INSTITUTE OF PHYSICS PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS

J. Phys. D: Appl. Phys. 38 (2005) 213–222 doi:10.1088/0022-3727/38/2/005

Nanocomposite dielectrics—properties
and implications
J K Nelson and Y Hu
Department of Electrical, Computer & Systems Engineering, Rensselaer Polytechnic
Institute, Troy, NY 12180, USA

Received 29 June 2004, in final form 13 October 2004

Published 6 January 2005
Online at stacks.iop.org/JPhysD/38/213

Abstract
The incorporation of nanoparticles into thermosetting resins is seen to
impart desirable dielectric properties when compared with conventional
(micron-sized particulates) composites. Although the improvements are
accompanied by the mitigation of internal charge in the materials, the nature
of the interfacial region is shown to be pivotal in determining the dielectric
behaviour. In particular, it is shown that the conditions and enhanced area of
the interface changes the bonding that may give rise to an interaction zone,
which affects the interfacial polarization through the formation of local
conductivity.
(Some figures in this article are in colour only in the electronic version)

1. Introduction and background thermally stimulated current measurements, and by changes

The burgeoning application of nanotechnology in the
semiconductor and biological fields was not mirrored in
the field of electrical insulation until quite recently, despite
a forward looking paper by Lewis [1] a decade ago. However,
recent activity in the formulation of nanodielectrics using, in
particular, both thermosetting resins and polyolefins has shown
some significant promise both in terms of the mechanical [2]
properties and when used as electrical insulants [3]. Clays
and inorganic oxides of nanometric dimensions are the most
common particulates used to provide the filler material, but
there is also, for good reason, interest in functionalizing the
particle surface to bring about preferred coupling.
It has been shown [4] that one of the features of such
nanodielectrics is the striking change brought about to the
magnitude and distribution of internal charge associated
with the electrical stressing of these materials. This has
been determined through a pulsed electroacoustic study
of nanomaterials in comparison with the same resin with
the incorporation of the same loading of micrometre-
sized particles. The expected Maxwell–Wagner interfacial
polarization associated with such composite materials
is significantly altered when the particulate dimensions
are reduced to about that of the polymer chain length (and
the concomitant interfacial areas increase dramatically). The
role played by internal charge can be confirmed through the
modification of a space–charge peak (the so-called ρ-peak) in
in dielectric spectroscopy, particularly at elevated temperatures
[4, 5]. What is, perhaps, not so clear is the mechanism by which
these changes take place. However, it is not only the magnitude
and distribution of the internal charge that changes, but there is
also a marked difference in the dynamics involved, particularly
with the charge decay process. As an example, table 1
documents the decay time constants associated with a TiO2 –
epoxy composite system in both micro and nano forms. The
top line provides the decay time constant of charge taken
from a pulsed electroacoustic measurement [4], while the
second line represents a similar time constant extracted from
an electroluminescence experiment [5] undertaken on the
same materials. While the specimen geometry of these two
experiments is different and so comparison cannot be made in
a vertical direction in table 1, nevertheless, the differences
between the nanocomposite and microcomposite in either
experiment are dramatic. Comparison of the values in table 1
in the horizontal direction indicates that both the decay of
Table 1. A comparison of the charge decay time constants in a
TiO2 composite through internal charge and electroluminescence
measurements.
38 nm 1.5 µm
20 ˚C TiO2 TiO2
Charge decay (s) 22 1800
Light decay (s) <60 1200

