Escolar Documentos
Profissional Documentos
Cultura Documentos
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.
DOI 10.1109/TDEI.2014.004314
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.
1517
1518
E
P 1 exp
E 0
(1)
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.
1519
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)
1520
Figure 2. (Continued).
Figure 3. Enlarged AFM images of epoxy/POSS composites: (a) 5% POSS, (b) 10% POSS.
1521
Figure 5. Schematic illustration showing the reaction and microstructure of uncured and cured epoxy/POSS systems.
1522
Figure 7. Temperature-dependent dielectric constant (a, b, c) and dielectric loss tangent (a, b, c) at different frequencies.
1523
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.
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(
1524
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).
(4)
1525
Figure 11. Weibull plots of the ac breakdown data of the epoxy resin and epoxy/POSS composites.
1526
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
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.
REFERENCES
[1]
[2]
[3]
[4]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
1527
1528