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X. Huang et al.: Electrical Properties of Epoxy/POSS Composites with Homogeneous Nanostructure

Electrical Properties of Epoxy/POSS Composites


with Homogeneous Nanostructure
1

Xingyi Huang1,2, Yong Li1, Fei Liu1, Pingkai Jiang1,3


Department of Polymer Science and Engineering and Shanghai Key Lab of Electrical Insulation and Thermal Aging,
Shanghai Jiao Tong University, Shanghai, China, 200240
2
State Key Lab of Power System, Tsinghua University, Beijing 100084, China
3
Shanghai Engineering Center for Material Safety of Nuclear Power Equipment, Shanghai, China, 200240
4

and Tomonori Iizuka , Kohei Tatsumi and Toshikatsu Tanaka


4
IPS Research Center, Waseda University, Kitakyushu, Fukuoka, Japan

ABSTRACT
The knowledge of the structure-property relationship at nanoscale level is important to
develop advanced dielectric polymer composites. Herein dielectric epoxy/polyhedral
oligomeirc silsesquioxanes (POSS) composites with homogeneous nanostructure were
prepared. Unlike the conventional inorganic nanoparticles (e.g., silica) used for polymer
nanocomposite preparation, the POSS molecules used in this work have three advantages:
a comparable size with the segments of polymer chains, being capable of reacting with the
base polymer, good solubility in many solvents. These three advantages make the POSS be
dispersed in polymers at a molecular level and thus their nano-effect could be fully utilized.
Microstructure analysis by transmission electron microscopy, atomic force microscopy and
X-ray diffraction confirmed the molecular-level dispersion of POSS in the epoxy
composites. On this base, the partial discharge erosion resistance, frequency/temperature
dependence of dielectric response, space charge distribution and breakdown strength of
the epoxy/POSS composites were investigated. Moreover, the correlation between the
nanostructure and properties of epoxy/POSS composites was documented.
Index Terms - Nanocomposites, epoxy resin, POSS, dielectric constant, nanostructure,
electrical conductivity, activation energy, space charge distribution, breakdown strength.

1 INTRODUCTION
DIELECTRIC polymer nanocomposites continue to receive
tremendous interests for high voltage application in the field of
engineering dielectric and electrical insulation [1-4]. Compared
with the conventional scaled polymer composites, the polymer
nanocomposites can exhibit remarkable property enhancement
such as increased breakdown strength/time [5], decreased
dielectric loss and leakage currents [6], and enhanced partial
discharge resistance [7]. Moreover, some unexpected results
have been observed in polymer nanocomposites. A typical
example is the breakdown strength of polymer composites with
very low metallic (e.g, silver) nanoparticle loading [8].
Generally, the addition of metallic inclusions can result in
significant decrease of breakdown strength of insulating
polymers [9]. However, the polymer nanocomposites with a very
low concentration of super-small metallic particles really can
exhibit significantly enhanced breakdown strength in comparison
with their base polymers [8]. Recently, the authors of this work
also found that the decoration of low concentration of superManuscript received on 30 August 2013, in final form 15 January 2014,
accepted 21 January 2014.

small silver particles on the surface of BaTiO3 can significantly


suppress the low-frequency dielectric loss and increase the
energy storage density of BaTiO3 based nanocomposites [10].
Another example is the dielectric constant of the nanocomposites
consisting of a low-dielectric-constant polymer and highdielectric-constant inorganic particles. In this case, the classic
effective medium theory always predicts that the nanocomposites
have dielectric constant higher than that of the base polymer [11,
12]. However, a dielectric constant lower than that of the based
polymer has been observed in several nanocomposite systems [5,
6]. It is now believed that, apart from the unique intrinsic
physical properties of the nanoparticles, the property
enhancement observed in polymer nanocomposites mainly
associated with the small size of nanoparticles and the unique
interface property of the nanocomposites [5, 13-17].
Large property enhancement in dielectric polymer
nanocomposites was often predicted in research perspectives and
reviews based on the available knowledge. However, sometimes
the predicted advantages cannot become reality. In other word,
not all dielectric polymer nanocomposites perform like those
predicted according to available reports. Poor dispersion of the
nanoparticles and weak interfacial strength between the