0022-3727/05/020213+10$30.00 © 2005 IOP Publishing Ltd Printed in the UK 213

J K Nelson and Y Hu
80
70
Nanoparticle counts
60
50
40
30
20
10
0
0 20 40 60 80 100 120
Nanoparticle diameter (nm)
Figure 1. Particle size distribution of TiO2 nanoparticles
determined by transmission electron microscopy.
luminescence and of charge is significantly affected by the
size of the filler particles, and suggests that internal fields are
mitigated for nanoparticle formulations.
2. System studied
The formulation studied here is a TiO2 –epoxy composite which
has been engineered in two forms using micro and nano
particulates. The conventional microparticles have an average
diameter of 1.5 µm and the nanomaterial has the particle size
distribution depicted in figure 1, with a mean size of 23 nm
determined by transmission electron microscopy. Processing
of these materials is critical in order to get proper dispersion of
the filler, cross linking, and avoidance of gaseous inclusions. In
practice, it is found that considerable shear forces are necessary
in order to prevent agglomeration, particularly in the case of
nanoparticles.
The system studied is based on a Diglycidyl Ether-
Bisphenol A (DGEBA) resin (Vantico CT1300) with an amine-
based cross-linking agent (Vantico NY956EN). Nanoparticles
from Nanophase having a purity better than 99.5% are made by
the metal vapour method. They contain 80% anatase and 20%
rutile. Microparticles from Alfa Aesar having 99.5% purity are
also made with a metal based method. The morphology of the
microparticles is rutile according to x-ray analysis. Particles
are dried by heating to 195 ˚C in vacuum for 12 h prior to
mechanically compounding with the resin at 40 ˚C using high
rates of shear. A sonic probe (Sonics ultrasonic processor
Model VC130) is additionally used to alleviate agglomeration.
The composite resin and hardener are then vacuum degassed
for 2 h at 35 ˚C before being mixed and specimens cast
in polished stainless steel moulds as has previously been
described [4]. A cure protocol (48 h at 25 ˚C followed by a
post-cure of 60 ˚C for 3 h) was followed, and the cross-linking
reaction checked with differential scanning calorimetry. This
is particularly important since some properties can be sensitive
to the degree of cross-linking achieved. An example of the
dispersion obtained for a 10% (by weight) microcomposite is
shown in figure 2.
Dielectric spectroscopy measurements were performed on
a Novocontrol Alpha Analyser type K in combination with a
Novocontrol active BDS-1200 sample cell. The sample cell
has a parallel gold plated electrode design. This set-up allows
214
140
Figure 2. Dispersion of 1.5 µm TiO2 particles in epoxy resin.
700
Tip electric field (kV/mm)
600
500 (b)
400
300
200
(a)
100
1 10 100 1000 10000
Life (hr)
Figure 3. The voltage endurance of a 10% (by weight) TiO2 –epoxy
composite in both (a) micro (1.5 µm) and (b) nano (23 nm) forms.
one to measure capacitance in the range of 10−15 –10−10 F,
conductivity up to 5 × 10−15 S, and tan δ down to 10−5 .
Facilities for calibration were used.
Conductivity measurements were performed at room
temperature in a guarded dry air cell. A voltage of up to
30 kV was supplied across the sample under test using a
Hipotronics HV power supply. The current was measured
using a Keithley 485 Picoammeter, which was in series with
the sample. Two opposing plane parallel brass electrodes were
used. The lower electrode was split into a circular measuring
electrode and an annular guard ring, which can effectively
negate the alternate conductive paths. At each voltage level,
the current was allowed to settle for 5 min before the reading
was taken. A compressive load of 104 Pa was applied to the top
plate to ensure a good contact between the metallized sample
and the electrodes. A metal enclosure was also used to cover
the measuring instrument and components under test, which
are connected with shielded cables.
3. Practical measures
It has already been demonstrated [4] that the mitigation of
internal charge provides an enhancement of the short-term
dielectric strength of a filled epoxy resin, and it has recently
also been shown that it is possible to realize strengths that
are greater than those of the base polymer. While the
dielectric withstanding voltage is important, from the industrial
perspective the voltage endurance of the material is perhaps a
more critical parameter. Figure 3 shows the voltage endurance

