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1484 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.

24 Cooperative Test Results

Dielectric Properties of XLPE/SiO2 Nanocomposites


Based on CIGRE WG D1.24 Cooperative Test Results
Toshikatsu Tanaka Alexander Bulinski Jrme Castellon
Waseda University National Research Council Canada Institut dElectronique du Sud
2-7 Hibikino, Wakamatsu-ku 1200 Montreal Road, M-58 University Montpellier 2
Kitakyushu, 808-0135 Ottawa, Ontario, K1A 0R6 34095 Montpellier Cedex 5
Japan Canada France

Michel Frchette Stanislaw Gubanski Josef Kindersberger


IREQ Chalmers University of Technology Technische Universitt Mnchen
1800 boul. Lionel-Boulet Hoersalsv. 11 Arcisstrasse 21
Varennes, Qc J3X 1S1 412 96 Gothenburg 80333 Mnchen
Canada Sweden Germany

Gian Carlo Montanari Masayuki Nagao Peter Morshuis


Universit di Bologna Toyohashi University of Technology Delft University of Technology
Viale Risorgimento 2 Tempaku, 2600 GA Delft
40030 Bologna Toyohashi, 441-8580 The Netherlands
Italy Japan

Yasuhiro Tanaka Serge Plissou Alun Vaughan


Tokyo City University IREQ University of Southampton
1-28-1 Setagaya-ku 1800, boul. Lionel-Boulet Southampton SO17 1BJ
Tokyo 158-8557 Varennes (Qubec) UK
Japan Canada J3X 1S1

Yoshimichi Ohki Clive W. Reed Simon Sutton


Waseda University 116 Woodhaven Drive and Suh Joon Han
3-4-1 Ohkubo, Shinjuku-ku Scotia, New York 12302 Dow Chemical Company
Tokyo 169-8555 USA Kingsbury Crescent
Japan Staines TW18 3AG
UK

ABSTRACT
A comprehensive experimental investigation of XLPE and its nanocomposite with fumed
silica (SiO2) has been performed by CIGRE Working Group D1.24, in cooperative tests
conducted by a number of members; covering materials characterization, real and
imaginary permittivity, dc conductivity, space charge formation, dielectric breakdown
strength, and partial discharge resistance. The research is unique, since all test samples were
prepared by one source, and then evaluated by several expert members and their research
organizations. The XLPE used for preparation of the nanocomposites was a standard
commercial material used for extruded power cables. The improved XLPE samples, based
on nanocomposite formulations with fumed silica, were prepared specifically for this study.
Results of the different investigations are summarized in each section; conclusions are given.
Overall, several important improvements over unfilled XLPE are confirmed, which augur
well for future potential application in the field of extruded HV and EHV cables. Some
differences/discrepancies in the data of participants are thought to be the result of
instrumental and individual experimental technique differences.
Index Terms Nanocomposite, XLPE, fumed silica, nano filler, characterization,
dielectrics, electrical insulation, dielectric performance, cooperative test

Manuscript received on 2 June 2011, in final form 20 July 2011.

1070-9878/11/$25.00 2011 IEEE


IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1485

1 INTRODUCTION IEEE ICPADM, and ISEIM. Work on PE nanocomposites


have predominated; with relatively few papers on XLPE
NANOCOMPOSITE materials have recently emerged as nanocomposites. Hence, we focused attention to XLPE/SiO2
dielectrics and electrical insulation. In particular, much work nanocomposites of the current work. The following references
has been done on nanocomposites from thermoset epoxies. to PE nanocomposite work cited below are: characterization
Nanocomposites from thermoplastic polymers such as [3-9; 22-26]; permittivity and dielectric loss [10-11; 27-43];
polyethylene, ethylene vinyl acetate, polypropylene, electrical conductivity [12-14; 44-56]; space charge [15-18;
polyimide, and silicone are also targets of research. 57-83]; dielectric breakdown [19-20; 84-98]; treeing [21; 99-
Polyethylene (PE) has long been used as extruded cable 109]; partial discharge resistance [110-115], and related topics
insulation; for HV and EHV cables, primarily as chemically [116-120].
cross-lined polyethylene (XLPE). The latter material has
received significant attention because of the large reduction in Polymer nanocomposites, of which XLPE/SiO2 is but one
space charge when relatively low levels (2-10 %) of inorganic example, are envisaged to combine the best properties of the
nanofillers are added. For this reason, both PE/MgO and filler inorganic nanoparticles with the processing versatility of
PE/SiO2 nanocomposites have been closely investigated; to- different polymers, via the dominance of the extensive
date, however, there has been relatively little work published interface regions; ending with enhanced, sometimes
on XLPE nanocomposites. synergistic or unique, properties.

A comprehensive experimental investigation of Objectives of the present paper are:


nanocomposites of XLPE with fumed silica (SiO2) was (1) To describe the range of dielectric properties of
performed by CIGRE Working Group D1.24, in cooperative XLPE/SiO2 nanocomposites prepared from commercial-
tests performed by a number of its members. The work covers
grade XLPE provided by one source.
materials characterization, real and imaginary permittivity, dc
conductivity, space charge formation, dielectric breakdown, (2) To recognize and analyze differences/ discrepancies in the
and partial discharge resistance. The research is unique, since results of participants.
all plaque test samples were prepared by one source and then (3) To derive conclusions on the effects of nano filler
evaluated by several expert members and their research inclusion on the dielectric properties of XLPE/SiO2
organizations. The XLPE used for preparation of the nanocomposites.
nanocomposites was a standard commercial material used for
extruded power cables. The improved XLPE samples, based 2 MATERIALS
on nanocomposite formulations with fumed silica, were 2.1 AS-RECEIVED SAMPLES
prepared specifically for this study. Three materials were Three types of samples were prepared for the CIGRE
compared in the investigation: unfilled XLPE, XLPE filled Working Group D1.24 study by the Dow Chemical Company
with 5 % non-functionalized fumed silica nano-filler, and based on a standard commercial grade cross-linked
XLPE filled with 5% functionalized fumed silica nano-filler. polyethylene (XLPE) with the base resin from a high pressure
All samples were heat-treated prior to experiments in LDPE reactor:
accordance with a set procedure. Overall, several important
improvements were exhibited by XLPE with fumed silica Unfilled XLPE
nanofiller over unfilled XLPE, auguring well for future XLPE with 5 % unfunctionalized nano-silica
potential application in the field of extruded HV and EHV
cables. It is noted that the formulations used for this XLPE with 5 % functionalized nano-silica
investigation, using 5% fumed silica nanofiller, were chosen
The high purity silica filler was a stoichiometric silicon
as a representative formulation that is not necessarily
dioxide (SiO2) prepared by a fuming process; hereafter
optimized. Some differences in the data of some participants
referred to as silica filler. The average primary particle size
are thought to be the result of instrumental or individual
was about 12nm and the BET surface area was estimated to be
experimental technique differences.
about 200 m2/g. The surface of the nano-filler was
Prior to the current investigation, CIGRE Working Group functionalized by a specific chemical coupling agent, selected
D1.24 examined the broad field of polymer nanocomposites to improve dispersion in the polyethylene.
and their potential application to the field of high voltage
Compounding of either filler into the polyethylene was
equipment. The work, covering material characterization,
carried out in an intensive compounding mixer in a manner to
dielectric and electrical properties, and assessment of
maximize dispersion and minimize aggregation of the nano
application potential, is recorded in two recent CIGRE
silica particles. The nano silica was dispersed in the
publications: Technical Brochure No. 451 [1] and Electra No.
polyethylene before the addition of the cross-linking additives.
254 article [2]. Comprehensive fundamental studies of the
Plaques were prepared by hot pressing the appropriate
dielectric and electrical insulation properties of thermoset and
quantity of pellets in a 200 mm x 200 mm x 1 mm mold.
thermoplastic polymer nanocomposites have also been
published over the past decade in the DEIS Transactions on Molded samples were initially held at 120 C for 10 minutes
Dielectrics and Electrical Insulation and presented at in the press, to allow uniform flow in the plaque mold for,
conferences such as IEEE CEIDP, IEEE ICSD, IEEE ISEI, followed by cross-linking fully at 180 C for 30 minutes.
1486 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

Plaque samples were removed from the press and cooled to 3 MATERIAL CHARACTERIZATION
room temperature.
3.1 SEM AND TEM OBSERVATION
2.2 HEAT-TREATMENT OF AS-RECEIVED SAMPLES The distribution of filler particles was examined by scanning
FOR REMOVAL OF CROSS-LINKING BY-PRODUCTS electron microscopy (SEM). For such materials, the optimum
The three XLPE materials used for cooperative tests are approach to a full morphological study would involve
shown in Table 2.1. XLPE stands for cross-linked microtomy, permanganic etching, replication and examination
polyethylene. Nominal thickness of all samples of such in the TEM (transmission electron microscope). However,
materials is 1 mm. Samples 1, 2 and 3 were provided by the since the principal objective of this study is to explore the
Dow Chemical Company, while samples H1, H2 and H3 were distribution of the filler rather than to explore both this and
heat-treated in each laboratory of the participants after they the morphology of the XLPE SEM examination was used in
received original samples. place of the much more difficult and costly option of TEM.
XLPE contains little in the way of large-scale morphological
Table 2.1. XLPE and XLPE nanocomposite specimens of 1 mm thickness features, as shown in Figure 3.1.
prepared for tests.
Name Material
Sample 1 Base XLPE
Sample 2 XLPE filled with 5 wt% non-functionalized
silica nano filler
Sample 3 XLPE filled with 5 wt%
functionalized silica nano filler
Sample H1 Heat-treated Sample No.1.
See conditions in Table 2.2.
Sample H2 Heat-treated Sample No.2.
See conditions in Table 2.2.
Sample H3 Heat-treated Sample No.3.
See conditions in Table 2.2.

Table 2.2. Vacuum heat treatment conditions for as-received XLPE and
XLPE nanocomposites samples.

