The Impact of Nanocomposite Formulations on Electrical Voltage Endurance
J. K. Nelson and Y. Hu
Department of Electrical, Computer and System Engineering
Rensselaer Polytechnic Institute
Troy, NY, 12180
E-mail: nelsoj@rpi.edu
Abstract: Previous work in which a conventional
micron-sized filler was replaced by nanomaterials in an
epoxy matrix has shown significant, and encouraging
enhancements in the electric strength of the composites.
The advantages gained were associated with the
mitigation of Maxwell-Wagner polarization and the
internal associated space charge, and an optimum
particulate loading established. This contribution seeks
to extend the previous work, by examining the
electrical voltage endurance and partial discharge in a
divergent field geometry. The voltage endurance tests
demonstrate that significant improvements in
endurance are also indicated. Similar results are seen in
the partial discharge measurements. In order to gain a
mechanistic understanding, the same electrode
configuration has also been subjected to
electroluminescence experiments in which both the
steady-state and temporally-resolved light emission has
been compared in these materials. Changes in the
magnitude and onset field of the emission suggest that
both the enhanced scattering of the nanocomposite and
the mitigation of internal charge play a pivotal role in
the enhanced voltage endurance obtained. Microscopy,
dielectric spectroscopy and free volume measurements
are also introduced to provide insight into the possible
underlying mechanisms involved.
INTRODUCTION
In earlier work [1], the dielectric properties of
nanofilled epoxy resin were documented. Compared to
an equivalent micro-filled composite, nanofilled resin
has shown superior electric strength characteristics.
The experimental results suggest that when the particle
size becomes comparable to the size of polymer chain,
the particles act cooperatively with the host matrix and
mitigate the interfacial polarization effects. The
nanofilled epoxy resin also gave quite a different pulsed
electro-acoustic response compared to microfilled resin.
Following the encouraging results of Henk et al. [3],
this contribution examines the impact on the very
practical issue of voltage endurance of such systems.
The associated partial discharge characteristics are also
investigated in an attempt to throw some light on the
underlying mechanisms. Electroluminescence and other
measurements are also carried out on the same
configuration in order to advance the discussion of the
underlying phenomena observed.
SAMPLE FORMULATION
The material used in this investigation was a Bisphenol
A epoxy (Vantico CY-1300 + HY 956) with 23 nm and
1.5 ìm TiO 2 particles incorporated in the host matrix to
form nano- and micro-composites respectively. As
indicated in previous work [1,2], the approximate
optimum loading of 10% by weight was chosen. For
this study of voltage endurance, the investigation was
carried out with a needle-plane electrode arrangement
to achieve a high divergent field. Needle electrodes
having a well-characterized tip radius of about ~4 ìm
were etched from 1 mm diameter tungsten rod by
sodium-hydroxide solution. Each needle tip was
examined, measured and documented by a
camera-equipped microscope before being molded into
the samples. The gap distance between the needle tip
and the plate was adjusted to 2 mm.
EXPERIMENTAL RESULTS
Voltage Endurance
Voltage endurance measurements have been performed
under 60Hz AC conditions. Due to the stochastic nature
of endurance experiments and the inevitable variation
between individual samples, the sample processing was
undertaken with great care to minimize the difference
from sample to sample. The experiment was carried out
700
Tip Electric Field
600
500 (a)
(kV/mm)
400
300
200 (b)
100
1 10 100 1000 10000
Life (hr)
Fig. 1. Voltage endurance characteristics for epoxy-TiO2
nanocomposites. (a) Nanofilled; (b) Microfilled
at different voltage levels. At each voltage level four
samples were tested simultaneously. The choice of four
samples is a compromise between accuracy and
expediency.
Fig. 1 depicts the life for nano- and micro- composites
as a function of the maximum field at a TiO2 loading
of 10% by weight. The tip field in Fig. 1 is that
calculated at the individual tip based on [4]
2V
E=
rln (4d / r )
where r is the tip radius and d is the inter-electrode gap.
The enhancement brought about by the nano-sized
filler is clear and very significant improvements in
endurance can be seen in the lower field regions which
are representative of working stresses in practical
apparatus. For example, at the tip field of 100 kV/mm,
the extrapolated life of the nano-composite will be
about 10,000 times longer than that of the conventional
micro-composite. This encouraging result shows
significant promise for the practical application of
nanodielectrics.