DOI 10.1109/TDEI.2014.004314

IEEE Transactions on Dielectrics and Electrical Insulation

Vol. 21, No. 4; August 2014

nanoparticles and the polymer, which are generally caused by


unsuitable processing, are considered as the main reasons [18].
However, other factors such as the improper understanding on
the nanocomposite terminology also are causes. How nano are
nanocomposites? How about the length-scale of the interaction
between the nanoparticles and the polymers? What is the lowest
level of nanoparticle dispersion and distribution should be
fulfilled in the polymer nanocomposites? So far, there is a large
body of literature about the nanoparticle filled dielectric polymer
composites, however, not too many of them paid attention to
these basic issues before giving the name of
polymer/nanoparticle blends as nanocomposites, which restricted
our understanding on the structure-property relationship of
nanocomposites and thus caused limited capability to design and
realize nanocomposites with high performances.
Although the current research is not intended to fully answer
the aforementioned questions, we performed a case study by
investigating an epoxy/polyhedral oligomeirc silsesquioxanes
(POSS) system which is the nearest approximation of ideal
dielectric polymer nanocomposites. Three advantages of this
system are worthwhile to be mentioned for the structure-property
relationship research. First, the single POSS molecules are very
small (about 1-3 nm) [19], which could exhibit remarkable small
size effect; Second, the end groups of POSS can react with the
polymer matrix and thus resulting in covalent bonding interface;
Finally, the POSS molecules can be dissolved in solvents at
molecular scale, making the composite processing be easier and
more controllable in comparison with other particulate
composites. These three advantages mean at first that the POSS
might be dispersed in polymers at a molecular level and thus the
nano-effect can be fully exhibited. Second, the size of the POSS
molecules is comparable with the length-scale of several
segmental units of the polymer chains, indicating that the
polymer superstructure and the chain dynamics in the interfacial
regions could be modified and thus significant property changes
of the composites are expected.
Reactive and nonreactive POSS/polymer composites have
been investigated by dielectric characterization in previous
researches [19-23]. The information about the structure-property
relationship at nanoscopic level, however, is still scarce. In this
work, reactive POSS/epoxy composites with homogeneous
nanostructure were prepared and the dielectric properties and
partial discharge erosion resistance of the composites as well as
the detailed microstructure information of the composites are
reported. The principle objective of this work is to try to reveal
the structure-property relationship of dielectric polymer
nanocomposites by investigating a system with homogeneous
nanostructure.

2 EXPERIMENTAL SECTION
2.1 RAW MATERIALS
Cycloaliphatic epoxy resin (6105, ECETMS) and curing
agent of methyl-hexahydrophthalic anhydride (MHHPA) were
purchased from DOW Chemical Company (USA) and Lon ca
group (Italy), respectively. Neodymium (III) acetyulacetonate
trihydrate (Nd(acac)3) was purchased from Aldrich-Sigma.

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Figure 1. Setup for partial discharge erosion experiment.

The POSS named as octa(aminophenyl)silsesquioxane was


purchased from Amwest Technology Company (Shenyang,
China). Other chemicals were obtained from Sinapharm
Chemical Reagent Co., Ltd, China.
2.2 SAMPLE PREPARATION
First, the POSS and Nd(acac)3 were dissolved in acetone and
epoxy, respectively. Afterwards, the epoxy resin/Nd(acac)3
solution was mixed with the POSS/acetone solution by
mechanical agitation. The resulting mixture was heated to
remove most of the acetone and then degassed at vacuum to
remove any residue of acetone. Subsequently, MHHPA were
added to the epoxy/POSS mixture with vigorous mechanical
stirring
and
degassed
in
vacuum.
Finally,
the
epoxy/POSS/MHHPA mixture was poured onto preheated
stainless steel molds, pre-cured at 135 C for 3 h, followed by
post-cure at 160 C for 14 h. All the epoxy/POSS composites
used for the following measurements have a thickness of 1000
mm 50 mm. The ratio of epoxide to anhydride and the ratiao of
Nd(acac)3 to epoxy + MHHPA were 100:85 and 3:1000,
respectively. The POSS content in the samples is 0, 2.5, 5, 7.5
and 10 wt%. All the samples were annealed at 160 C for 10 h at
a vacuum oven before measurements.
2.3 Charaterization
Transmission electron microscopy (TEM, JEOL JEM-2100)
was used to analyze the dispersion of POSS in the epoxy resin
matrix. TEM specimens (about 70 nm in thickness) were
trimmed by using an ultramicrotome (Ultracut-1, UK) with a
glass knife at room temperature. The TEM specimens were
also used to perform the atomic force microscopy (AFM)
analysis by using a Nanoscope IIIa scanning probe
microscope (Digital Instruments). Tapping mode and a silicon
tip (0.125 mm in length with about 500 kHz resonant
frequency) was used in air condition during the AFM
measurement.
X-ray diffraction (XRD) patterns of POSS and the
epoxy/POSS composites were collected on a Rigaku D/MAX2200/PC diffractometer with nickel-filtered Cu target K
radiation at 40 kV and 20 mA. All the measurements were
carried out at room temperature and the data were collected as
a scanning rate of 4 /min.