Temperature Duration Test Participants


60 C 7 days Castellon, Gubanski, Nagao,
Ohki and T. Tanaka
60 C 8 days Pelissou
80C 12 h Y. Tanaka
80C 5 days Montanari
80C 7 days Ohki and T. Tanaka
As-received XLPE samples contain residual cross-linking
by-products such as acetophenone, cumylalcohol and even Figure 3.1. SEM micrograph showing the typical morphology of a peroxide
crosslinked XLPE (etched, replicated surface).
moisture in nature. In order to obtain proper characteristics of
base XLPE and nanocomposite XLPE materials, it is
To examine the microstructure of each material system,
necessary to remove them by heating in vacuum. Table 2.2
internal surfaces were exposed by ultramicrotomy using an
shows conditions for heat treatment of as-received samples. It
RMC MT-7 system fitted with an RMC CR-21 cryo-stage.
was suggested that they should be conditioned at 60 C for a
These were then etched using a 1 % solution of potassium
week, as a default procedure. Conditions are somewhat
permanganate dissolved in an acid mix containing 5 parts
different from each of the experimenters as shown in Table
sulphuric acid, 2 parts dry orthophosphoric acid and 1 part
2.2. During pre-experimental stage, 80 C were selected as
water, using standard permanganic etching and recovery
some of the experimenters considered it appropriate to obtain
protocols [121, 122]. Finally, the etched samples were
more representative characteristics.
mounted onto aluminum SEM stubs, sputter coated with gold
It should be noted that the maximum permissible operating and examined in the SEM. As anticipated, the etched
temperature of the conductor of an XLPE insulated power unfilled sample of XLPE showed no significant
cable is 90 C which is higher than that of paper, PVC and PE morphological features when examined by SEM and,
insulated power cables. This temperature was taken into therefore, no images are included here. Figure 3.2 below
consideration to perform heat treatment of as-received XLPE shows representative micrographs of the XLPE specimen
specimens. Therefore, it can be said that temperatures like 60 containing the untreated nano filler. From both these images
and 80 C are in the safety margin. it is evident that the filler particles span a wide size range
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1487

~300 nm 30 Pm are visible here), but that they are


uniformly distributed throughout the material. The large
objects appear to be just filler particles rather than
aggregates of smaller particles. Information concerning the
size distribution of the filler particles used to prepare this
material would be useful. Similar images for the XLPE
containing the treated filler particles (Sample 3) are shown in
Fig. 3.3. These appear equivalent to those in Fig. 3.2,
although perhaps, the distribution of particle sizes appears
displaced somewhat to smaller dimensions.

(a)

(a)

(b)
Figure 3.3. SEM micrographs of etched surfaces of the XLPE containing the
treated nano filler (Sample 3).

3.2 DSC MEASUREMENT


The melting behavior of the XLPE samples was determined
by differential scanning calorimetry (DSC), using a Perkin
Elmer DSC7 system running Pyris software. All melting traces
were obtained at a heating rate of 10 K min-1 following
calibration of the instrument using high purity indium. Figure
3.4 shows melting traces of the as-received materials. All
materials exhibit a simple melting transition at a temperature
(b) that is typical of a peroxide crosslinked, low density
Figure 3.2. SEM micrographs of etched surfaces of the XLPE containing the polyethylene [123]. Although there is negligible difference
untreated nano filler (Sample 2).
between the peak enthalpies of the three materials, indicating
Although permanganic etching followed by SEM is not an comparable degrees of crystallinity, it is evident from these
appropriate way to study the morphology of materials which data that both of the nanocomposites (Samples 2 and 3) melt at
contain lamellae that are as small and defective as those in a significantly lower temperature (102 C) than the equivalent
XLPE, the above images demonstrate that the technique is unfilled system (104 C). A number of explanations can be
highly effective at revealing the location and size distribution proposed for this, including reduced lamellar thickening
of filler particles in nanocomposites. Both of the during the initial phases of crystal formation or reduced
nanocomposite systems shown here contain aggregates of lamellar reorganization during the DSC scan. Previous studies
silica with dimensions of the order of micrometres, together of semicrystalline polymers containing nanofillers have
with a wide spectrum of particle sizes within the sub- demonstrated that interactions between the two components
micrometre range. can affect the behavior of the polymer as it crystallizes in
1488 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

complex ways. For example, in the case of systems based


upon montmorillonite (MMT), evidence exists to suggest that
the presence of this nanoclay can inhibit the formation of
crystalline structures in polymers as different as Nylon and
polyethylene [124, 125]. Conversely, Hu and Lesser [126]
have reported that, while MMT serves to reduce molecular
dynamics in poly(trimethylene terephthalate), an increase in
the enthalpy of crystallization nevertheless occurs. In short, 300 min Annealing
the fact that the addition of a nanofiller results in modified
melting behavior of the host polymer is not, in itself,

Endothermic
surprising and is most likely related to some
polymer/nanofiller interaction. 100 min Annealing

30 min Annealing

10 min Annealing

0 min Annealing

40 60 80 100 120 140


o
Temperature / C
Sample 1
(a)

0.10

Increasing annealing time


-1
Heat flow difference / W g

0.05

0.00

-0.05

Figure 3.4. DSC melting traces of the three material systems, as received.
-0.10
During the peroxide crosslinking process, small molecular 40 60 80 100 120
by-products are generated, which should be removed prior to o
analysis of the samples. While this can be readily achieved by Temperature / C
thermal treatment in vacuum, such a process also has the (b)
Figure 3.5. DSC melting data showing the effect of annealing on the lamellar
potential to affect the morphology of the polymer. population of the unfilled XLPE sample (Sample H1): (a) DSC melting traces
Consequently, a series of cyclic annealing experiments were (b) heat flow difference traces obtained by subtracting the melting endotherm
conducted to explore the extent and kinetics of annealing. obtained with no annealing from that of each of the annealed specimens.

Figure 3.5a shows that annealing the unfilled XLPE at 60 C Figure 3.5b shows that the magnitude of the annealing peak
(Sample H1) results in the formation of a shoulder at ~70 C, increases monotonically with annealing time in an
which progressively increases in size with annealing time; approximately logarithmic manner. While it is difficult to
from this figure, it would appear that the majority of annealing envisage this continuing indefinitely, the above clearly
is complete within about 60 min. However, subtracting the indicates that this process continues for an extended period of
melting curve obtained from the non-annealed sample (Sample time. However, the fraction of material that is affected is
1) from each subsequent melting trace reveals a rather relatively small, suggesting that such annealing protocols do
different picture. not have a major influence on the morphology of the polymer.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1489

3.3 GAS-CHROMATOGRAPHY SPECTRA


[u105] 2.5
D-methylstyrene
2
[u10 ] 2.5
5

Abundance
2 1.5
Acetophenone Butylated Hydroxytoluene
Abundance

D-methylstyrene
1.5 1
Butylated Hydroxytoluene
0.5
1
Tetradecane
Acetophenone 0
0.5 11 12 13 14 15 16 17 18
Time [min]
0
11 12 13 14 15 16 17 18
Time [min] (a) As-received Nano-Filled XLPE (Sample 2)
(a) As-received XLPE (Sample 1)

[u105] 2.5
[u105] 2.5 2
D-methylstyrene

D-methylstyrene

Abundance
2
1.5 Butylated Hydroxytoluene
Abundance

1.5 Butylated Hydroxytoluene


1

1 0.5
Acetophenone
0.5 0
11 12 13 14 15 16 17 18
0 Time [min]
11 12 13 14 15 16 17 18
Time [min] (b) Heat-treated Sample H2 (60 C) (Sample H2)
(b) Heat-treated XLPE (60 C) (Sample H1)

[u10 ] 2.5
5
[u105] 2.5
Butylated Hydroxytoluene Butylated Hydroxytoluene
2
2
Abundance
Abundance

1.5
1.5
1
1
0.5
0.5
0
0 11 12 13 14 15 16 17 18
11 12 13 14 15 16 17 18 Time [min]
Time [min]
(c) Heat-treated Sample 2 (80 C) (Sample H2)
(c) Heat-treated XLPE (80 C) (Sample H1)
Figure 3.7. Gas-chromatography spectra for XLPE filled with non-
Figure 3.6. Gas-chromatography spectra for unfilled XLPE. functionalized nano filler.
1490 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

3) contain cross-linking by-products. After heat treatment at


[u105] 2.5
60 C for a week, they are still present. Heat treatment at 80
D-methylstyrene C for a week leads to disappearance of almost all by-
2
products. It can be derived from the above figures that cross-
Abundance

linking residues diminish by heat treatment at 80 C for a


1.5 Tributyl phosphate
week in vacuum. Temperature 60 C is inadequate. But it
Butylated Hydroxytoluene should be noted that it depends on how sensitive a specific
Acetophenone
1 performance such as tan and space charge is to their
remaining content.
0.5
3.3 EVALUATION OF RESIDUES ON PD ERODED
0 XLPE NANOCOMPOSITE WITH RAMAN
11 12 13 14 15 16 17 18
MICROPROBE SPECTROSCOPY
Time [min]
(a) As-received XLPE filled with functionalized nano filler Many studies have reported that the inclusion of nano filler
(Sample 3) serves to reduce damage to insulator surfaces caused by
localized electrical activity, i.e. partial discharges (PDs).
Maity et al. [127], for example, studied the degradation
[u105] 2.5 behavior of epoxy/metal-oxide nanocomposites and showed
D-methylstyrene that degradation was reduced for the filled epoxy specimens
2 compared with unfilled ones. They also proposed a
mechanism for this effect, which was based upon the idea
Abundance

1.5 that the polymer resin is eroded by PDs, to leave behind a


Butylated Hydroxytoluene nanoparticle rich surface layer which is resistant to further
degradation. Since silica exhibits characteristic Raman bands
1 around 500 cm-1 [128], where the spectrum of polyethylene
is devoid of features [129], the effect of PD aging on the
0.5 three material systems was examined using confocal Raman
microprobe spectroscopy.
0
11 12 13 14 15 16 17 18
Time [min]
(b) Heat-treated Sample 3 (60 C) (Sample H3)

[u10 ] 2.5
5
Butylated Hydroxytoluene

2
Abundance

1.5
Intensity

0.5

0
11 12 13 14 15 16 17 18
Time [min]
(c) Heat-treated Sample 3 (80 C) (Sample H3)
Figure 3.8. Gas-chromatography spectra for XLPE filled with functionalized
nano filler.