Partial Discharge
In order to gain a better understanding of the aging
process of both the systems, partial discharge
measurements were undertaken. Fig. 2. depicts the
nano- and micro-composite partial discharge
characteristics as a function of voltage and has been
Discharge Magnitude (pC)
250
200
150 (b)
100
50
0
-50 5 6 7 8 9
Voltage (kV)
Fig. 2. Partial discharge behaviour. (a) Nanofilled;
(b) Microfilled.
found reproducible with different specimens. The
voltage was applied to the samples with a standard
protocol (steps of 500V every two minutes).
The two systems again show different behaviour. The
nanofilled resin has a higher inception voltage of ~7.5
kV when compared with the conventional material
exhibiting about 6 kV which suggests that the
Coulombic electric field is different. It is also evident
that, for the same voltage level, nanocomposites have a
lower discharge magnitude. Furthermore, with
increasing voltage the microcomposite gives a faster
increase in the discharge magnitude. These features are
consistent with the enhancements in endurance seen in
Fig. 1., and would appear to be a general characteristic
of nanocomposites [3].
Electroluminescence
(1) In an attempt to further understand the voltage
endurance results, sensitive electroluminescene studies
have been carried out (both static and dynamic) for the
same geometrical configuration using an EMI 8789QB
13-dynode photomultiplier operating in scintillation
counting mode. Comparative electroluminescence onset
fields are shown in Fig.3. which again suggests that it
is not the geometrical (Laplacian) field that is
responsible for the light onset. The onset field of
nano-filled epoxy of 400kV/mm is more than two times
that of the micro-filled epoxy (178kV/mm) and the base
resin which are indistinguishable.
Further insight has been obtained by examining the
1200
Light Output (Arb. units)
Onset for base resin
1000
and M icrocomposite
800
600
400
200
Nanocomposite
onset
0
0 200 400 600 800 1000
Tip field (kV/mm)
Fig. 3. Electroluminescence onset field
(a)
transient emission during a stepwave application of
voltage. Fig. 4. provides such a comparison for the
10 11 micromaterial in (a) and the nano equivalent material
in (b). Under the application of high field (above the
electroluminescence onset level), light output of the
nano-filled epoxy immediately rose to its peak value
and then decayed over time, while light from the
micro-filled resin progressively increased until a
steady-state level was attained. On removal of the
energization, the light from nano-filled resin
disappeared within 2 minutes, while that from
micro-filled lasted much longer, approximately for 40
minutes. This gives a strong indication that dramatic
differences in the internal charge behaviour exist
between nano- and micro- composites.
Pulsed Electroacoustic Study
The internal charge distribution in rutile composites
 Light output (Arb.
2000
1500
units)
1000
500
On Off
0
0 100 200
Time (mins)
Light Output (Arb.
1500
1000
units)
500
On
0
0 50 100 150
Tim e (mins)
Fig.4. Electroluminescence time response (a)
micromaterial, (b) nanomaterial
has been studied by Nelson et al. [1] using a pulsed
electroacoustic technique (PEA) on laminar samples
subjected to 3 kV steady DC fields. The result shows
that after several hours of stressing, the micro- and
nano-filled resin exhibit significant changes in the
internal space charge and electric field. For the
nanofilled resin, homocharge accumulated near the
electrode, while in the microfilled case, heterocharge
built up in front of the cathode and substantially
augmented the field above the nominal (Laplacian)
value.
DISCUSSION AND APPRAISAL
The improvement in electrical properties in divergent
fields (voltage endurance and partial discharge)
strongly suggests that internal field modification is, at
least, a contributing factor. The dynamic response of
the different materials in the electroluminescence
measurements also implies significant differences in
the space charge behaviour. In base resin and
nanocomposite, charge injection and accumulation in
the tip vicinity was dominated by homocharge as has
been confirmed by PEA studies [1]. As the space
charge built up, it reduced the local field near the tip,
thus reducing the light output. The reduction in local
field continues until the charge injection and charge
migration reach a balance when the system is in an
equilibrium state. On the contrary, for the micro-filled
resin, the accumulation of space charge near the tip was
of the opposite sign, which enhanced local field and
increased electroluminescence output until it reached a
steady state. The times to reach equilibrium for all
three samples appeared similar (30-60 minutes).
However, the time for the microcomposite to reach the
steady state after the field was removed was apparently
(a) much longer than those for the base resin and
nanocomposite. Once again, this points to the
likelihood of interfacial polarization associated with the
interfaces presented by the micron-sized particulates,
and clearly shown in the micrograph of Fig.5. This
would be consistent with the development of the
300 heterocharge shown in [1] from pulsed electroacoustic
measurements.