Discharge Magnitude (pC)
250
200
150
100
50
0
5 6 7 8
Voltage (kV)
Figure 4. Partial discharge characteristics of divergent field gaps in 10% (by weight) TiO2 –epoxy composite in both (a) micro (1.5 µm) and
(b) nano (23 nm) forms.
characteristic of both the micro- and nanocomposites subjected
to long-term endurance tests using a divergent field formed by
moulding an electrolytically etched tungsten point electrode,
having a tip radius of about 4 µm, in a sample exhibiting an
inter-electrode gap of 2 mm. The resulting point-plane gaps
were stressed with a 60 Hz alternating voltage, and figure 3
expressed in terms of the calculated tip stress to minimize
differences between individual point electrodes. At a tip stress
of, say, 200 kV mm−1 , it is evident that the endurance has been
enhanced by 3 21 orders of magnitude.
The partial discharge characteristics on the same system
are allied measurements and are depicted in figure 4. Two
features are clear. First, the discharge inception voltage for the
nanocomposite is enhanced, which is expected on the basis of
the previous electroluminescence characteristics [5] in which
light emission was increased because of the accumulation
of heterocharge in front of the cathode for the micrometre-
sized filler. Second, the magnitudes of discharges are reduced
throughout the voltage range. Both these attributes are clearly
also desirable in the industrial context.
3.1. Free volume
While there are some indications that the enhancement in
the breakdown characteristics for nanocomposites may be
related to the known modification in the internal charge, it
has been postulated that the tethered entanglement associated
with nanocomposites will reduce the polymer free volume [6].
The free volume theory of breakdown [7, 8], which has been
well authenticated for the intrinsic breakdown of polymers,
would then provide an explanation for the improvements
cited. The definition of free volume is somewhat varied.
However, in the context of the Artbauer [7] theory of electric
breakdown, whether it includes nanovoids or artefacts that are
not attributable to the chemical structure, is not important. The
‘loosening’ of the material is the relevant issue.
Free volume measurement [9] by the PVT method was
performed on both the nanocomposite and microcomposite
for the temperature range 300–500 K. The results, as depicted
in figure 5, indicate that, in fact, the opposite is true. The
nanoformulation exhibits an increase in free volume when
compared with the base resin, whereas the micromaterial
does, indeed, show a reduction in free volume. The
data in figure 5 have been shown to be reproducible and
statistical tests show them to be meaningful. The base epoxy
system has a glass transition temperature, Tg , of 63.8 ˚C
determined by differential scanning calorimetry and the
Nanocomposite dielectrics—properties and implications
(a)
(b)
9 10 11
1.04 Relative free volume in epoxy composites
1.02
1.00
hnano/hepoxy
0.98
hmicro/hepoxy
hr(−)
0.96
0.94
0.92
0.9
360 380 400 420 440 460 480 500
T (K)
Figure 5. The relative free volume for TiO2 –epoxy nano- and
microcomposites extracted from PVT measurements [9].
micro- and nanocomposites have a Tg of 73.9 ˚C and 52.4 ˚C,
respectively [4].
The finding of an increase in free volume for
nanocomposites shows that the Artbauer [7] theory cannot
be invoked to explain the properties and suggests that there
must be a more compressible layer or phase associated with
the interfaces where the molecular mobility is higher than in
the bulk. This is supported by photoluminescence data [5],
which indicate that the molecular environment changes in the
presence of sub-micrometre particles. Although these particles
had not been deliberately functionalized, it suggests that there
may be other surface molecules contributing to the effects seen.
Furthermore, it would be expected that the incorporation of
TiO2 particles having a permittivity ≈100 into such a resin
would increase the real part of the relative permittivity through
the Lichtenecker–Rother rule for chaotic mixing. Although
measurements [10] taken for microcomposites do, indeed,
show this effect, dielectric spectroscopy for the nanoparticles
(at frequencies high enough that interfacial and quasi-dc
conductivity effects do not mask the spectra) reproducibly
indicate a reduction in the real part of the permittivity below
that of the base resin when measured at 23 ˚C. This has also
been seen in other systems (such as SiO2 –polyolefin) and is a
clear indication that the large surface areas and higher surface
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J K Nelson and Y Hu