Gas-chromatography spectra were obtained for three kinds 3000 2500 2000 1500 1000 500
of XLPE to clarify how heat treatment influenced remaining Wavenumber Shift / cm-1
by-products. Results are shown in Figures 3.6, 3.7 and 3.8. It
is evident that as-received XLPE samples (Samples 1, 2 and (a) Unfilled XLPE (Sample 1)
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1491

oxidation reactions. The strong peak at 1042 cm-1 in the


uppermost spectrum is a feature that we have not seen before,
is not typical of this specimen and its origin requires further
investigation.
3.4 CHARACTERIZATION SUMMARY
(1) It was found from SEM observation that XLPE-based
nanocomposite systems used for the present investigation
contain some filler particles of the order of 10 Pm in size,
together with a wide spectrum of particle sizes within the
Intensity

sub-micrometer range.
(2) There is no change in polymer morphology or
crystallinity due to nano filler addition to XLPE according
to DSC measurement. But it was clarified that XLPE
nanocomposites (Samples 2 and 3) melt at a slightly
lower temperature (102 C) than base XLPE (Sample 1)
(104 C). This suggests that nanoparticles will suppress
the formation of crystalline order as a result of
polymer/nanoparticle interactions.
(3) It was elucidated from the gas-chromatography spectra
that cross-linking residues diminish by heat treatment at
3000 2500 2000 1500 1000 500 80 C for a week in vacuum, while some might remain by
Wavenumber Shift / cm-1
heat treatment at 60 C for a week.
(4) It is generally considered that nano particles leave from
(b) XLPE with non-functionalized nanoslica (Sample 2)
their matrix polymer if a polymer nanocomposite is
Figure 3.9. Confocal Raman spectra acquired from PD aged specimens of
unfilled XLPE (Sample 1) and XLPE containing non-functionalized nano subjected to partial discharges (PDs), and then tend to
silica (Sample 2). accumulate on the surface of the nanocomposite. In the
case of XLPE, the existence of such silica products was
Figure 3.9a shows a selection of Raman spectra acquired not confirmed at least by the Raman spectroscopy.
from different points on a PD aged sample of unfilled XLPE.
The bottom two spectra contain the expected polyethylene 4 PERMITTIVITY AND DIELECTRIC LOSS
peaks below 1000 cm-1, plus some additional features around
500 cm-1, which can be associated with oxygen-containing Complex dielectric permittivity consists of the real ' and
species such as O-C=O (deformation mode at 629 cm-1) and the imaginary '' parts (both frequency dependent, and the
C-C-O (symmetric stretching mode at 595 cm-1) [130]. dissipation factor, tan (4.2), is a ratio of the two parts as
represented by the formulas (4.1).
Similar features were previously observed in samples of
polyethylene that contained a cavity within which partial    (4.1)
discharge activity has occurred [131] and in degradation
residues formed through electrically-enhanced polymer     (4.2)

degradation reactions when conducted in air [132]. The upper
two spectra are, however, very different in that they show no If permittivity measurements are performed in the frequency
evidence of features associated with polyethylene. Both of domain, the conductivity losses are also taken into account in
these spectra are dominated by fluorescence, the lower one the total measured losses, that is, tan = + / . When
also weakly showing the D and G bands of disordered sp2 tends to 0, the major contribution to losses is given by
hybridized carbon. These two spectra therefore contain the conductivity. The is a contribution factor from conduction.
characteristic features previously seen in electrical trees grown An electrode system consists of 10 50 mm upper electrode
in polyethylene [133]. Figure 3.9b shows equivalent data with 1 mm thick specimen electrically stressed usually at 1-
obtained from the nanocomposite containing the 15Vrms. Higher voltage such as 140 and 150 V were used in
unfunctionalized filler; the specimen containing the some cases.
functionalized filler gave equivalent results and, as a result, Heat treatment in vacuum was conducted to remove cross-
these are not included here for the sake of brevity. linking by-products and moisture to lead to proper acquisition
Comparison of sub-figures (a) and (b) of Figure 3.8 reveals of data in nature. The relative permittivity is between 2.2 and
that the same features are present in both; certainly, there is no 2.3 [134] for low density polyethylene, while it must be
clear evidence for an accumulation of nano silica on the slightly larger than this value, around 2.4, for XLPE.
surface of the aged nanocomposite. This is not to say that this
does not occur but, rather, that any accumulation is Experimental results from each research institute are shown
insufficiently great for it to be distinguishable from polymer in Sections 4.1 to 4.5 below.
1492 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

4. 1 EXPERIMENT 1

(a) Frequency dependence of real permittivity (a) Frequency dependence of imginary permittivity

(b) Frequency dependence of real permittivity (b) Frequency dependence of imginary permittivity

(c) Frequency dependence of real permittivity


(c) Frequency dependence of imginary permittivity
Figure 4.1. Frequency dependence of real permittivity of unfilled XLPE,
XLPE with 5 wt% silica nano filler and XLPE with 5 wt% functionalized Figure 4.2. Frequency dependence of imaginary permittivity of unfilled
silica nano filler after heat treatment at 60 C for a week. XLPE, XLPE with 5 wt% silica nano filler and XLPE with 5 wt%
functionalized silica nano filler after heat treatment at 60 C for a week.
Remark: The first run was made just after the heat treatment, while the Remark: The first run was made just after the heat treatment, while the
second run was made one week later after the heat treatment. second run was made one week later after the heat treatment.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1493

The measurements were performed by using IDA 200 (7) There is a small difference in the imginary permittivity
dielectric spectrometer operating within the frequency of XLPE with 5 wt% unfunctionalized silica nano filler
range 10 -4 - 10 3 Hz. The samples were places between and XLPE with 5 wt% functionalized silica nano filler.
contact electrodes in a Keithley 8009 test fixture and the The former seems to be little lower in the low frequency
applied sinusoidal voltage was 144 V rms. Repeatability of region, and a little bit higher in the high frequency
the data was checked in two sets identical experiments, region than the latter.
where the first one was done directly after the thermal
Prior to the above described experiments, the following
treatment and the second one a week later.
two series of experiments were carried out. One was to
Figures 4.1 and 4.2 show the frequency dependence of clarify the effects of heat treatment (at 60 C for a week) and
the real and imaginary parts of dielectric permittivity, the other was to investigate the temperature dependence of
respectively, as measured on 1 mm thick XLPE samples permittivity. In the case of unfilled XLPE, not much
with the contact electrodes. The data shown are for difference was noticeable between original and heat-treated
unfilled XLPE (Sample H1), XLPE with 5 wt% samples, neither in real nor imaginary parts of the
unfunctionalized silica nano filler (Sample H2) and XLPE permittivity.
with 5 wt% functionalized silica nano filler (Sample H3).
The values obtained in this experiment for real It was found that the heat treatment caused in XLPE
permittivity are about 2, which are smaller than the nanocomposites a large reduction in real permittivity below
hypothetical level of 2.4, probably because of the use of 1 Hz, and in imaginary permittivity in the whole range of the
contact electrode system. Nevertheless, comparison frequencies as measured. The initial monotonically
among three kinds of XLPE samples can easily be made. increasing character of real permittivity with decreasing
It is recognized that there is no difference in real frequency, as seen below 1 Hz, for both kinds of XLPE
permittivity and a slight decrease in imaginary nanocomposites turned into a weakly varying dependence.
permittivity for the data obtained directly after and one XLPE with 5 wt% functionalized silica nano filler showed
week later following the heat treatment, as comparing the however larger valuses than those for XLPE with 5 wt%
two sets of the measurements. unfunctionalized silica nano filler. They respectively were
equal to 2.44 and 2.36 at the frequency of 10-4 Hz before the
Distinct features observed after the heat treatment are as heat treatment, while they became reduced to 2.10 and 2.04
follows: after it. Simultaneously, a clear interfacial polarization peaks
in the imaginary permittivity of the two XLPE
(1) Unfilled XLPE (Sample H1) exhibits almost the same
nanaocomposites shifted to much lower frequencies
real permittivity over the whole measured frequency
following the heat treatment. The peak maximum moved
range from 10-4 to 103 Hz, e.g. 1.99 - 1.98, while the two
from ~ 5 x 10-2 to the range below 10-4 Hz. This
kinds of XLPE nanocomposites (Sample H2 and Sample
modification is considered to result from the removal of
H3) indicate an increase at the low frequencies, most
residual moisture and cross-linking by-products, whereas the
probably caused by interfacial polarization.
small differences observed between the two different XLPE
(2) The trend that the permittivity increases with the nanocomposites may indicate that the functional fillers tend
decrease of the frequency in the low frequency region is to adsorb the cross-linking residues.
in XLPE with 5 wt% unfunctionalized silica nano filler
Investigations of the temperature dependence of real and
less noticable than in XLPE with 5 wt% functionalized
imaginary permittivity were performed at 22, 45 and 70 C
silica nano filler.
for the heat treated samples. Real permittivity of unfilled
(3) The steady permittivty value is lower (e.g. 1.90 at 1 XLPE decreases with the increase of temperature within a
kHz) in XLPE with 5 wt% unfanctionalized silica nano few % in the whole frequency ragnge from 10-4 to 103 Hz. In
filler and higher (e.g. 2.03 at 1 kHz) in XLPE with 5 the case of XLPE nanocomposites, it similarly showed a
wt% functionalized silica nano filler than (e.g. 1.98 at 1 negative temperature dependence in the high frequency
kHz) in unfilled XLPE. range from 10-2 to 103 Hz.
(4) The level of imaginary permittivity (losses) is much On the contrary, an opposite temperature dependence
larger in XLPE nanocomposites than in unfilled XLPE. appeared in the low frequency range from 10-2 to 10-4 Hz, i.e.
real permittivity tend to increase with the increase of
(5) Imaginary permittivity in unfilled XLPE is as low as
temperature. It became largest at 70 C at 10-4 Hz.
around 10-4 and shows an unusual discontinuity at
Furthermore, it has to be noticed that XLPE with 5 wt%
around 1 Hz, which is attributed to the instrumental
functionalized silica nano filler exhibited larger permittivity
limits at this low loss level.
valuses than XLPE with 5 wt% unfunctionalized silica nano
(6) Imaginary permittivity shows a similar trend in both filler. At the same time, imaginary permittivity increased
XLPE with 5 wt% unfunctionalized silica nano filler and with the increase of temperature for all the three kinds of
in XLPE with 5 wt% functionalized silica nano filler. XLPE materials, as its frequency dependence curves are
Their values lie in the range between 10-1 at the lowest shifted up to higher level, except for the minimum regions
frequency and 10-3 at the upper frequency range. around 10 to 102 Hz.
1494 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

