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Advances in Materials Science and Engineering

Volume 2014, Article ID 549275, 6 pages
http://dx.doi.org/10.1155/2014/549275

Research Article
Tunable Nanodielectric Composites

Daniel Qi Tan,1 Yang Cao,1,2 Xiaomei Fang,1 and Patricia C. Irwin1

1
GE Global Research Center, Niskayuna, NY 12309, USA
2
Department of Electrical and Computer Engineering, University of Connecticut, Storrs, CT 06269, USA

Correspondence should be addressed to Daniel Qi Tan; tan@ge.com

Received 12 November 2013; Revised 22 January 2014; Accepted 12 February 2014; Published 25 March 2014

Academic Editor: A. G. Barbosa de Lima

Copyright 2014 Daniel Qi Tan et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

This paper presents a progress update with the development of nanodielectric composites with electric field tunability for various
high energy, high power electrical applications. It is demonstrated that nonlinear electrical/dielectric properties can be achieved
via the nanostructure and interface engineering. A high level summary was given on the progress achieved as well as challenges
remaining in nanodielectric engineering towards high energy density capacitors for energy storage and conversion, nonlinear
dielectrics for tunable device, and high voltage varistor for surge suppression.

1. Introduction with controlled microstructures so that desirable electrical

properties can be greatly enhanced [1, 6]. On the other hand,
The rapid expansion of renewable energy applications dielectric response of materials can be utilized to facilitate
demands higher efficiency and higher density energy stor- the formation of nanostructures [7]. In this paper, progress
age and energy conversion systems [1, 2]. Various DC-AC, updates are given as exemplary cases on the development
AC-AC conversions are needed for solar and wind farms, of nanoenabled composite materials for high energy density
while primary and secondary electrochemical devices are in capacitors for energy storage and conversion, field tunable
need for transportation and telecommunication applications. nonlinear dielectrics, and miniaturized varistors for high
Advanced devices and components are critical enablers for voltage/high current transient suppression.
these emerging applications. As an example, in a typical elec-
trical converter/inverter, state-of-art DC-link capacitors take
up about 30% total volume and weight. In addition, the wide 2. Experimental
usage of renewable energy resources such as wind and solar
posts challenges in grid stability. Advanced passive and active In this investigation, polyetherimide (PEI), silicone, cya-
devices will be needed for future grid for harmonic filtration, noethyl cellulose, polyimide, and poly(vinylidene difluoride)
static/dynamic volt-ampere reactive (VAR) compensation, were used as the polymer matrices in the investigation.
transient suppression, and so forth [3, 4]. Nanoparticles of interest include oxides of silicon, niobium,
All these advanced apparatus and future electric power aluminum, zinc, bismuth, antimony, cobalt, titanium, and
infrastructure rely on the breakthroughs of material engi- barium titanate and lead zirconates, with the particle size in
neering and better understanding of the device physics [1]. the range of 10 to 100 nm. Polymer nanocomposites were
For instance, the development of high dielectric constant prepared by first dissolving a polymer resin in a solvent at
materials and the understanding of the behavior of dielectric room temperature with a magnetic stirrer and then mixing
materials under extremely high electric fields are critical for with nanoparticles of 250 vol% in a high-energy sonicator
energy storage applications [5]. In addition, better under- (Sonics & Materials, Inc. Newtown, CT). The films were
standing and control of charge transport cross interfaces solvent cast onto a glass slide and dried at 100 C for two
are crucial for nonlinear devices. The advance in nanotech- hours followed by a vacuum dry at 120 C to 150 C overnight.
nology offers a unique opportunity to engineer materials Ceramic composites were formulated with at least 85 mol%
2 Advances in Materials Science and Engineering

ZnO and other oxide additives. A conventional mixed oxide Relationship between fillers and composite properties
process was used for powder processing. Green compacts of 700 PEI

Composite breakdown strength

Oxide-3
1 diameter were pressed using a uniaxial hydraulic press and 600 Oxide-2 Oxide-4
then sintered at temperatures of 8501000 C. PZ Oxide-1
500
DC breakdown test was conducted following ASTM D149

(kV/mm)
400
(method A) using a ball-plane electrode configuration. The Al
sample was immersed into insulation oil and DC voltage 300
was applied at a ramp rate of 500 V/s until the sample 200
failed. Dielectric responses were measured using a broadband Si
100
dielectric spectrometer from Novacontrol GmbH. Scanning
electron microscopy (SEM) imaging was done using a Zeiss 0
30 <100 200 300 500 720 1400 661
Supra 55VP (Carl Zeiss AG, Oberkochen, Germany). Trans-
Filler breakdown strength (kV/mm)
mission electron microscopy (TEM) imaging was taken using
a FEI Tecnai F20 transmission electron microscope. Figure 1: The breakdown strength of PEI nanocomposites with
various fillers of about 5 wt% loading. PZ stands for lead zirconate.
3. Results and Discussions All polymer films were processed using a solvent cast.