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X. Huang et al.: Electrical Properties of Epoxy/POSS Composites with Homogeneous Nanostructure

A home-made rod to plane electrode system illustrated in


Figure 1 was used to evaluate the erosion depth of epoxy resin
and the epoxy/POSS composites caused by partial discharge.
As shown in Figure 1, the system consists of a tungsten rod
electrode (diameter: 1 mm, radius of tip: 0.5 mm) and a brass
plane electrode. For measurement, a sample is placed between
the tip of the rod electrode and the surface of the plane
electrode and finally the air gap between the rod tip and the
sample surface is 2 mm [24-27]. The surface of the samples
was eroded because of partial discharge exposure, and the
maximum erosion depth was used to evaluate the partial
discharge resistance. AC voltage of 4 kVrms with a frequency
of 600 Hz is applied across the rod to plane electrode system
with a sample for 72 h. The erosion depth and profile were
measured by a laser microscope (KEYENCE VK-9510) on
aged sample surfaces.
Frequency and temperature dependence of dielectric
response of the epoxy resin and the epoxy/POSS composites
were measured by a Novocontrol Concept 40 broadband
dielectric spectrometer (GmbH, Germany). All the samples
used for dielectric measurements have a diameter of 20 mm.
Gold electrodes were deposited on the front and rear surfaces
of the samples. Dielectric constant and dielectric loss tangent
were collected in the frequency range of 0.1 Hz to 1 MHz at
different temperatures.
Glass transition temperatures were obtained by differential
scanning calorimetry (DSC 200 F3, NETZSCH, Germany).
The samples encapsulated in an Al pan were first heated to
250 C and held at this temperature for 5 minutes to eliminate
the thermal history and then cooled to room temperature. Then
the samples were heated up to 250 C at a rate of 10 C/min.
The DSC curves of this step were collected for determining
the glass transition temperatures.
Pulsed electro-acoustic (PEA) method was used to measure
the space charge distribution in epoxy resin and the
epoxy/POSS composites. All the samples were sandwiched
between a ground Al electrode and a semiconducting carbon
black filled polymer top electrode in the PEA system. For
each measurement, a -16kV/mm DC electric field was applied
for 1.5 h and then the sample was short-circuited. A real-time
recording software was used to collect the space charge
distribution during the field application and the short-circuit
stage. All the measurements were performed at room
temperature.
Breakdown strength measurements were performed by
using an AHDZ-10/100 AC dielectric strength tester
(Shanghai Lanpotronics Corp., China) with copper ball
electrodes of fixed diameter (10 mm for the bottom and top
ones). The samples were placed between the electrodes
immersed in the pure silicone oil, and then a 50 Hz ramp
voltage was applied across the top and the bottom electrodes
and was increased at a rate of 2 kVrms/s until the sample was
punctured. All the measurements were performed at room
temperature and ten breakdown tests were repeatedly
performed on each sample.
The breakdown data were treated by two-parameter
Weibull statistical distribution method. According to this

method, the cumulative probability of electrical failure, P, can


be written as

E
P 1 exp
E 0

(1)

where E is an experimental breakdown strength; is the shape


parameter which reflects the scatter of the data; E0, the scale
parameter, is the characteristic dielectric breakdown representing
the breakdown strength at the cumulative failure probability of
63.2%. The scale parameter is usually used to compare the
difference in breakdown strength among different specimens.
According to the recommendation of the IEEE Std 930-2004
standards, a simple and good approximation for the most likely
probability of electric failure is presented in the equation

Pi

i 0.44
100 %
n 0.25

(2)

where i is the i-th result when the values of the E are sorted in
ascending order and n is the number of specimens; for this
work, n = 10.

3 RESULTS AND DISCUSSION


3.1 MICROSTRUCTURE ANALYSIS
All the samples (i.e., the pure epoxy and the epoxy/POSS
composites) were characterized by TEM and AFM in order to
accurately analyze the effect of the POSS addition on the
microstructure of the cured epoxy resin. The left column of Figure
2 shows the representative TEM images of the epoxy resin and the
epoxy/POSS composites. One can see that the pure epoxy resin
exhibits a homogeneous structure, which does not display any
appreciable inhomogeneity even at the nanoscale level. The epoxy
composite with 2.5% POSS almost has the same microstructure
with the pure epoxy resin, indicating the POSS was dispersed in the
epoxy resin at a molecular level. Starting from the epoxy
composites with 5% POSS, a very small amounts of darker
domains with diameter lower than 20 nm can be observed. These
darker domains should be attributed to the small crystals of POSS
molecules because of their higher mass contrast in comparison with
the epoxy molecular chains. Despite the appearance of small
crystals, their density and size do not show a clear dependence of
the POSS concentration in the composites. Even at the composites
with 10% POSS, there is only several small darker domains in the
view and thus their density is still very low.
Shown in the middle and right columns of Figure 2 are
the AFM height and phase images of epoxy resin and
epoxy/POSS composites, respectively. Figure 3 provided
the enlarged AFM height and phase images of the epoxy
composites with 5% and 10% POSS. It should be noted that
the pure epoxy resin shows an intrinsic nanostructured
morphology, in which one type of domains are attributed to
the epoxy molecules, while another type of domains are
ascribed to the curing agent molecules. Light contrast
between two phases could be observed because of the weak
mass contrast between the epoxy molecular chains and the
curing agent. Unlike the pure epoxy resin in which
the contrast between epoxy and curing agent is light, the