4. 2 EXPERIMENT 2 between samples with non-functionalized (H2) and


functionalized (H3) nanofillers. Below approx. 1 Hz the
absolute values of the imaginary permittivity are larger for
unfilled XLPE than for filled XLPEs but for frequencies
higher than 1 Hz the opposite is true.
Figures 4.4 and 4.5 show the frequency dependence of the
real and imaginary permittivities of the base XLPE (Sample
H1) as a function of temperature. The real permittiivty
decreases with the increase of temperature, indicating a
negative temperature dependence. The imaginary permittivity
decreases with the increase of frequency in the low frequency
region (below ~ 1 Hz) but tends to increase with the increase
of frequency in the higher fequency region. Hence, the
imaginary permittivity for sample H1 seems to have a positive
temperature dependence in the low frequency region, while it
clearly has a negative temperature dependence in the high
frequency region.

(a) Frequency dependence of real permittivity

Figure 4.4. Frequency dependence of real permittivity of base XLPE (Sample


(b) Frequency dependence of imginary permittivity H1) as a function of temperature.

Figure 4.3. Frequency dependence of the real and imaginary permittivities for
unfilled XLPE (Sample H1), XLPE with 5 wt% silica nanofiller (Sample H2)
and XLPE with 5 wt% functionalized silica nanofiller (Sample H3) after heat
treatment at 60C for a week.
Note that the loss tangent, tanG = H/H.

Figure 4.3a shows frequency dependence of the real


permittivity of Samples H1, H2 and H3 after heat treatment at
60 C in vacuum for a week. Absolute values of the real
permittivity are reasonable in this experiment.Real
permittivity of all three types of XLPE samples indicates a
slight decrease with the increase of frequency in the frequency
range from 10-2 to 104 Hz. It is the lowest for unfilled XLPE
(Sample H1), followed by XLPE with functionalized
nanofiller (Sample H3) and XLPE with non-functionalized
nanofiller (Sample H2). However, the difference between
samples H2 and H3 is negligible. Imaginary permittivities
have a minimum values at around 10 Hz, as shown in Figure
4.3b. This minimum is better defined in the unfilled XLPE Figure 4.5. Frequency dependence of the imaginary permittivity for unfilled
than in both nanocomposites. There is not much difference XLPE (Sample H1) as a function of temperature.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1495

4. 3 EXPERIMENT 3 4. 4 EXPERIMENT 4

2.38
2.37 Sample H1
Sample H2
2.36 Sample H3
2.35
Real Permittivity H'

2.34
2.33
2.32
2.31
2.30
2.29
2.28
-4 -3 -2 -1 0 1 2 3 4 5 6 7
10 10 10 10 10 10 10 10 10 10 10 10
Frequency (Hz)
(a) Frequency dependence of real permittivity
(a) Frequency dependence of real permittivity

(b) Frequency dependence of imginary permittivity (b) Frequency dependence of imginary permittivity
Figure 4.6. Frequency dependence of real and imaginary permittivity (20 C)
Figure 4.7. Frequency dependence of real (a) and imaginary (b) permittivity
of unfilled XLPE (Sample H1), XLPE with 5 wt% silica nano filler (Sample
of unfilled XLPE (Sample 1 and Sample 1H), XLPE with 5 wt% silica nano
H2) and XLPE with 5 wt% functionalized silica nano filler (Sample H3) after
filler (Sample H2) and XLPE with 5 wt% functionalized silica nano filler
heat treatment at 60 C for a week.
(Sample H3) in a low frequency region.

It is important to note that only these data are relevant to


Frequency dependence of real and imaginary permittivity
Fourier decomposition of dc discharging currents (or
was investigated from 10-3 to 106 Hz, using a Novocontrol
depolarization currents) as shown in Section 5. Real
ALPHA-A analyzer in combination with an active ZGS
permittivity is near 2.4, which is reasonable. Permittivity was
sample cell. Some data of imaginary permittivity exhibited
investigated especially in a low frequency region below 1 Hz.
negative values in the low frequency range below 10 Hz, and
Figure 4.7 shows the frequency dependence of real (a) and
in the high frequency range at 1 MHz in this experiment.
imaginary (b) permittivity of Samples 1, H1, H2 and H3 in a
Such data were excluded in Figure 4.6. Real permittivity are
low frequency region from 10-5 to 1 Hz. Heat treatment was
smaller than 2.4. Both values of real and imaginary
made at 80C for 5 days in this case, in which higher
permittivity increase when nano filler is added, as found in
temperature was used than in experiments described in the
Section 4.2. The former increases by filler functionalization
preceding sections 4.1, 4.2 and 4.3. Similar characteristics can
as opposed to the data of Section 4.1, while the latter
be observed for change due to heat treatment as compared to
decreases. It was confirmed that dielectric response is
the results shown in the preceding section 4.3.
relatively invariant in the temperature range from 20 to 50C
for heat-treated samples. Heat treatment is to reduce losses Comparatively large real permittivity is observed in the low
especially at low frequency. frequency region for unfilled XLPE. It reduces due to heat
1496 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

treatment, as recognized from the curves for Sample 1 and with and without heat treatment (Samples 1, 2, 3, H1, H2
Sample 2 (Sample 2 data not shown in this figure). The former and H3). It was also confirmed in this case that heat
exhibits larger real permittivity than the latter. Imaginary treatment at 80 C for 1 week leads to a reduction of
permittivity is large for unfilled XLPE (Sample 1), either, with permittivity. As far as real permittivity for Samples H1, H2
a peak at about 5 x 10-4 Hz, as this trend is recognized in and H3 is concerned, as shown in Figure 4.8, it is almost
Figures 4.3 and 4.5. The heat treatment in this experiment independent of frequency in the high frequency region from
leads much reduction in both real and imaginary permittivity. 1 to 106 Hz. It is especially to be noted that almost the same
It is recognized that much more reduction in real and data are obtained from 103 to 106 Hz as compared with data
imaginary permittivity is made in the heat treatment at 80 C from 1 to 103 Hz. Real permittivity at 100 Hz is 2.52, 2.51
than at 60 C. It is suspected that cross-linking by-products and 2.50 for Samples H1, H2 and H3, respectively. This
must still remain after heat treatmet at 60 C for a week. trend is the same with other data as shown in the high
frequency region in Sections 4.2, while absolute values are
In summary: different unfortunately.
(1) Real and imaginary permittivity is smaller for unfilled
XLPE than for both XLPE nanocomposites in the low Imaginary permittivity in Figure 4.8 shows a similar trend
frequency region. with other data of Sections 4.2 and 4.3. That is, it increases
(2) Real and imaginary permittivity is smaller for XLPE with with the decrease of frequency in the low frequency region.
5 wt% functionalized silica nano filler than for XLPE But it is different in that it has a hump at 103 Hz for filled but
with 5 wt% silica nano filler in the low frequency region. non-functionalized XLPE (Sample H2) and around 10 Hz for
filled and functionalized XLPE (Sample H3). This could be an
4. 5 EXPERIMENT 5 effect of changing temperature during the measurement. The
real part of the complex permittivity decreases with increasing
2.70
temperature. For the imaginary part of the complex
2.67 Sample H1 permittivity no distinctive behavior could be observed.
Sample H2
2.64 Sample H3
In summary:
Real Permittivity H'

2.61
(1) It was confirmed that heat treatment leads to much
2.58 reduction in permittivity and gives us proper values. This
2.55 reduction is significant for real permittivity at the low
2.52
frequency region. Significant change of imaginary
permittivity: loss peaks shift to lower frequencies or
2.49
diminish.
2.46 (2) Real permittivity of XLPE with modified silica is lower
10
-3 -2
10
-1
10
0
10 10
1 2
10 10
3 4
10 10
5 6
10
7
10 than of unfilled XLPE or XLPE with non-modified silica.
Frequency (Hz) (3) For frequencies above 1 Hz the imaginary permittivity
does not change significantly with the introduction of 5
(a) Frequency dependence of real permittivity wt% of nano silica, while a change is recognized for low
frequencies.
(4) In the low frequency region, XLPE unfilled (H1) and
XLPE filled with non-modified silica (H2) show
increased permittivity, which does not show up in XLPE
with modified silica (H3).
(5) Silica filled XLPE exhibits an additional loss peak:
(i) around 3 x10-2 Hz for non-modified particles
(ii) around 2 x102 Hz for modified particles
(estimated from digital data)
(6) Losses for XLPE with modified silica are the lowest
overall.