1.2
Uncured epoxy resin
1.1

1.0
0.9

0.8
0.7
Absorbance

0.6
0.5

0.4

0.3
0.2

0.1
-0.0
-0.1
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
2.2 Cured epoxy resin

2.0

1.8

1.6

1.4
Absorbance

1.2

1.0

0.8

0.6

0.4

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)

Figure 6. FTIR spectrum of uncured and cured DGEBA resin.

energy density associated with nanoparticles affect the local NH2-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH2

environment.

Primary Secondary Primary

4. The nature of the interfacial region Amine Amine Amine

4.1. Fourier transformed infra-red measurements Figure 7. Structure of the triethylene tetra amine (TETA).

To trace the chemical changes introduced by particles,
Fourier transformed infra-red (FTIR) spectroscopy was used.
Absorption spectra were obtained on a Magna-IR 560
spectrometer in transmission mode. Potassium bromide
(KBr) pressed pellets were prepared as a carrier for liquid
state resin and hardener. The spectra of composite and
cured resin samples were obtained by using cast thin films
directly.
The base resin (DGEBA), has been well studied and
documented by FTIR [11, 12]. By comparing the spectrum
of the base resin and composites in figure 6, one can
recognize the curing process as the decrease of the intensity
of the characteristic epoxide band [11] at 915 cm−1 and the
increase of the intensity of the characteristic band of C–N
bonds [11] at 1071 cm−1 . The expected increase in the
intensity of –OH groups is difficult to locate. The reason is
related to the structure of the triethylene tetra amine (TETA)
curing agent shown in figure 7 [13]. Among the four reactive
amine groups, the two on the extremities will act as the primary
amines. The two secondary amine groups in the middle will
be less active than the primary. After three steps of the
polymerization reaction as shown in figure 8, only one –OH
group stays on the cross-linked network.
Nanocomposite and microcomposite FTIR spectra are
shown in figure 9. The spectra show two major
differences between the two composites at 600–700 cm−1 and
1050–1150 cm−1 . Around 1070 cm−1 , the nanocomposite
shows two low split peaks in contrast to the single high peak in
the microcomposite. These two split peaks are also observed
in the uncured resin in the same band. This shows that in