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Figure 2. TEM and AFM images of epoxy resin and epoxy/POSS composites: a, a and a denote the TEM, AFM height and AFM phase images of the pure
epoxy resin, respectively; a, b, c, d and e denote TEM images of epoxy resin, epoxy resin with 2.5% POSS, epoxy resin with 5% POSS, epoxy resin with 7.5%
POSS and epoxy resin with 10% POSS, respectively.
(Continued)

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X. Huang et al.: Electrical Properties of Epoxy/POSS Composites with Homogeneous Nanostructure

Figure 2. (Continued).

Figure 3. Enlarged AFM images of epoxy/POSS composites: (a) 5% POSS, (b) 10% POSS.

epoxy/POSS composites exhibit clearer nanostructured


morphology. As shown from b to e in Figure 2, darker
nanodomains, which should be attributed to the POSSrich regions, appear in the epoxy composites. These dark
domains were homogeneously dispersed in the epoxy
resin and their average size is around 10 nm.
As the
concentration of POSS increases, the distance between the
adjacent POSS nanodomains decreases while the size of
the nanodomains remained almost invariant. These results
indicated that the POSS nanodomains do not tend to
assemble with the increase of the POSS concentration
below 10%. Large domains of POSS are not observed in
the AFM images, and other results are consistent with the
TEM analysis.
Besides TEM and AFM analysis, XRD technology was
also used to further confirm the molecular-level
dispersion of POSS in the epoxy resin matrix. Figure 4
shows the XRD patterns of the POSS, the epoxy/POSS
composites and the pure epoxy resin. One can see that the
pure POSS shows a peak at 2 = 5.7, which should be
ascribed to the long-range order in the solid POSS [28].
In addition, there exist a broad halo from 2 = 15 to 2 =
30, which should be associated with the Si-O-Si linkages
[28]. In the epoxy/POSS composites, however, the XRD
patterns become similar to that of the neat epoxy resin. As
can be seen in Figure 4, all the epoxy/POSS composites
only show a typical amorphous pattern of epoxy at about
2 = 16.5, indicating the disappearance of POSS
crystalline structure in the epoxy matrix. These results

point out the molecular level dispersion of POSS in the


epoxy resin, in agreement with the microstructure
observation by TEM and AFM.
Taking the aforementioned microstructure analysis into
account, a schematic reaction and microstructure presentation
of the epoxy/POSS composites was presented in Figure 5. For
the pure epoxy resin, the curing reaction is started by the

Figure 4. XRD patterns of POSS, epoxy/POSS composites and the pure


epoxy resin.

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Figure 5. Schematic illustration showing the reaction and microstructure of uncured and cured epoxy/POSS systems.

reaction of acid anhydride with the epoxide ring under the


catalysis of Nd(acac)3, to generate a monoester with a
carboxylic acid ion, which in turn reacts with another
anhydride.
Once the POSS was introduced, addition reaction between
the amino groups of the POSS and epoxide ring was also
involved in the curing reaction between the POSS and the
epoxy. It is considered that the chemical reaction between the
POSS and the epoxy resin/curing agent is the key to obtain
molecular dispersion of the POSS and nanostructured
morphology of the epoxy/POSS composites. In fact, the amino
groups can not only react with the epoxide rings from the
epoxy precursor but also react with the anhydride from the
curing agents. Such a fact indicates that the uncured epoxyanhydride system with POSS may still maintain the same ratio
of epoxide ring to the anhydride in comparison with the
uncured epoxy-anhydride system without POSS.
3.2 PARTIAL DISCHARGE EROSION RESISTANCE
Figure 6 shows the maximum depth of erosion caused by
partial discharge for the pure epoxy and the epoxy/POSS
composites. One can see that the addition of the POSS shows
significant improvement of erosion resistance in the epoxy
composites. For example, the average maximum erosion depth
for the pure epoxy resin is about 270 m, whereas the
composite sample with 2.5% POSS only shows a maximum
erosion depth of 167 m. That is, the average maximum

erosion depth of the epoxy resin was decreased by 38% after


the introduction of 2.5% POSS. Starting from the POSS
concentration of 5%, the further increase of POSS loading
only shows a slight improvement of erosion resistance in the
epoxy composites. For instance, at a POSS concentration of
10%, the average erosion depth of the epoxy composite was
only decreased by 20% in comparison with the epoxy
composite with 2.5% POSS (i.e., from 167 to 135 m).

Figure 6. Maximum erosion depth caused by partial discharge of the pure


epoxy resin and epoxy/POSS composites.

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X. Huang et al.: Electrical Properties of Epoxy/POSS Composites with Homogeneous Nanostructure

Figure 7. Temperature-dependent dielectric constant (a, b, c) and dielectric loss tangent (a, b, c) at different frequencies.