4. 6 DISCUSSION AND CONCLUSIONS FROM


PERMITTIVITY MEASUREMENTS
According to the gas chromatography/mass-spectroscopy
(b) Frequency dependence of imginary permittivity study, some of cross-linking residues may remain after the
Figure 4.8. Frequency (10-2 to 106 Hz) dependence of real permittivity (a) and heat treatment of cross linked XLPE samples at 60 C for a
imaginary permittivity (b) for three kinds of XLPE after heat treatment at 80 week. No cross-linking residues have been detected after the
C for 1 week.
heat treatment at 80 C for a week. Absolute values of the real
The frequency dependence of the real and imaginary and imaginary permittivity are unfortunately different under
permittivity was measured for three kinds of XLPE samples the apparently same condition by each of participants. But
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1497

comparative study is possible. There are three influential discussion, it can be said that the real permittivity can be
factors that should be taken into deep consideration, i.e. determined by the balance of the effects from the residues
and the nano particles. The residues will increase the
(i) Cross-linking residues
permittivity, while the small amount of nano particles will
(ii) Nano filler particles decrease it. In conclusion, nanocomposite XLPE,
preferably with surface modification, will have a smaller
(iii) Coupling agents for surface modification permittivity than neat XLPE.
Table 4.1. Qualitative comparison of the real permittivity among Samples H1, In the low frequency region, there is a significant
H2 and H3. difference in the real permittivity among the three kinds of
(a) Real Permittivity in High Frequency Region. XLPE materials. It is the lowest for neat XLPE (Sample
Participants Large or Small Ranking Heat Treatment H1). Value of the real permittivity in the low frequency
Gubanski H1 < H2 < H3 60 C region is the lowest for neat XLPE (Sample H1) heat-
Bulinski H1 < H3 < H2 treated at 60 C. On the contrary, one of the data obtained
by the heat treatment at 80 C indicates that it is the lowest
Frchette H1 < H2 < H3
for XLPE nanocomposite (Sample H3). If cross-linking
Montanari ---- 80 C
residues are reduced to the minimum by a proper heat
Morshuis H3 H2 < H1
treatment, it might be possible to realize the lowest
(b) Real Permittivity in Low Frequency Region permittivity in the low frequency region.
Participants Large or Small Ranking Heat Treatment
The following conclusions on nano filler effects are derived
Gubanski H1 < H2 < H3 60 C
from the above discussion.
Bulinski H1 < H3 < H2
Frchette H1 < H2 < H3 (1) In the high frequency region, there is not much difference
Montanari H1 < H3 < H2 80 C in the real permittivity among the three kinds of samples.
Morshuis H3 < H2 < H1 (2) In the low frequency region, there is a significant
difference in the real permittivity among the three kinds
Samples are heat-treated to remove the cross-linking residues of samples.
out. But the first concern is that some of them are suspected to
remain after the heat treatment especially at 60 C. In principle, (3) In both cases, nano filler particles are considered to
such residues are considered to play a role to increase the real reduce the real permittivity, when a proper heat treatment
and imaginary permittivity, as was clarified in Samples 1, 2 is made to remove cross-linking residues.
and 3 before the heat treatment. The next concern is whether (4) Apparent increase of the real permittivity by nano filler
or not nano filler particles will interact with cross-linking addition may be caused by cross-linking residues.
residues. If there is some interaction, the nano particles will
adsorb the residues on their surfaces. Surface treatment might Table 4.2. Qualitative comparison of imaginary permittivity among Samples
act to adsorb or release the residues. It is important to analyze H1, H2 and H3.
the dielectric spectroscopy data obtained in this research by
dividing the frequency region into two, i.e. a high frequency (a) Imaginary Permittivity in High Frequency Region.
region and a low frequency region. It is difficult to clearly Participants Large or Small Ranking Heat Treatment
define the boundary between high and low frequency regions. Gubanski H1 < H3 < H2 60 C
It depends on the data obtained individually by the participants. Bulinski H1 < H3 H2
But it is safe to define that the former is above 1 kHz and the Frchette H1 < H3 < H2
latter is below 0.1 Hz. Montanari ----- 80 C
Morshuis H3 H2 < H1
Table 4.1 shows the ranking from small to large values of the
(b) Imaginary Permittivity in Low Frequency Region.
real permittivity in the high frequency region (a) and in the
low frequency region (b). Participants Large or Small Ranking Heat Treatment
Gubanski H1 < H3 < H2 60 C
In the high frequency region, there is not much difference Bulinski H3 H2 < H1
among the three kinds of samples in general, although a Frchette H1 < H3 < H2
slight difference is recognized. Under such a marginal Montanari H1 < H3 H2 80 C
condition, the real permittivity of neat XLPE (Sample H1)
Morshuis H3 < H2 < H1
is smaller than that of nanocomposite XLPE (Samples H2
and H3), when the samples are heat treated at 60 C, but The imaginary (loss) permittivity is sensitive to impurities in
such a tendency is reversed after the heat treatment at 80 C. general. In our case, the increase of this parameter must be
Therefore, if no residues remain, the real permittivity might caused by the existence of cross-linking residues and nano
decrease by the addition of nano filler. Comparing Samples particles. Surface treatment is expected to reduce the loss
H2 and H3, the surface modification may act to reduce the permittivity. Table 4.2 shows the ranking from small to large
real permittivity. Modified surfaces are considered to make values of the imaginary permittivity (dielectric loss) in the
more adsorption or release of the residues. From the above high frequency region (a) and in the low frequency region (b).
1498 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

In the high frequency region, the dielectric loss is smaller for


neat XLPE (Sample H1) than for nano filled XLPE (Samples
H2 and H3) when heat treatment temperature is 60 C. It
means that the existence of nano particles or some remaining
residues will increase dielectric loss. On the contrary, the
opposite data are obtained, when heat treatment temperature is
80 C. Therefore it is possible to postulate that nano particles
will reduce the loss, although the residues will increase it.
Comparing Sample H2 and H3, the loss for H3 is equal to or
smaller than that for H2. It means that the surface treatment
will work to reduce the dielectric loss in the high frequency
region.
In the low frequency region, it is not decisive which is Test procedures
smaller, the loss of neat XLPE (Sample H1) or that of filled - Poling field 20 kV/mm, room
XLPE (Sample H2 and H3). But it seems that the latter temperature
become smaller than the former after a sufficient heat - Polarization: up to steady state
treatment. Comparing Sample H2 and H3, the loss for H3 is condition is reached
equal to or smaller than that for H2. It means that the surface
treatment will work to reduce the dielectric loss in the low
Figure 5.1. Schematics of an electrode system for DC conductivity
frequency region, too. measurement. Active electrode diameter: 10 mm, sample thickness: 1 mm.
Thus it is possible to postulate that some cross-linking
residues remain even after the heat reatment at 60 C. Such
residues decrease by the heat treatment at 80 C to make nano
particle effect observable as the dielectric loss.
The conclusions which state that losses are lower with
nanocomposites and that the loss results at low frequency must
match with conductivity results are not completely true. Firstly,
the prevalence of conductivity occurs at very low frequencies
and is typical of a linear behavior with slope close to 1, which
is not the case here. Secondly, there are contrasting results
between Sections 4.4 and 4.5. It is suspected that the
techniques are different. One is based on discharging current,
while the other is based on a measurement bridge, and that the
sharp decreasing behavior shown by H3 in Figure 4.8b is not
often observed. In addition, the very low frequency behavior
of permittivity is due not only to the presence of by-products,
but also to interface polarization (Maxwell-Wagners-Sillars)
due to the significant volume influence of nano interfaces. Figure 5.2. Comparison of DC current density at room temperature among
unfilled XLPE, filled XLPE non-functionalized and filled XLPE
5 DC CONDUCTIVITY functionalized (Samples 1, 2 and 3) before and (Samples H1, H2 and H3) after
heat treatment.
DC charging current measurement was performed by means
of a three terminal cell system with its gold coated electrodes,
Since heat treatment is to exclude extrinsic influences from
as shown in Figure 5.1. Steady state currents were obtained
cross-linking by-products and moisture, we should compare
under the electric field 20 kV/mm. Figure 5.2 shows dc
data after heat treatment to investigate the effects of nano filler
current density data between unfilled XLPE (Sample 1 and
addition and surface treatment of nano filler. It is recognized
Sample H1), filled XLPE (Sample 2 and Sample H2) and
in Figure 5.2 (Sample H1, H2 and H3) that there is a
(Sample 3 and Sample H3) before and after heat treatment. As
significant effect of nano filler addition for dc conductivity.
dc conductivity is proportional to current density, a term of dc
Furthermore, surface treatment of nano filler is also effective
conductivity is used as expression. As is indicated in Figure
to reduce dc conductivity.
5.2, dc conductivity is much reduced if XLPE is filled with 5
wt% silica nano fillers. Heat treatment for 5 days at 80 C In summary:
contributes further reduction in dc conductivity, except in the
(1) In general, heat treatment reduces dc conductivity, with
case of unfilled XLPE. Surprisingly, there is almost no effect
some exception.
of heat treatment in dc conductivity for unfilled XLPE (data
not shown here), which underlines the potential of nanofillers (2) Nano filler addition significantly reduces dc
as nucleation items for by-products and contaminants. conductivity.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1499

(3) Surface treatment (functionalization) additionally


reduces dc conductivity. I (t)
Measured
Sample H3 (5 % nanofiller + surface treatment + thermal PE Sample
Measurement
treatment) shows the lowest conductivity Electrode

DC conductivity reduction might support such a mechanism pA


that nano fillers will act as charge carrier traps, and will Thermal diffuser
strengthen their function if they are functionalized. 'T 'T

6 SPACE CHARGE
Figure 6.2. TSM (Thermal Step Measurement) method for space charge
6.1 MEASUREMENT SYSTEM measurement.

Two types of measurement systems were used to measure


space charge in XLPE samples, i.e. the pulsed electro-acoustic
(PEA) method and the thermal step (TS) method, as shown in 6.2 SPACE CHARGE BY PEA METHOD 1
Figures 6.1 and 6.2, respectively [135-137]. Electrode HIGH FIELD TEST
diameter is 8 to 10 mm for PEA method and 40 mm for
TSM method. 150
The PEA method is based on the effect of an electric field 100 cathode anode

Charge density [C/m ]


3
induced acoustics wave on space charge. By detecting the
acoustic wave generated by the space charge, one could know 50
the space charge distribution in the dielectric. Space charge
can be measured either under voltage on condition or under 0
voltage off condition.
-50
Trigger
-100
HVDC
-150
R = 1 M: -200
C = 220 pF
-50 0 50 100 150 200
Thickness [ Pm]
Specimen
(a) Unfilled XLPE (Sample H1)

To scope 100
Transducer
Charge density [C/m3]

40
40
cathode anode
Absorber
dB
dB
50

Figure 6.1. PEA (Pulsed Electro-acoustic) method for space charge 0


measurement.