High energy density capacitor dielectrics, field tunable com-

posite dielectrics, and metal oxide varistors (MOVs) are taken procured and mixed with a polymer resin in the wet state.
as examples in this section to demonstrate the achievable Figure 2(c) shows the image of precursor SiO2 particles. After
electrical/dielectric properties via the nanodielectric and performing in situ polymerization of the polyamic acid, a
interface engineering to fulfill the aforementioned develop- polymer nanocomposite containing 5 vol% SiO2 nanoparti-
ment needs. cles was synthesized. Great particle dispersion was achieved
as shown in Figure 2(d). In order to achieve high energy
3.1. Nanofilled Polymer Film for Capacitors. Capacitors rep- density in a nanodielectric composite, a compromise between
resent a big family of non-Faradic energy storage com- increase in dielectric constant and decrease of dielectric
ponents used in applications ranging from decoupling in strength when doing nanodielectric engineering appears to
circuit board to series capacitive compensation banks at be the direction.
power transmission class. The state-of-art polymeric film
capacitors are based primarily on low permittivity polymers 3.2. Field Tunable Nonlinear Composites. The success of nan-
such as polypropylene or polyester. One natural approach odielectric engineering depends on several factors, includ-
for higher energy density capacitor is the synthesis of higher ing (1) higher dielectric constant polymer matrix, (2) high
permittivity composites with higher dielectric strength by permittivity ceramic fillers with low (hysteresis) loss, (3)
incorporating ceramic fillers into polymer matrix. This is proper dispersion, and (4) good interfacing between filler and
because the energy density of a film capacitor takes the simple polymer matrix [8, 9]. This becomes even more critical when
form of 1/2 K2 , where K is the dielectric constant and is the particle polarity is increased resulting in higher dielectric
the dielectric strength of the polymer film. constant. Among the polar ceramic materials are ferroelectric
Although the dielectric constant can be increased to (FE) and antiferroelectric (AFE) particles, whose impact
some extent at higher particle loading level, increasing the on dielectric properties and dispersion are still not well
dielectric strength remains a great challenge. Instead, the understood [9]. Figure 3 shows the increase of the effec-
addition of particles exceeding 10 wt% usually results in tive dielectric constant of nanocomposites from addition of
the considerable loss of dielectric strength of the polymer. particles. Typically, the dielectric constant contrast between
Figure 1 is a graphical comparison of the DC breakdown high- ceramic filler and polymer matrix is so high that the
strength for various nanofilled PEI films. With more con- electric field concentration in polymer phase will reduce the
ductive fillers, lower breakdown strength is not surprising. breakdown strength of the nanocomposites. In addition, high
However, the insulating ceramic fillers of higher breakdown dielectric constant contrast also leads to low electric field
strength do not improve the electrical field endurance of the penetration into the particles and thus the reduced overall
nanocomposites. energy storage density in the composites.
With decreasing particle size, interfacial fraction In order to enable the nonlinear tunability of polymer,
increases and the particle-polymer interface adhesion also we leveraged ferroelectric BaTiO3 and antiferroelectric lead
becomes critical. Poor particle dispersion and interaction zirconate nanoparticles (nPZ). The electric filed tunable
with polymer matrix is shown in Figures 2(a) and 2(b). It behavior of the composites was further studied under high
can be seen that both dry alumina and silica particles are electric fields. The nonlinear dependence of the dielectric
agglomerated and remain to be in poor dispersion even constant of the polymer composites was fully exhibited as the
after mixing using a high energy ultrasonic vibration. The electric field is increased exceeding the coercive field of lead
high surface energy and new chemistry on the nanoparticle zirconate (nPZ) as shown in Figure 4. The higher the electric
surface tend to bond the particles together tightly. field and loading fraction of particles, the higher the dielectric
In order to minimize the particle surface effect, colloidal constant was reached. The field tunable behavior of com-
particles that were already well dispersed in a solvent were posites enabled by the polar particles can be applicable for
Advances in Materials Science and Engineering 3

(a) (b)

(c) (d)

Figure 2: TEM image of 5 vol% nanoparticles dispersing in polymer films. (a) Dry Al2 O3 , (b) dry silica, (c) colloidal SiO2 , and (d) colloidal
SiO2 in a polyimide.

140

120

100
Dielectric constant

80

60

40

20

0
0 20 40 60
BaTiO3 fill loading (vol%)

Silicone (2.7)
High k (19)

Figure 3: The dielectric constant of nanocomposites as a function of volume pertentage loading of BaTiO3 nanoparticle in silicone and
cyanoethyl cellulose with dielectric constant of 2.7 and 19, respectively.
4 Advances in Materials Science and Engineering

Dielectric constant versus electric field nano-AFEs

90

Dielectric constant
60

30

0
0 50 100 150 200
E (V/m)

PVDF
20% NPZ
40% NPZ

Figure 4: Room temperature dielectric constant under an increased electric field. Values were obtained from the hysteresis loop
measurements of a PVDF polymer containing nPZ particles (10 Hz).