It has been shown in T. Tanaka group that the addition of


inorganic nanoparticles such as silica and titania into polymers
could significantly improve the partial discharge resistance of
the corresponding composites [23-27]. The POSS used in this
work consists of an inorganic silica core having eight organic
aminophenyl substituents capable of reacting with both epoxy
and curing agent [23]. Therefore, in combination with the
microstructure analysis, the partial discharge resistance of the
epoxy/POSS composites can be understood by the facts that
the POSS takes part in the curing reactions and then becomes
the chain segments of the thermoset network [7]. In such a
case, the macromolecular chains of the epoxy resin are
segmented by POSS molecules. On the other hand, the
incorporation of the POSS molecules into the epoxy resin
macromolecular chains can result in high tightness. These two
factors are important to increase the partial discharge
resistance of the epoxy/POSS composites [7].
3.3 COMPLEX DIELECTRIC CONSTANT
Figure 7 shows the temperature-dependent dielectric
constant and dielectric loss tangent of the epoxy resin and the
epoxy/POSS composites at 1 Hz, 1000 Hz, and 1 M Hz. In the
case of dielectric constant, we can see that: (i) the
epoxy/POSS composites generally have slightly higher
dielectric constant than that of the pure epoxy resin; (ii) lower
dielectric constant in the epoxy/POSS composites only
appears when three conditions (i.e., very low temperatures,
high frequencies and high POSS concentration) are satisfied
simultaneously; (iii) the dielectric constant difference between
the epoxy/POSS and epoxy resin is marginal at low
temperatures and becomes larger as the temperature increases;
(iv) the epoxy composites with high POSS loading shows

lower values in comparison with the sample with low POSS


loading. Regarding the dielectric loss tangent, it is observed
from Figure 7 that, at the whole temperature and frequency
range, all the epoxy/POSS composites exhibit higher values in
comparison with the pure epoxy resin. In addition, the
dielectric loss tangent difference caused by the POSS loading
in the composites is marginal.
In order to understand the aforementioned dielectric
response and to know the mechanism behind the observed
dielectric phenomena, the frequency-dependent imaginary
dielectric constant and frequency-dependent electrical
conductivity from room temperature to 220 C were provided
in Figure 8. At low frequencies, the imaginary dielectric
constant decreases rapidly with the increase of the frequency,
particularly at high temperatures. For the epoxy resin and the
epoxy/POSS composites, the slopes of the imaginary
dielectric constant in the low frequencies/high temperatures
are -1, which is typically originating from dc conductivity
effect [29]. These results are confirmed by the corresponding
frequency-dependent electrical conductivity plots shown in a,
b and c of Figure 8, in which a dc conductivity plateau is
observed at low frequencies and high temperatures. In
addition, compared with the pure epoxy resin, the dc
conductivity plateau in the epoxy/POSS composites starts to
appear at relatively lower temperatures and the transition from
dc conductivity to frequency-dependent conductivity shifts to
high frequencies. It has been proved in previous reports that
the electrical conduction of epoxy resin mainly originates
from the movement of ionic carriers (i.e., migration towards
the counter-electrode) [29, 30]. Here the significant increase
of electrical conductivity in the epoxy/POSS composites
indicates that the introduction of POSS leads to an increase of

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Figure 8. Frequency-dependent imaginary part of dielectric constant (a, b, c), frequency-dependent electrical conductivity (a, b, c) and imaginary part of
electric modulus (a, b, c) at different temperatures.

ionic carriers and thus strong ionic relaxation. In fact, the


rapid increase of dielectric constant in the epoxy/POSS
composites, particularly at low frequencies/high temperatures,
should be mainly attributed to the electrical conductivity
effect. When the charge exchange between the sample and the
electrode does not take place, hetero charges would
accumulate in the electrode surfaces, which in turn cause the
increase of dielectric constant.
At low electric field and temperatures higher than glass
transition temperatures, the dc electrical conductivity in
dielectric polymer materials follows the Arrhenius law [31],
E

a
(3)
)
kT
where Ea and k are the activation energy of the electrical
conduction process and Boltzmann constant, respectively. In
order to quantitatively evaluate the effect of POSS addition on
the dc electrical conductivity of the epoxy/POSS composites,
the glass transition temperatures of the epoxy resin and the
epoxy/POSS composites were first measured (see Figure 9a,

exp(

the addition of POSS results in slight decrease of the glass


transition temperatures of the epoxy resin, but the glass
transition temperatures of the epoxy/POSS composites are
almost independent on the POSS content), then the plots of
electrical conductivity beyond the glass transition points of the
corresponding samples against the reciprocal temperature
were shown in Figure 9b. One can see that, at temperatures
higher than the glass transition points, the dc electrical
conductivity of the epoxy resin and the epoxy/POSS
composites follows the Arrhenius law well. The activation
energy values calculated from the slopes of the solid lines,
which are least-squares linear fits to the experimental data, are
1.82, 2.49 and 2.77 eV for the epoxy resin, the epoxy
composite with 5% POSS and the epoxy composite with 10%
POSS, respectively. The higher activation energy indicates
that, compared with the pure epoxy resin, the variation of
electrical conductivity or the ionic relaxation is more sensitive
in the epoxy/POSS composites.
For further characterizing the ionic relaxation (electrical
conduction) relaxation, it is of interest to know the effect of