The TSM is based on a diffusion of a thermal wave across -50


the dielectric that generates a temporary local disequilibrium
of the space charge. This disequilibrium is reflected at the -100
electrodes by a variation of the influencing charges, which
allows determining the distribution of the electric field and
charge density in the sample. Measurement can be made either -150
in short-circuit condition or under dc applied field [135]. TSM -50 0 50 100 150 200 250
is a non-destructive technique allowing space charge Thickness [ Pm]
measurement just after the manufacturing process (on virgin
sample) or after electrical poling. (b) XLPE filled with non-functionalized nano filler (Sample H2)
1500 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

100 100
cathode anode anode
cathode
Charge density [C/m ]
3

Charge density [C/m ]


50

3
50

0 0

-50 -50

-100 -100

-150 -150
-50 0 50 100 150 200 -50 0 50 100 150 200
Thickness [Pm] Thickness [ Pm]
(c) XLPE filled with functionalized nano filler (Sample H3) (c) XLPE filled with functionalized nano filler (Sample H3)
Figure 6.3. Space charge distributions observed at 25 oC during the Figure 6.4. Space charge distributions observed at 50 oC during the
application of a dc electric field of 100 kV/mm for smaples after heat application of a dc electric field of 100 kV/mm for smaples after heat
treatment at 80 C in vacuum for a week. treatment at 80 C in vacuum for a week.

100 Samples were heat-treated at 80 C in vacuum for a week,


and then hot-pressed to reduce thickness from 1 mm down to
cathode anode
Charge density [C/m ]

140 or 280 m for space charge measurement. Space charge


3

50 was measured at a relatively high electric stress of 100


kV/mm. Figures 6.3 and 6.4 show space charge distribution at
0 25 oC and 50 oC, respectively. Figure 6.3 shows data at 25 oC,
i.e. heterocharge in cathode appears in unfilled XLPE, and it
almost disappears in filled XLPE. XLPE filled with
-50 functionalized nano filler exhibits more distinct disappearance
than XLPE filled with non-functionalized nano filler. As such,
-100 the suppression of hetero space charge formation by nano
filler is confirmed in XLPE. Surface treatment will promote
such reduction. It is to be noted that this behavior was already
-150 found in LDPE. At the higher temperarues of 50 oC, homo
-50 0 50 100 150 200 250
charge tends to be formed, as shown in Figure 6.4. In this
Thickness [ Pm] case, there is not much difference in space charge distribution
between unfilled XLPE and filled XLPE.
(a) Unfilled XLPE (Sample H1)
Gas-chromatography/mass- spectrometry spectra presented
100 above indicate that crosslinking residues remains after heat
cathode anode treatment at 60 C for a week, but they almost diminish after
Charge density [C/m ]

heat treatment at 80 C for 1 week. Surprisingly, space charge


3

50
distribution does not seem to be influenced by heat treatment
in this experiment (data not shown).
0
It is speculated that:
(1) Hetero space charge is formed in unfilled XLPE.
-50
(2) Homo space charge is introduced in filled XLPE.
-100 (3) Only a balance of positive and negative charges becomes
observable.
-150
-50 0 50 100 150 200 6.3 SPACE CHARGE BY PEA METHOD 2
Thickness [ Pm] The measurements were performed with a Five Labs, Ltd.,
20 kV PEA Space Charge Measurement System and Tektronix
(b) XLPE filled with non-functionalized nano filler (Sample H2) 7404, 4 GHz, 20 GS/s digital oscilloscope. The resolution of
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1501

the measurement system is ~ 17 m. All measurements were and the space charge measurements were performed in the
performed at room temperature (~ 20 1 C). PEA test cell, i.e. without any interruptions of the specimen
The measurements were conducted on 1mm thick samples assembly.
(i.e., as received from the sample provider) and on ~85 m In the case of thick samples (1 mm) not subjected to any dc
thick samples obtained by hot-pressing the original 1 mm field prior to the space charge measurements at 6 kV/mm, no
plaques. space charge is observed, as shown in Figure 6.5a. When a
field of 20 kV/mm is applied for some time and then removed,
only a small amount of a heterocharge is observed in all three
types of XLPE samples, as shown in Figure 6.5b by the
measurement under 6 kV/mm. Initially, unfilled XLPE shows
more of the charge but after 120 h all three materials show the
similar amount. This observation is relevant to the cathode
side of the samples, for which the measurement results are
more reliable than for the anode side due to a relatively weak
signals and noisy spectra. The results of heterocharge
formation seem to indicate that after one week at 60 C in
vacuum the specimens still retained some of the crosslinking
byproducts [138-140]. From the changes in space charge
distributions in all three materials with the time of exposure to
a dc field (Figure not shown here), it was concluded that: (1)
the amount of the heterocharge in the unfilled XLPE does not
change significantly between 1 h and 120 h at 20 kV/mm (at
the cathode side) and, (2) the density of heterocharge in both
nanocomposites increases gradually with time and after 120 h
(a) DC Voltage Application Time: Zero reaches the level similar to that in the unfilled XLPE.
Figure 6.6 shows space charge distributions in the 85 m
thick samples subjected to 50 kV/mm and measured at the
same, 50 kV/mm field. Only a small amount of heterocharge
extending relatively deep into the bulk of the samples could be
observed in both XLPE samples with nanofillers. The
distribution for unfilled XLPE indicates small amount of
homocharge at the cathode.

(b) DC Voltage Application Time: 120 h


Figure 6.5. Space charge distributions in the 1 mm thick XLPE specimens
with and without nano-filler after different periods of time of exposure to a 20
kV/mm dc field at room temperature. The space charge measurements were
performed at 6 kV/mm.

All specimens were thermally pre-treated in a rough vacuum


at 60C for one week to reduce the content of cross-linking
by-products. Compression of the specimens to obtain thinner
samples was performed after the vacuum treatment of 1 mm
plaques. The thick, 1 mm samples were subjected to a dc field Figure 6.6. Space charge distributions for the 85 m thick XLPE specimens
with and without nano-filler after 2 h of exposure to a 50 kV/mm dc field at
of 20 kV/mm for various periods of time and then measured room temperature. Space charge measurements were performed at the field 50
for the space charge distribution at a field of 6 kV/mm. Thin, kV/mm.
85 m specimens were subjected to a dc field of 50 kV/mm
and measured for the space charge distribution under the In summary:
same, 50 kV/mm field. Both the dc charging of the samples (1) No space charge is observed at a field of 6 kV/mm.
1502 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

(2) Charging the samples at a field of 20 kV/mm leads to Figure 6.7 shows the space charge distribution and stored
formation of a small and comparable amounts of total charge for unfilled and filled XLPE (Samples 1, 2 and 3)
heterocharge in all three types of samples. before and (Samples H1, H2 and H3) after heat treatment at 80
(3) A 50 kV/mm field applied for 2 h generates small C for five days. The samples were subjected to an electric
amounts of heterocharge in both nanocomposites and field of 20 kV/mm at room temperature. As can be seen,
some amount of homocharge in the base XLPE. without treatment the nanofilled samples (Samples 2 and 3)
keep significant amounts of space charge (about the same of
the unfilled material, Sample 1), with mostly homocharge at
6.4 SPACE CHARGE BY PEA METHOD 3 the anode and a mix of homo and heterocharge at the cathode
(see depolarization patterns). Removal of the cross-linking
byproducts by thermal treatment reduces significantly the
space charge density. It can be speculated that homo charge
injection is likely to take place if nano filler is added. The
presence of heterocharge at the test voltage (corresponding to
the operation field) can be speculatively explained by the
presence (recently proved) ultra-fast charge packets [140,
141]; these are presumably solitons, which are associated with
the relaxation mechanisms and mechanical properties of
polymer chains. These vary with the presence of nano fillers,
so that the transport and accumulation mechanisms can
change. Heterocharge can be explained in this way rather than
the effect of crosslinking by-products, at least close to
operating stress.

In summary:
(1) Filled XLPE samples show lower space charge
accumulation than unfilled XLPE samples.
(2) The lowest space charge amount is obtained when nano
filler is surface-treated.
(3) Thermal treatement reduces space charge particularly for
filled XLPE samples.

It has been observed that homo charge injection is likely to


take place if nano filler is added [139, 140]. Therefore, the
reduction of hetero charge observed might appear from a
balance between positive and negative charges and/or from
(a)
soliton formation and transport.