216

O OH
R1NH2 + CH2-CH-R2 I R1NH-CH2-CH-R2
Primary amine
R1 O R1
II
NH + CH2-CH-R3
R2-CH-CH2
OH
Secondary amine
III
R 1, R 2, R 3 Carbonyl group
Figure 8. Cross-linking reactions [13].
the nanocomposite, fewer C–N bonds were produced in the
curing process, which implies that the cross-link density in
nanocomposites is less than in the equivalent micromaterial.
Two possible mechanisms can cause the cross-link density
decrease. One is the etherification mechanism [13]. Normally,
if the epoxide ring reacts with the amine group, a three-
dimensional network will be formed with an increase in C–N
bonding. The FTIR spectrum shows that both microparticles
and nanoparticles have –OH groups on the surface [14]. By
adding particles to the polymer, the number of surface hydroxyl
groups in the material is increased. If the concentration
of hydroxyl groups is high enough, the epoxide rings will
open up and react with the hydroxyl groups instead of with
the amine groups. Due to the much larger surface area
of nanometric particles, there will be more –OH groups
at the surface of the particles in the nanocomposite than
in the microcomposite. Another contributing factor to the
surface –OH group is the drying process. As has been
shown by previous thermogravimetric analysis, the dried
nanoparticles may have almost twice the surface –OH group
density than the as-received nanoparticles [14]. As a result,
in the nanocomposite, some epoxide rings will react with
–OH groups at the interface and the cross-link density in the
nanocomposite will be decreased. Besides the etherification, if
the curing agent preferably tends to attach onto the surfaces, a
very thin layer of curing agent will surround the particles. This
may keep the curing agent around the particles from reacting
with the resin. This ‘curing agent concentration’ mechanism
will also decrease the cross-link density.
To elucidate these two mechanisms, an under-cured resin
sample with only 80% of nominal curing agent was prepared.
Nanocomposite dielectrics—properties and implications
Secondary amine
OH
N-CH2-CH-R3
R2-CH-CH2
OH
Tertiary amine
R1-NH-CH2-CH-R2
O-CH2-CH-R3
OH
Ether group
By reducing the curing agent, the cross-link density and C–N
bonding will be decreased leaving some unopened epoxide
rings. Figure 10 gives the FTIR spectrum of the under-cured
resin. Two split peaks were observed at the 1050–1150 cm−1
bands, which is almost the same as in the nanocomposite
case. The similarity between these two cases suggests that
common properties exist in both of them—the decreased cross-
link density and unopened epoxide rings.
Based on the above analysis, the spectrum around
1050–1150 cm−1 appears to be the cross-link characteristic
region. In all the FTIR spectra, the base resin gives the highest
single peak, which indicates the most thorough cross-linking
reaction. The microcomposite’s spectrum shows a lower single
peak, and the nanocomposite’s peak is the weakest and is split.
These findings suggest that both micro- or nano-TiO2 will
affect the cross-link density through the surface –OH groups.
However, due to the huge surface area of nanoparticles, the
–OH group in nanocomposites has a much more significant
influence on the cross-link density. As a result, the network
will be left with unopened epoxide rings.
4.2. Dielectric spectroscopy
As a secondary tool in examining the polymer’s behaviour,
dielectric spectroscopy has been used to provide some insight
into the effects of particles on the network environment.
To complement the FTIR results, dielectric spectroscopy
was applied to nano- and microcomposites, under-cured
resin and normal base resin samples. Measurements have
been conducted at temperatures of 298, 313, 328, 343,
358, 373 and 388 K. Dielectric responses were recorded
in the frequency range 10−4 –106 Hz. Each sample goes
217
J K Nelson and Y Hu

2.8 Microfilled
2.6
2.4
2.2
2.0
1.8
1.6
Absorbance

1.4
1.2
1.0
0.8
0.6
0.4
0.2
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)

2.0 Nanofilled

1.8

1.6

1.4
Absorbance

1.2

1.0

0.8

0.6

0.4

0.2

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)

Figure 9. FTIR spectra of micro- and nanocomposites.

2.2
Under-cured resin
2.0

1.8
Absorbance

1.6

1.4

1.2

1.0

0.8

0.6

0.4

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)

Figure 10. FTIR spectra of under-cured resin.

