PVDF-HFP macromolecular chains intro- U ¼ EdD (1)
duces many epoxy groups. At high temperatures, the mobility of
charge carriers and the rotation of dipoles would be signi- where E is the electric eld and D is the electric displacement.
cantly enhanced because of the existence of epoxy groups in the Fig. 8a shows the electric displacement–electric eld (D–E)
poly(glycidyl methacrylate) brushes, which results in signi- loops of the PVDF-HFP-GMA/BT nanocomposites at 20 MV m1.
cantly enhanced electrical conduction and interfacial polariza- The electric displacement increases with the BT loading under
tion. As a consequence, the PVDF-HFP-GMA exhibits the the same electric eld. The energy storage densities of the
highest dielectric constants at low frequencies and high PVDF-HFP-GMA/BT nanocomposites are shown in Fig. 8b. It
temperatures, as shown in Fig. 7a2. The dielectric loss factor 300dc can be observed that the energy storage densities increase with
sdc the BT loading and electric eld. The enhanced energy density
from dc conduction follows 300 dc ¼ , where f is the electric
2pf in the nanocomposites mainly originates from the increased
eld frequency. This is why we observe a linear relationship of
38
dielectric constant. When the nanoparticle loading is higher
the dielectric loss factor versus frequency for the PVDF-HFP- than 40%, the increase of energy density in the nanocomposites
GMA at high temperatures and low frequencies (Fig. 7b2). Aer becomes more rapid with the increase of electric eld, indi-
the introduction of the BT nanoparticles, the epoxy groups from cating the nanocomposites start to exhibit strong nonlinear
the GMA reacted with the amino groups, which not only causes dielectric properties. The breakdown strength of the PVDF-HFP-
a reduction of the number of epoxy groups, but also results in GMA/BT nanocomposites is shown in Fig. S4† (in the ESI). One
covalent bonding between the nanoparticles and the polymer. can see that the breakdown strength rapidly decreases with the
Both exhibit signicant suppression of the charge transport increase of the BT nanoparticle. This is mainly caused by the
in the polymer matrix, and thus result in a weak frequency electrical property mismatch between BT and the base polymer.

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Fig. 7 Frequency dependent dielectric properties at various temperatures for (a1–c1) GMA-BT-40, (a2–c2) PVDF-HFP-g-GMA and (a3, b3, c3)
PVDF-HFP: (a) dielectric constant, (b) dielectric loss factor and (c) electrical conductivity.

Thermal conductivity of PVDF-HFP-GMA/BT nanocomposites nanocomposites was also evaluated. Fig. 9 shows the thermal
conductivity of the PVDF-HFP-GMA/BT and PVDF-HFP/BT
Increasing the thermal conductivity of electronic components is
nanocomposites. The thermal conductivity of both the PVDF-
becoming more and more important because of the increased
HFP-GMA and PVDF-HFP nanocomposites is enhanced by the
requirements in thermal management.41 High thermal
introduction of BT nanoparticles. For example, the thermal
conductivity is benecial to the fast release of heat generated
conductivity of the PVDF-HFP-GMA nanocomposites with 50%
from the electric current, ensuring stability of the dielectric
BT is 0.701 W K1 m1, about 2.67 fold higher than that of the
materials. Therefore, the thermal conductivity of the

Fig. 8 (a) Electric displacement–electric field (D–E) loops and (b) energy storage density of the PVDF-HFP-GMA/BT nanocomposites.

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Fig. 9 (a) Thermal conductivity of the PVDF-HFP-GMA/BT and PVDF-HFP/BT nanocomposites at room temperature; (b) temperature
dependent thermal conductivity of the PVDF-HFP-GMA/BT nanocomposites.

polymer matrix. Compared with the PVDF-HFP/BT nano- Acknowledgements

composites, the thermal conductivities of the corresponding
PVDF-HFP-GMA/BT nanocomposites are higher. For example, The authors gratefully acknowledge support from the National
at 40 vol% BT loading, the thermal conductivity of the PVDF- Science Foundation of China (nos. 51107081, 51277117), the
HFP-GMA nanocomposite is 0.594 W K1 m1, about 16% Research Fund for the Doctoral Program of Higher Education
higher than that of the PVDF-HFP nanocomposites. The higher (Grant nos 20100073120038, 20120073110031), and the
thermal conductivity should be due to the strong PVDF-HFP- Shanghai Leading Academic Discipline Project (Grant no.
GMA/BT interface, which reduces the interface thermal resis- B202). The authors also thank the Special Fund of the National
tance of the nanocomposites. Compared with the polymer Priority Basic Research of China under Grant 2014CB239503
composites lled by other llers, such as BN and AlN, the and State Key Laboratory of Electrical Insulation and Power
thermal conductivity enhancement by BT is relatively low.41,42 Equipment (EIPE13208).
First, this is because the BT particles used in this work have a
low intrinsic thermal conductivity. On the other hand, the BT
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