6.5 SPACE CHARGE BY PEA METHOD 4


Heat treatment was conducted at 80 C for 12 h. DC voltage
of 20, 30 and 40 kV was applied to 1 mm thick XLPE samples
(Samples 1, 2 and 3, Samples H1, H2 and H3) at room
temperature. Measurement time was 1 h. Change in space
charge distribution due to heat treatment was not recognizable
in this experiment. Space charge distributions were measured
under the electric field 30 and 40 kV/mm as shown in Figure
6.8a. However, no remarkable space charge was observed in
this experiment. Space charge distributions in untreated (as
received) samples were also measured. However, no
remarkable space charge was observed in them, too. By using
thinner XLPE samples (different from the cooperative test
samples), Figure 6.8b was obtained. It shows the electric filed
(b) (50 to 200 kV/mm) dependence of space charge distributions
in XLPE. Packet charge appears above the electric field 50
Figure 6.7. Space charge distribution at 20 kV/mm (a) and stored total charge
(b) in unfilled and filled XLPE (Samples 1, 2 and 3) before and (Samples H1, kV/mm, while there is no packet charge like this up to the
H2 and H3) after heat treatment at 80 C for five days. field 40 kV/mm.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1503

6.6 SPACE CHARGE BY THERMAL STEP METHOD


The thermal step method was used instead of the PEA
method in this experiment [143-145]. Space charge
measurement was made in short-circuit condition.

(a)

(a) Electric field at anode

(b)
Figure 6.8. Space charge distributions (a) in Samples H1, H2 and H3
subjected to the moderate electric field 30 and 40 kV/mm after heat treatment
at 80 C for 12 h, and space charge distributions (b) in an XLPE sample under (b) Electric field at cathode
high dc electric field.

It is interesting to note that multiple packet charge start to


repeat from the field 200 kV/mm. As shown in Figure 6.8b,
the charge density of the packet-like charge show the value of
about 100 C/m2, and it enhances the local electric field in the
sample. Since the enhanced electric field sometimes becomes
more than twice of the applied average electric field, such
packet-like charge seems to be significant for the breakdown
of the sample.
From the point of view of the breakdown, the observed levels
of the space charge distributions show in Figure 6.8a are too
small to affect the breakdown strength. This packet charge is
expected to be suppressed by nano filler addition [61],
although data are not presented here. To investigate the
relationship between breakdown and space charge formation, (c) Total charge
we need to measure the space charge distribution under higher
dc electric field (higher than 100 kV/mm). To carry out the Figure 6.9. Remnant electric fields at anode and cathode and summed (total)
measurement under higher dc electric field, thinner sample charge for three kinds of XLPE samples subjected to heat treatment at 60 C
(less than 200 Pm) is needed. for a week as a function of the electric field up to 30 kV/mm.
1504 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

(1) The remnant electric field in unfilled XLPE tends to


increase as the applied electric field increases from 5
kV/mm. The maximum remnant electric field is +5.5
kV/mm and -5.3 kV/mm at the anode and at the cathode,
respectively.
(2) The remnant electric field is much reduced to almost zero
when XLPE is filled with nano filler. Exception is
observed at the anode at 30 kV/mm for XLPE filled with
functionalized filler. Polarity of the electric field is
changed from positive to negative in this case.

(a) Electric field at anode (3) The same observation can be obtained for the remaining
total charge. That is, the charge increases as the electric
field is increased from 5 kV/mm. It is much reduced when
XLPE is filled with nano filler. There is some exception
for XLPE filled with functionalized filler at 30 kV/mm.

Dominant charge for neat XLPE is negative. Therefore


electrons injection at the cathode is probable. The total trapped
charge is reduced when XLPE is filled.
Figure 6.10 shows the remnant electric fields at anode and
cathode and summed (total) charge for three kinds of XLPE
samples subjected to heat treatment at 60 C for a week as a
function of time for poling at 30 kV/mm. The poling was
made at 70 C for the time up to 897 h. Following observation
can be made.
(b) Electric field at cathode
(1) Filled XLPE shows a lower remnant electric field over a
whole poling period than unfilled XLPE. XLPE filled
with functionalized filler exhibits the lowest electric field
of all.
(2) The remnant electric field at the anode is positive (hetero
charge) in its polarity for unfilled XLPE and XLPE filled
with non-functionalized filler, while it is negative (homo
charge) for XLPE filled with functionalized filler. The
remnant electric field at the cathode is negative (homo
charge) for all three kinds of XLPE samples.
(3) The remnant electric field surprisingly decreases at the
anode in unfilled XLPE and XLPE filled with
functionalized filler, as a poling time increases. It is
almost independent of poling time in XLPE filled with
(c) Total charge non-functionalized filler.
(4) The remnant electric field at the cathode is almost
Figure 6.10. Remnant electric fields at anode and cathode and summed (total) independent of poling time in the case of filled XLPE,
charge for three kinds of XLPE samples subjected to heat treatment at 60 C
for a week as a function of poling time up to 897 h at 30 kV/mm. while that at the anode tends to decrease with the increase
of poling time.
XLPE samples were heat-treated at 60 C for a week. The above behaviors can be interpreted from double injection
Voltage up to 30 kV was applied to thick XLPE samples of for XLPE filled with functionalized filler, i.e. electron
1 mm thickness at 70 C for up to 897 h for poling. Then the injection and hole injection.
samples were short-circuited during 30 minutes before
measurements. After that, electric field and trapped charge
were measured. Concluding Remarks

Figure 6.9 shows the remnant electric fields at anode and (1) Filled XLPE seems to accumulate less space charge than
cathode and remaining summed (total) charge for three kinds unfilled XLPE.
of XLPE samples as a function of the electric field up to 30 (2) XLPE filled with functionalized filler exhibits the lowest
kV/mm. The following things can be derived from the figure. electric field of all.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1505

(3) Double injection seems to take place in the case XLPE 7 DIELECTRIC BREAKDOWN
filled with functionalized filler. Compensation of negative and
positive charge might take place during a long time in poling. 7.1 AC BREAKDOWN STRENGTH 1

6.7 SUMMARY OF SPACE CHARGE


MEASUREMENTS
Bulinski (Low Field) PEA
(1) No space charge is observed at the field 6 kV/mm.
(2) Heterocharge remains after the application of the field 20
kV/mm. No difference in the amount of heterocharge is
recognized by this remnant charge detection method.
(3) Thinned samples of 85m thickness subjected to the field
50 kV/mm gave such results that small amount of
Figure 7.1. Schematics of a cell for AC breakdown tests.
heterocharge exist for filled XLPE, while homecharge is
observable for unfilled XLPE.
Montanari (Low Field) PEA
(1) Filled XLPE samples show lower space charge
accumulation than unfilled XLPE samples.
(2) The lowest space charge amount is obtained when nano
filler is surface-treated.
(3) Thermal treatment reduces space charge particularly for
filled XLPE samples.
Tanaka and Ohki (High Field) PEA
(1) Hetero space charge is observed in unfilled XLPE.
(2) Homo space charge is introduced in filled XLPE.
(3) Only a blance of positive and negative charges is
considered to become observable.
Y. Tanaka (High Field) PEA
(1) No analizable or significant space charge was observed for
1mm thick samples of the three kinds subjected the field
30 and 40 kV/mm.
Castellon (Low Field) TSM
(1) Filled XLPE seems to accumulate less space charge than
unfilled XLPE.
(2) XLPE filled with functionalized filler exhibits the lowest
electric field of all.
(3) Double injection seems to take place in the case of XLPE
filled with functionalized filler. Compensation of negative
and positive charge might take place during a long time in
poling.

In summary:
(1) Heterocharge is formed for unfilled XLPE.
(2) Hetrocharge reduces by the addition of nano filler.
(3) Homocharge is comparatively easy to be injected into
filled XLPE. Figure 7.2. Histogram of AC breakdown strength of unfilled XLPE and filled
(4) Charge compensation takes place when nano filler is XLPE with (a) the scale parameter and (b) the shape parameter.
added. AC dielectric breakdown strength tests were performed by
(5) Charge packet appears at the extremely high electric field means of a test cell with 2 spherical electrodes (diameter 30
near breakdwon. But no nano filler effct was clarified in mm) in silicone oil at room temperature (Figure 7.1). Applied
this experiment. voltage was raised at the rate of 30kVrms/min. Data were
1506 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

obtained in the form of two parameters of the Weibull Samples were heat-treated at 60 C in vacuum for 8 days. Ac
distribution, i.e. the scale parameter and the shape parameter. (60 Hz) breakdown tests were carried out in silicone oil with
They represent the breakdown strength [kVrms/mm] and the plane/plane electrodes (6.4 mm) using a cell as shown in Figure
data scatter , respectively. 7.3. Applied voltage was increased at the rate of 500 Vrms/s.
About 40 of breakdown measurements were made on each of
Figure 7.2 shows ac breakdown strength of unfilled XLPE
the 3 samples (~1 mm thick), and outliers of data were removed
and filled XLPE with (a) the scale parameter and (b) the shape
from statistics. Flashovers were treated as suspended data.
parameter of Weibull distribution. From comparison of the
Figure 7.4 shows ac breakdown strength of unfilled XLPE and
scale and shape parameters experimentally obtained, results
filled XLPE in Weibull distribution. From comparison of ac
can be summarized as follows:
breakdown strength (63.2% value) among three kinds of XLPE
(1) Neither nano filler addition nor surface treatment of nano samples, following results can be derived.
filler raises much of ac breakdown (BD) strength in the
(1) There is no striking effect of nano filler on the change of
case of XLPE samples provided this time.
ac breakdown strength.
(2) Both nano filler addition and surface treatment of nano
(2) Addition of functionalized nano filler seems to cause only
filler would work to reduce BD data scatter.
a slight increase by 2 % to unfilled XLPE.
(3) Heat treatment seems to increase ac breakdown strength
(3) Inversely, addition of non-functionalized nano filler seems
by a few % for nano filled XLPE samples.
to cause a slight decrease by 5 % to unfilled XLPE.
(4) Highest ac breakdown strength was obtained with XLPE
(4) Highest ac breakdown strength was obtained with XLPE
filled with functionalized nanofiller after heat treatment.
filled with functionalized nanofiller after heat treatment.
7.2 AC BREAKDOWN STRENGTH 2 7.3 IMPULSE BREAKDOWN STRENGTH

Figure 7.5. Schematics of a needle to plane electrode system to measure


dielectric breakdown by impulse voltage
Remarks: sample thickness: 1 mm, needle tip radius: 10m and electrode
distance: 0.5 mm.
Figure 7.3 A test cell for ac breakdown
Impulse breakdown tests were conducted by using a needle
to plane electrode system as shown in Figure 7.5, which was
immersed in silicone oil. Breakdown tests were made by
applying one shot impulse. It was confirmed that the
breakdown occurred at the wave front. Figure 7.6 shows
results of impulse breakdown voltages for three kinds of
XLPE samples.
Obtained results can be described as follows.
(1) There is no significantly positive effect of nano filler on
the change of impulse breakdown voltage.
(2) Heat treatment works to increase impulse breakdown
voltage all three kinds of XLPE.
(3) Addition of 5% non-functionalized nano filler to XLPE
causes to reduce impulse breakdown voltage slightly.
(4) Addition of functionalized nano filler seems to cause a
slight recovery from the once lowered breakdown voltage.
Figure 7.4 AC breakdown strength of unfilled XLPE and filled XLPE in
Weibull distribution (5) Highest impulse breakdown voltage was obtained with
Remarks: XLPE: H1, XLPE+FnF: H3, XLPE+UnF: H2 XLPE filled with functionalized nano filler after heat
ACBD Field (kV/mm): kVrms/mm treatment.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1507

Figure 7.6. Impulse breakdown voltages for three kinds of XLPE samples.