218

Figure 11. Loss tangent data at different temperatures: (from bottom to top: 25 ˚C, 40 ˚C, 55 ˚C, 70 ˚C, 85 ˚C, 100 ˚C, 115 ˚C, respectively)
(a) 10% nanocomposite, (b) 10% microcomposite.
through the measurement at seven different temperatures.
Multiple samples for each category were made and measured.
The results show good reproducibility at temperatures
below 100 ˚C. Above 100 ˚C, the variance between samples
becomes larger but is still of the same order. Besides the
different dispersion of the particles, the variance at elevated
temperatures could also be associated with the post-cure
process (despite the precautions taken), which is associated
with the –OH group from the particle surfaces as discussed in
section 4.1. It should be noted that the formulation and post-
cure protocols were not the same as those in [10]. In the
low-frequency, high-temperature domain, permittivities rise to
anomalously high values which is consistent with the work of
Griseri [13].
The loss tangent plots in figure 11 show that the
nanocomposite and microcomposite materials have quite
different dielectric behaviour. The loss tangent of the micro-
composite exhibits an increase with frequency without any
noticeable strong dispersion in the mid-frequency range.
The nanocomposite, on the other hand, shows two different
patterns. In the 25–70 ˚C temperature range, the loss tangent
data show a monotonically increasing trend without any
Nanocomposite dielectrics—properties and implications
Table 2. Calculated activation energies.
TiO2 nanocomposite TiO2 microcomposite
Below Tg 1.3 ± 0.1 eV 1.1 ± 0.1 eV
Above Tg 1.8 ± 0.1 eV 2.5 ± 0.1 eV
peaks, whereas above 85 ˚C (i.e. above the glass transition
temperature, Tg ), the loss tangent of the nanocomposite
displays broad peaks, which shift to higher frequencies with
increase in temperature. This indicates that the relaxation
processes involved in nanocomposites above Tg are thermally
activated.
To facilitate analysis, the loss tangent data were grouped
into two categories: below Tg (25–70 ˚C) and above Tg
(85–115 ˚C). The activation energy was calculated by the
normalization method [15] by shifting the frequency spectra
laterally and determining the frequency shift required to bring
the curves into coincidence. Table 2 shows the calculated
activation energy results.
Below Tg , both materials have similar activation energies,
while above Tg the microcomposite shows a much higher
219
J K Nelson and Y Hu
1.E+07
1.E+06
Real relative permittivity
1.E+05
1.E+04
1.E+03
1.E+02
1.E+01
1.E+00
1.E-04 1.E-03
Figure 12. Comparison of the real part of relative permittivity at 115 ˚C.
activation energy. This shows that when the temperature
is above Tg , the nanocomposite network has more mobility
than the equivalent microcomposite. With the free volume
measurement results at the above Tg temperature (see
figure 5), the mobile network activated by the temperature in
nanocomposites can be expected to contribute to the observed
increase of free volume. While the interface interactions
have been approached in section 4.1 from the cross-linking
perspective, there is also increasing speculation that this zone
may also be described in terms of a Gouy–Chapman layer as
discussed in section 5.
As shown in figure 12, the under-cured resin gives lower
real permittivity than base resin. This implies a connection
between the cross-link density and the real part of the
permittivity. In the under-cured sample, due to the insufficient
curing agent, some epoxide rings will be kept. Compared
to the linear C–O–C linkages formed by the opening-up of
epoxide rings, the unopened epoxide rings may be expected
to give a different dielectric response. The decrease in the
number of C–N bonds could also contribute to the lower
permittivity. Similar results have been seen in other epoxy
resin composites [16].
In the nanocomposite, due to the curing agent
concentration around the particles and the large surface area,
there will be a surfeit of unreacted epoxy resin, which would
give rise to the low permittivity observed at room temperatures,
cited in section 3.1. At elevated temperatures the attracted
curing agent around the nanoparticles may be stimulated to
react with unopened epoxide rings. At the same time, the
remaining –OH groups on particle surfaces may also take part
in bonding.
5. Discussion and appraisal
In the partial discharge and voltage endurance tests, the
composites based on nanoparticles clearly showed properties
superior to traditional microcomposites. Combined with the
earlier pulsed electroacoustic (PEA) and electroluminescence
results [10], the improvement shown in the nanocomposite case
appears to be closely related to the control of internal charges
in the bulk. In turn, the mitigation of internal charge normally
associated with interfacial polarization in composite structures
is believed to be related to the interfacial area introduced by
nanoparticles.
220
microcomposite
nanocomposite
base resin
less-cured resin
1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07
Frequency/Hz
Recently Tschope [17] and Lewis [18] have extended
the Gouy–Chapman layer theory to solids. In composites,
an interaction zone can be expected between particles and
the epoxy network. When the particles’ size is reduced to
less than 100 nm, the interface between the particles and their
surrounding becomes very important. For an evenly dispersed
nanocomposite system with uniform sized spherical particles
the interparticle distance, l, can be expressed as