Figure 5: TEM image of polyimide containing 15 vol% 40 nm BaTiO3 nanoparticles through in situ polymerization of 2,2-bis[4-(3,4-
dicarboxyphenoxy) phenyl]propane dianhydride (BPADA) with 4,4 -oxydianiline (ODA). Film was solution cast and dried and completely
imidized at elevated temperatures.

various devices such as antenna and phase shifters requiring junctions. However, the underlying oxide processing requires
frequency tunability. A breakdown strength of >300 kV/mm high sintering temperatures (10001300 C) for densification.
was also achieved in the polar nanodielectric composites, As a result, compositional and microstructural heterogeneity
rendering an energy density of up to 15 J/cm3 . and large average grain sizes (typically from a few microns
TEM imaging shows the great dispersion and particle dis- to tens of microns, as shown in Figure 6(a)) as well as
tribution in the polymer achieved using properly processed high porosity caused by exaggerated grain growth during
particles and mixing method (Figure 5). The fractured cross- high-temperature sintering limit the performance of existing
section image of the film reveals only cohesive fracture within MOVs. Also shown in Figure 6, fine microstructures can be
polymer rather than adhesive failure at interface indicating a obtained for nanoenabled MOVs which can be sintered at
strong polymer-particle bonding. reduced temperatures (<1000 C). More varistor junctions in
a unit MOV device can be provided so that higher voltage
3.3. Nanoenabled Nonlinear Resistor (Varistors). High capac- can be applied or smaller device can be fabricated for an
ity, high density power system may be subject to high equivalent voltage requirement.
voltage transients and surge protection devices are widely Higher breakdown voltage (>1 kV/mm) and excellent
used. Compared with other protection devices such as TVS, electrical performance were achieved using the nanopowder
metal oxide varistor (MOV) as an example of ceramic-based precursors, new composition, and sintering profile. The
nonlinear dielectric material at low voltage provides a good electric field dependence of current for the MOV processed
combination of high voltage scalability, peak current car- under different sintering conditions is shown in Figure 7. Not
rying capability, and fast response speed [10]. Nanoenabled only the resistance of the ceramic composites decreases in
dielectric composites were also studied in both metal oxide a nonlinear way with an increase in the electric field, but
varistors and polymer based varistors. MOV is made of bulk also the transition field for the nonlinearity is pushed up
ceramic containing predominate grain-boundary barrier by 10 times. This will enable miniaturization of MOVs and
Advances in Materials Science and Engineering 5

(a) (b)

Figure 6: SEM images of microstructures of a commercial metal oxide varistor (a) and nanoenabled MOV sintered at 850 C (b).

104

60
3
10
Electric field (V/mm)

20
2
10

101

100
1010 108 106 104 102 100
Current density (A/cm2 )
GE nano-MOV
Commercial MOV

Figure 7: Nanoenabled MOVs with higher breakdown voltage after sintering at lower temperatures. The commercial MOVs made of coarse
powder precursors were tested for comparison.

high voltage surge suppression. Besides, when the nano-sized (3) High energy density (15 J/cm3 ) can be achieved in
metal oxide precursors were mixed with polymers to form nanodielectric composites containing nonlinear fer-
composites, the similar - characteristics can be observed. roelectric particles, with proper particle morphology,
The field tuning behavior of the resistance can be fulfilled in dispersion, and particle-polymer adhesion.
the nanodielectric composites.
(4) 10x increase of voltage withstanding capability with
low leakage current and higher nonlinearity can be
4. Conclusions realized in nanoenabled varistors. Refined and uni-
It is demonstrated that novel electrical/dielectric properties form submicron structures can be further explored in
can be achieved via the nanodielectric engineering and polymer based tunable resistors.
interface engineering.
Further optimization of the performance of these electric
(1) Nanodielectric composites can be processed to host
device/component based such principles is undertaken.
variety of ceramic particles and great particle disper-
sion and bonding with the host polymers can be ful-
filled. The loading fraction and particle morphology, Conflict of Interests
however, need to be controlled not to dramatically
lower the dielectric strength. The authors declare that they have no conflict of interests
(2) Electrically tunable composites were processed and regarding the publication of this paper.
a nonlinearly dependent dielectric constant was
demonstrated by mixing polar nanoparticles with Acknowledgment
either low-K polyimide polymer or high-K PVDF
polymers. The challenges are making the composite Part of the work was sponsored by US Department of Defense
tunable at very low electric fields. under Contract of FA9451-08-C-0166.
6 Advances in Materials Science and Engineering

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