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X. Huang et al.: Electrical Properties of Epoxy/POSS Composites with Homogeneous Nanostructure

Figure 9. (a) DSC curves with the glass transition temperatures of the epoxy resin and the epoxy/POSS composites; (b) Arrhenius plot of dc electrical
conductivity of the epoxy resin and the epoxy/POSS composites at the temperatures higher than the glass transition temperatures of the corresponding samples,
and the solid lines are least-squares linear fits to the experimental data; (c) Arrhenius plot of relaxation peak frequency of electrical conductivity of the epoxy
resin and the epoxy/POSS composites, and the solid lines are least-squares linear fits to the experimental data.

Figure 10. Space charge distribution in the epoxy resin and the epoxy/POSS composites when the electric field was applied 1.5 h (a) and space charge
distribution in epoxy resin and epoxy/POSS composites at 2 seconds after short-circuit (b).

POSS addition on the relaxation time of the epoxy/POSS


composites. However, the loss spectra shown in a, b, c of the
Figure 8 do not show appreciable relaxation phenomena. In
this case, the electric modulus format was used [32]. The

imaginary part of electric modulus can be defined as

(4)

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Figure 11. Weibull plots of the ac breakdown data of the epoxy resin and epoxy/POSS composites.

Figure 8a-c shows the frequency-dependent imaginary


electric modulus of epoxy resin and epoxy/POSS composites
at higher temperatures, which exhibit a Debye-like narrow
relaxation peak at low frequencies and the peak shifts to low
frequencies as the temperature decreases. This peak has been
assigned to the electrical conduction relaxation because that it
is narrow and takes place at low frequency range, which are
the typical characteristics of charge migration process [31].
Figure 9c shows influence of temperature on the relaxation
frequency of the narrow peak for the pure epoxy and
epoxy/POSS composites. It can be seen that the addition of
POSS results in a high relaxation peak frequency. That is, the
relaxation time of electrical conduction in epoxy/POSS
composites becomes shorter. In addition, Figure 9c also shows
that the data of any sample follows an Arrhenius law. As
expected, the activation energy calculated from the electric
modulus data of any sample is very close to that calculated
from the temperature-dependent electrical conductivity data
shown in Figure 9b.
3.4 SPACE CHARGE BEHAVIOR
Figure 10a shows the space charge distribution in the epoxy
resin and the epoxy/POSS composites after 1.5 h of
application of -16 kV/mm DC electric field. We can see that
both homo charges and hetero charge are not clearly
appreciable. However, the charge accumulation in the samples
would be seen when the samples were just short-circuited.
Figure 10b shows the space charge distribution in the epoxy
resin and the epoxy/POSS composites at the moment of 2 s
after 1.5 h of application of -16 kV/mm DC electric field. A
large amount of homo charges accumulated in the vicinity of
the ground electrode, while only a small amount of homo
charges accumulated in the vicinity of the top electrode. This

result indicates that the charge injection mainly takes place in


the ground electrode. Figure 10b also shows that the pure
epoxy resin exhibits the largest accumulation of homo charges
near the ground electrode. After the addition of POSS into the
epoxy resin, the accumulation of charge becomes smaller with
the increase of POSS from 2.5% to 5%, whereas it also can be
seen that the accumulation of charge shows a slight increase
with further increase of POSS from 7.5 to 10%. The absence
of hetero charges in the epoxy resin and epoxy/POSS
composites means that the impurities, which are generally the
source of hetero charges, in both epoxy resin and epoxy/POSS
composites is at a very low level. This result indirectly means
most of the amino groups of POSS were reacted with the
epoxide rings or anhydride during the curing process of the
samples.
3.5 BREAKDOWN STRENGTH
Breakdown strength is of great important for evaluating the
practical application of the epoxy/POSS composites. Shown in
Figure 11 are the Weibull plots of the breakdown strength of
the epoxy resin and epoxy/POSS composites. Table 1 lists the
characteristic breakdown strength and the scale factors. A
careful comparison of the data leads to such a conclusion: all
the epoxy/POSS composites shows comparable breakdown
strength with the pure epoxy resin. In other words, the
addition of POSS does not cause significant influence on the
breakdown strength of the epoxy/POSS composites.
Provided that the samples have the same size (diameter,
thickness) and that the testing conditions (e.g., electric field
frequency, temperature, electrodes, moisture, etc) are fixed,
the breakdown strength of a composite composed of two
components should be mainly determined by the dielectric
constant difference between the two components, composite