(b)
Off
200
Fig. 5. Photomicrograph showing interfaces
formed by embedded microparticles
By reducing particle size to nanometric dimensions, the
interface area between the particles and the polymer
will increase dramatically. Assuming particles have a
diameter D and are dispersed uniformly in the bulk,
then, each particle has six nearest neighbours at a
volumetric filler-loading fraction, f. Using the ball
model of Henk et al. [3] we can calculate the
polymer/particle interface area per unit volume:
6f
Interface area = (2)
D
Calculation for D = 23 nm and f =0.03 (10% nanofilled
epoxy by weight) gives an area of 7.8 km2m-3, while the
10% filled microcomposite with the particles of 1.5 ìm
diameter has an interface area of 0.11 km2m-3, which is
considerably smaller.
It is suggested that nano-sized filler can greatly
mitigate the significant interfacial polarization -
Maxwell-Wagner effect, which is a general
characteristic for conventional fillers. When the filler
size is reduced to the nanoscale, the mobility and
conformation of the matrix near the particles can be
significantly changed. The interactions between the
particles and polymer matrix near the surface of the
particles cause a layer to be established, which is the
“interaction zone” [5]. Due to the large surface area of
nanoscale particles these interaction zones in the
nanocomposite are much more extensive than in a
microcomposite. Sternstein and Zhu [6] pointed out
that nanoscale particles could enhance the chain
entanglement near the fillers, which is reflected on the
viscoelastic behaviour of the composites. This
phenomenon shows the environment change brought by
the nanoparticles that has also been suggested by red
shift in the wavelength measured during
photoluminescence studies [1].
Overlapping of the interaction zones form bridges
between the particles and will create a substantially
different environment from the rest of the matrix.
Recently, Tschope has applied the Gouy-Chapman
model to the solid phase and proposed a space charge
model [7]. In his model, space charge layers in certain
directions can form paths of high conductivity. These
local short circuit paths could be responsible for the
time response of the field switch-off observed here in
the electroluminescence measurements. Due to the local
short circuit paths, the expected recombination of space
charges in a nanocomposite could be accomplished
much faster. Additionally, the very large surface area
associated with nanocomposites may also accentuate
the effects of end-functionalized polymers adsorbed
onto the surface of the particles [5]. If the curing agent
is preferentially adsorbed onto the filler surface, this
could form a region around the particles having a lower
cross-link density than the rest of the matrix. In this
way, the interaction zone may be characterized by a
very different mobility.
Until recently, the authors had assumed that some of
the electrical property enhancements associated with
nanofillers accrued from an assumed reduction in free
volume [6]. However, recent PVT measurements
taken at the National Research Council of Canada on
this nanocomposite system point to an increase in free
volume. Relative free volume (defined as
hcomposite / hepoxyre sin , where h is the computed free
volume value) decreased by the addition of micro-sized
TiO2 (-6 to -9%), but increased by the incorporation of
nano-sized TiO2 (+2 to +3%). A similar result is seen
in epoxy silicate nanocomposites [8]. This result
suggests the presence of a highly mobile interlayer
between the filler and the matrix that would seem to be
the key to the enhanced voltage endurance and other
property changes seen. In this context, it is instructive
to examine the changes in relative permittivity for the
system depicted in Table 1. taken at 1 kHz, 23 ºC.
While it is clear that the incorporation of rutile (år
100) of micron dimensions has increased the
permittivity of the base resin as would be expected (and
can be predicted based on chaotic mixing), the
nanofiller has resulted in an anomalous reduction in
permittivity suggesting that there has been some
impairment of dipole movement at the interfaces;
perhaps resulting from -OH group bonding. This again
points to the modification of the local environment.
Table 1. Permittivity of TiO2 composites
Rel. Permittivity, år
Base resin 5.68
10% Micro TiO2 (Measured) 6.01
10% Micro TiO2 (Calculated)* 6.19
10% Nano TiO2 (Measured) 4.5
* based on the Lichtenecker-Rother law for chaotic mixing
In summary, one may speculate that the primary action
in improving voltage endurance is to reduce the
internal charge responsible for aging through
interfacial effects. If, indeed, this interaction zone is the
primary agency in determining electrical behaviour,
then clearly the engineering of nanodielectrics should
be centered on chemical modifications of the interface.
ACKNOWLEDGEMENTS
The authors are indebted to Prof. J. Fothergill, Dr. L.
Utracki and Mr. J. Thiticharoenpong who all
contributed to this work in different ways.
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