  
4π 1/3
l=r −2 , (1)
3v
where r is the radius of the particle and v is the volume
fraction [19]. The distance between the 23 nm particles for
the 10% nanocomposite would be about 37 nm. This result
suggests that the system is dilute, and there would not be much
overlap between particles or the interfacial regions. However,
as shown in the distribution of particle sizes in figure 1, there
are some large particles with diameters up to 100 nm. In
addition, despite the precautions taken, it is known that there
will be some agglomeration in the bulk resulting in local
overlapping interfacial regions. Indeed, the insensitivity of the
bulk conductivity (see later) to the size of the particles further
confirms that the percolation limit has not been reached. One
may thus speculate that, because these interfacial zones exist
locally, there may be local modifications of the conductivity
without significant changes in the bulk properties, as confirmed
by experimental results [3, 5]. Such local conductivity can
provide paths for charges to move relatively freely along
limited distances, and may provide an explanation for the faster
time response observed in nanocomposites (table 1). This is a
feature of the double layer model proposed by Lewis [18].
Figure 13 shows the comparison of the relative
permittivity between nano- and microcomposites at 115 ˚C. In
the low frequency region, the real and imaginary permittivities
of the nanomaterial are parallel to each other with a slope
of −1 on a log–log plot. This is strong evidence of
a ‘low frequency dispersion’ [15]. This low frequency
dispersion may be regarded as being primarily associated
with charge carriers present in the material with limited
movement. The microcomposite, on the other hand, shows
a real permittivity which has only half the slope of the
imaginary part. One may speculate that this phenomenon
 Nanocomposite dielectrics—properties and implications

1.E+07
nanocomposite-real
1.E+06
nanocomposite-
1.E+05 imaginary
Relative permittivity
microcomposite-real
1.E+04

1.E+03
microcomposite-
imaginary
1.E+02

1.E+01

1.E+00

1.E-01

1.E-02
1.E-04 1.E-03 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07

Fequency/Hz

Figure 13. Comparison of relative permittivity at 115 ˚C.

3.50E-13 1.E+01

Relative permittivity (imaginary)

Volume conductivity (S/cm)

Microcomposite
3.00E-13 Nanocomposite
2.50E-13 1.E+00

2.00E-13

1.50E-13 1.E-01
1.00E-13 nanocomposite
microcomposite
5.00E-14
1.E-02
0% 10% 20% 30% 40% 50%
1.E-04 1.E-02 1.E+00 1.E+02 1.E+04 1.E+06 1.E+08
Loading (% by weight) Frequency

Figure 14. Comparison of volume conductivity as a function of Figure 15. Permittivity comparison at 25 ˚C.
loading.

may also result from the limited conduction associated with between the nanoparticles and the epoxy resin matrix. These
the interaction zones and explain the favourable mitigation bonds between reactive radicals on the particle surfaces and
and relaxation of the internal charge. Lewis [18] has also the epoxy resin are probably the origin of the Gouy–Chapman
pointed out that the observed unusual high permittivity of layer. This would be consistent with the observed differences
nanocomposites at low frequencies would result from an out- in the cured structure for the nanocomposite indicated by the
of-phase dipole moment developed by the charges accumulated FTIR results. However, it has become clear that these interface
at the particles’ poles. Such augmentation of the permittivity regions are pivotal in determining the dielectric properties of
would create values substantially greater than those derived nanodielectrics, and dominate by virtue of the large interfacial
from a Maxwell–Wagner theory alone. areas involved.
A bulk dc-conductivity measurement was also undertaken
to study the effects of the local conductivity on the bulk Acknowledgments
material. The experimental method is introduced in section 2.
The results are shown in figure 14. At all the tested The authors are indebted to Drs L Schadler, R MacCrone,
loading levels, the nanocomposite has slightly lower bulk C W Reed and L Utracki who have contributed to this work in
conductivity than the microcomposite. This result is consistent
numerous different ways.
with the dielectric measurement result at 25 ˚C, in which
the nanocomposite has a lower imaginary permittivity than the
microcomposite as shown in figure 15. The results indicate References
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