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X. Huang et al.: Electrical Properties of Epoxy/POSS Composites with Homogeneous Nanostructure

microstructure, and defect magnitude and density in the


samples [33]. Therefore, the observed comparable
breakdown strength in the epoxy resin and the epoxy/POSS
composites can be attributed to several factors. First, it
should be attributed to the homogenous nanostructure of
the epoxy/POSS composites (Figures 2 and 3), which is
similar to the intrinsic microstructures of the epoxy resin.
In the epoxy/POSS composites, the POSS takes part in the
curing reactions and becomes the chain segments of the
thermoset macromolecular networks and thus does not
produce any physical interface. Second, appreciable defects
such as large pores and voids are hardly observed in the
composites, as shown in TEM images. Third, the benzene
ring from the aminophenyl groups of POSS may have more
or less positive effect on maintaining a high breakdown
strength in the epoxy/POSS composites. It has been shown
in previous reports that the aromatic groups are beneficial
to enhance the breakdown strength of polymer films [34,
35]. Finally, it is considered that the comparable dielectric
constant of the POSS and epoxy resin is an important
reason. The inorganic core of POSS has a low intrinsic
dielectric constant of 2.2 to 2.5, whereas the aminophenyl
groups have a higher dielectric constant of about 7.
Provided that the dielectric constant of POSS would not be
changed significantly even the aminophenyl groups were
reacted with the base polymer, it is reasonable to predict
that, at room temperature, the oct(aminophenyl) POSS have
a comparable dielectric constant in comparison with the
epoxy resin (the dielectric constant is about 4 at room
temperature). In fact, the results shown in Figure 5 have
evidenced such a prediction.
Table 1. Weibull parameters obtained from Figure 11.
Sample

E0 (kV/mm)

Epoxy resin
Epoxy + 2.5% POSS
Epoxy + 5% POSS
Epoxy + 7.5% POSS
Epoxy + 10% POSS

33.73
34.81
33.71
33.58
34.55

13.20
6.76
12.06
8.47
10.58

4 CONCLUSIONS
Reactive POSS/epoxy composites with homogeneous
nanostructure were successfully prepared and their partial
discharge resistance, dielectric response, space charge
distribution and breakdown strength were investigated. The
main experimental conclusions are listed as below:
The POSS is dispersed in the epoxy resin at a molecular
level and thus the epoxy/POSS composites show a
homogeneous nanostructure. The introduction of small
fraction of POSS (i.e., 2.5%) can result in an apparent
resistance of partial discharge erosion, whereas the further
increase of POSS loading only shows a marginal improvement
of partial discharge erosion resistance.
The addition of POSS causes slight influence on dielectric
constant of the epoxy/POSS composites at low temperatures
and high frequencies. At low frequencies and higher
temperatures, significant increase of dielectric constant is

observed in the epoxy/POSS composites. Lower dielectric


constant in the epoxy/POSS composites can only be observed
when three conditions including very low temperatures, high
frequencies and high POSS concentration are satisfied
simultaneously. The dielectric loss tangent of the epoxy/POSS
composites is always higher in comparison with the pure
epoxy resin.
An electrical conduction relaxation is observed in the pure
epoxy resin and the epoxy/POSS composites at high
temperatures and low frequencies, and the addition of POSS
results in higher activation energy and shorter relaxation time
of the epoxy composites, indicating that the variation of
electrical conductivity or the ionic relaxation is more sensitive
for the epoxy/POSS composites in comparison with the pure
epoxy resin.
In the epoxy resin and the epoxy/POSS composites, only
homo charges accumulated near the ground electrode after the
application of 1.5 h of -16 kV/mm DC electric field. The
absence of hetero charges means that the impurities maintain a
very low level in both epoxy resin and epoxy/POSS
composites. This result may indirectly indicate that the POSS
were fully reacted with the base polymer during the curing
and annealing processes of the composites.
The pure epoxy resin and the epoxy/POSS composites have
comparable characteristic breakdown strength, regardless of
the POSS loading within 10%.
The current study shows that the chemical reaction between
POSS and the base polymer degree is the key to make the
epoxy composites have improved properties or maintain the
excellent properties of the base polymer. The disadvantages of
the epoxy/POSS composites are the high dielectric constant
and high dielectric loss caused by the intrinsic properties of
the POSS used. However, these issues might be further
resolved by choosing other reactive POSS.

ACKNOWLEDGMENT
The authors gratefully acknowledge supports from the
National Science Foundation of China (Nos. 51107081,
51217117), the Research Fund for the Doctoral Program of
Higher Education (Nos. 20100073120038, 20120073110031),
the State Key Lab of Power System (No. SKLD13KZ02), the
Shanghai Leading Academic Discipline Project (No. B202)
and the Special Fund of the National Priority Basic Research
of China under Grant No.2014CB239503.

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Xingyi Huang (M13) was born in Shandong
Province, China. He received the Ph.D. degree of
Materials Science at Shanghai Jiao Tong University in
2008. Since 2013, he has been an associate professor
of the Department of Polymer Science and
Engineering and Shanghai Key Lab of Electrical
Insulation and Thermal Ageing, Shanghai Jiao Tong
University. He was a Visiting Junior Researcher
(2011.4-2012.3) and an Adjunct Researcher (2012.42013.3) at Waseda University, Japan. His interests are
the
preparation
of
nanostructured
polymer
nanocomposites with desirable dielectric properties and dielectric polymer
composites with high thermal conductivity.
Yong Li was born in Zhejiang Province, China in
1986. He received the B.S. (in 2009) degree and M.S.
(in 2012) degree from Zhejiang University and
Shanghai Jiao Tong University, respectively.
Currently, he is a teacher in Hangzhou No.2 High
School of Zhejiang Province, China.

1528

X. Huang et al.: Electrical Properties of Epoxy/POSS Composites with Homogeneous Nanostructure


Fei Liu was born in China in 1982. He received the
B.S. and M.S. degrees in electrical engineering in
2003 from Xian Jiaotong University and in 2006
from Shanghai Jiao Tong University, China,
respectively. Since 2006, he has become an employee
of Shanghai Jiao Tong University, China. In 2008, he
became a Ph.D. student in electrical engineering at
Shanghai Jiao Tong University.

Pingkai Jiang was born in Jiangxi province, China in


1960. He received the Ph.D. degree in electrical materials
and insulation technology in 1995 at Xian Jiao Tong
University. Currently, he is Director of Shanghai Key Lab
of Electrical Insulation and Thermal Ageing and Director
of Research Center of Dielectric and Electrical Insulation
at Shanghai Jiao Tong University. He also is a full
professor of Department of Polymer Science and
Engineering at Shanghai Jiao Tong University. He has
worked on electrical ageing of polymeric insulating
materials, new VPI materials for insulation of large generators & motors, fire
retardant materials for electrical insulation, water treeing phenomena in XLPE and
polymer nanocomposites for dielectric application.
Tomonori IIZUKA (D.Eng) was born on 20 April
1982 in Japan. He received the B.Eng degree from
Salesian Polytechnic Advanced Course in production
system Engineering in 2005, the M.Eng. degree from
Waseda University in 2007, the D.Eng. degree from
Waseda University in 2012, and is presently a
Research Associate at Waseda University Research
Center in Tatsumi Laboratory, His research interests
are focused on development and evaluation of
electrical insulation materials of polymer nanocomposites for electronics device packaging. IEEE DEIS Japan Chapter
Student Award 2007. He is a member of the IEEJ and IEEE.

Kohei Tatsumi was born in Osaka, Japan in 1953. He


received the B.Eng. and the M.Sc. degrees in
metallurgical engineering from Waseda University
Tokyo, Japan, in 1976 and in 1978 respectively, and
the Dr. Ing. degree in physical metallurgy from
Technische Hochschule Aachen, Germany in 1983. He
joined Nippon Steel Corporation, Japan in 1983,
where he became the head of advanced material
research division in 2001 and a member of boards of
Nippon Steel Materials in 2008, respectively, and
temporarily worked for Tokyo Institute of Technology as a lecturer in
production engineering during 2002-2003. Since 2010 he has been a professor
at graduate school of Information, Production, and Systems, Waseda
University. He was a recipient of the Nikkei BP Technology Prize in 1991 and
the best paper Award of ASME/JSME Joint Conference in 1992. His research
interests cover the area of electronic materials, including SiC crystals for
power devices, high temperature resistant packaging, polymer composite and
nano size particles. He is a member of the Japan Institute of Metals, Japan
Institute of Electronics Packaging and Japan Society of Applied Physics

Toshikatsu Tanaka (SM95-F00). He is Professor at


IPS Graduate School, Waseda University. Ph.D.
(Osaka University). He worked for CRIEPI for 38
years, and temporarily for Salford University in UK,
Rennselaer Polytechnic Institute and General Electric
in the USA, and Kyushu University in Japan. His
interest has covered polymer nanocomposites,
insulation diagnostics, electrical properties of
polymers, and dielectric failure and aging
mechanisms of polymers, as well as superconducting
technologies, laser-induced lightning, fuel cells, lithium secondary batteries,
and energy storage in electric power systems. He is a recipient of the Ministry
of Science and Technology Prize in 2000, IEEJ Technology Progress Award in
1988, IEEE Whitehead Memorial Lecture Award in 2001 and IEEE Dakin
Award in 2002. He is active in IEEJ, IEEE, and CIGRE. He is an IEEJ Life
Fellow and a CIGRE Distinguished Member.

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