7.4 SUMMARY OF BREAKDOWN MEASUREMENTS


Following results are obtained on dielectric breakdown
characteristics of unfilled XLPE and filled XLPE. (b)
(1) There is no significantly positive effect of nano filler on Figure 8.1 A needle-plane electrode system with air gap of 0.1 mm and with a
the change of ac and impulse breakdown strength. On the tungsten needle electrode of 1 mm diameter for PD erosion evaluation.
contrary, data scatter is greatly reduced.
(2) XLPE filled with functionalized nanofiller after heat
treatment gives the highest ac and impulse breakdown
strengths, although the difference is not so marked.
These results, with XLPE, are similar to breakdown
behaviors of polyethylene (i.e. not XLPE) nanocomposite [84-
89]. In contrast, prior work on XLPE/SiO2 using recessed
electrode (i.e. more grading) [5] gave slightly higher
breakdown values. It is generally accepted that dc breakdown
strength is increased by nano filler addition [19, 20, 89-95],
but only a small increase in ac BD strength is found from the
present investigation. In the case of treeing, it is evident [21,
99-107] that treeing lifetime is enormously prolonged.

8 PD RESISTANCE (a) Erosion pit depth


8.1 PD EROSION 1

(b) Cross-sectional area of a formed pit

Figure 8.2. Evolution of PD erosion depth (a) and PD erosion area (b) with
aging time for Samples H1, H2 and H3.
(a)
1508 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

Figure 8.3. Average erosion speed for three kinds of XLPE (Samples H1, H2
and H3).
(a) Erosion depth
An electrode system as shown in Figure 8.1 was used for
partial discharge (PD) aging. Voltage 10 kVrms (250 Hz) was
applied to three kinds of XLPE samples of 1 mm thickness for
time up to 750 h (50 Hz equivalent time). Applied voltage
corresponds to 5 times PD inception threshold.
Two types of erosion data were obtained, i.e. erosion pit
depth and cross-sectional area of a formed pit. Their temporal
change is shown in Figure 8.2 obtained for 2 specimens for
each material. Average progressing speed for the cross-
sectional area is shown in Figure 8.3. Following observations
can be derived from these figures.
(1) Nano-filled XLPE exhibits much improved endurance to
PDs than non-filled XLPE.
(2) In particular, the best performance is possessed by XLPE
filled with surface-treated filler.
(b) Eroded volume
8.2 PD EROSION 2 Figure 8.5. PD erosion depth (a) and PD erosion volume (b).

An electrode system as illustrated in Figure 8.4a was used for


PD erosion evaluation of three kinds of XLPE samples. On
each sample, 4 rod electrodes were placed on different places
and connected to a high voltage transformer by a 50 k
resistor to limit the current in case of a flashover. The rod
electrodes were made of steel of 6 mm in diameter with a
sharp edge at the end of the sample. All samples were exposed
to surface discharges for 50 h at a voltage of 10 kVrms (50 Hz)
(a) Electrode for surface erosion
at the rod electrode. After the exposure, the eroded spots were
cast with RTV-silicone rubber and those negatives were
scanned by a 2D-laser profiler (type: nanofocus scan). This
was necessary because a direct scan did not give good results.
The scanning resolution in X- and Y- direction was 10 m, in
Z-direction (height) better than 50 nm. Two scans (in the
direction of the X- and Y-axis) were combined and post
processed to reduce scanning errors. Additionally, the tilt of
the surface of the cast if existing was analyzed and
corrected.

(b) Profile of eroded area From these data, the eroded volume was calculated in an area
of 5 mm around the center of the rod electrode, as shown in
Figure 8.4. Electrode of 6 mm diameter (Similar to IEC (b) Electrode) for
surface erosion by PDs (a) and a profile of eroded area (b). Figure 8.4b. As a second value to describe the depth of the
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1509

erosion, the parameter 95% erosion depth was introduced. Annex


This parameter represents the depth, above which 95% of all Table A1. Data and Contributors.
scanned values in the analyzed area are located, i.e. 5% of all
scanned values are below this value. The advantage of this Sections Contributors
parameter compared to the maximum erosion is its good 4.2, 6.3 Bulinski
6.6 Castellon
immunity to scanning errors, whereas the value of the 4.3 Frchette
maximum erosion depth can be corrupted by one single 4.1 Gubanski
scanning error. 8.2 Kindersberger
4.4, 5, 6.4, 7.1, 8.1 Montanari
Figure 8.5 shows results of PD erosion depth (a) and PD 4.5 Morshuis
erosion volume (b). The erosion of the XLPE samples shows 7.3 Nagao
consistent values for the eroded volume and the 95% erosion 7.2 Plissou
depth. The erosion values of all 3 samples are in the same 3.3, 6.2 Tanaka, T. and Ohki
6.5 Tanaka, Y.
order of magnitude, but small differences can be noticed.
3.2 Sutton and Han
While one of the XLPE samples filled with non-functional 3.1, 3.4 Vaughan
nano filler shows less erosion than the unfilled XLPE sample,
the erosion values for some of the XLPE samples filled with
functional nano filler are higher (median values). Therefore, 9 CHRACTERIZATION DISCUSSION
an effect of the filler treatment on the PD resistance seems SEM observations have confirmed that nano silica filler
probable. Nonetheless, it should be considered that the span of particles are uniformly distributed throughout XLPE matrix.
the erosion of all samples is quite large and the results cannot They span a wide size range from about 300 nm to 30 Pm. The
be considered significant as only 4 values per samples are large objects appear to be just particles rather than aggregates
available. of smaller particles. No big difference in size distribution is
clearly recognized between unfilled and filled XLPE samples,
(1) Addition of nano fillers does not necessarily decrease PD but the distribution of particle sizes appears displaced
erosion depth by this evaluation method. somewhat to smaller dimensions for filled XLPE.
(2) Test method and data analysis methods should be further From DSC measurement, most of the cross-linking residues
investigated. can be removed after the heat treatment at 60 C for 60 min.
8.3 DISCUSSION OF PD RESISTANCE However the peak of the heat flow difference increases
monotonically with annealing time in an approximately
By using a rod-to-plane electrode structure with a gap, a logarithmic manner, and therefore it can be postulated that
significant effect of nano filler was found on PD resistance of some residues remains even after such a heat treatment for a
XLPE as follows. Filled XLPE exhibits much improved week or so. Some of the dielectric studies may be sensitive to
endurance to PDs than unfilled XLPE. The best performance the remaining residues. Some of the participants preferred the
was possessed by XLPE filled with surface-treated filler. On heat treatment at 80 C for that reason. According to DSC
the other hand, no apparent improvement was made by filler measurement, there is no apparent change in crystallinity due
addition when an electrode system similar to the IEC (b) to nano filler addition to XLPE. But it was clarified that a
electrode was used. melting point is shift down from 104 C for unfilled XLPE to
Difference between the above two experiments are as 102 C for filled XLPE. This suggests that nanoparticles will
follows: suppress the formation of crystal as a result of polymer/
nanoparticle interactions.
(1) Electrode systems are different. The former generates
more or less void discharges, while the latter brings about By the GC/Mass spectroscopy measurement, it was
surface discharges, although applied voltage was the same elucidated that some of cross-linking residues remains after
10 kVrms for both the cases. the heat treatment at 60 C for a week, while no residues are
detected after the heat treatment at 80 C for a week in
(2) Erosion depths are different. They have values from 100 vacuum. This is in good agreement with the conclusion from
to 300 m for the former, while they are about 50 m. the DSC measurement. Nano particles thought to remain on
The first difference is not enough to explain the discrepancy the surface after PD exposure cannot be detected by the
appearing in the two results. The second difference must be a Raman spectra measurement.
potential reason. Time of exposure to PDs is not long enough From the analysis of material characterization, the following
to evaluate improvement in the latter experiment. This conclusions are made:
reason is postulated from the data in shorter time in the
former electrode system. In the case of the latter electrode (1) Nano filled samples for our test are defined as XLPE
system, roughness of the eroded surface should be also filled with nano silica particles of 300 nm to 30 Pm in
evaluated. size with their macroscopic homogeneous dispersion.
Experimental data used in the paper were provided by (2) Some interactions between nano particles and XLPE
contributors for their respective sections as shown in Annex matrices can exit so as to suppress the formation of
Table A1. crystalline order.
1510 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

(3) No measurable amount of cross-linking residues exist in function is considered to reduce impurities and thereby
the case of the heat treatment at 80 C for a week, while heterocharge. Furthermore, it was proposed elswhere that
some of them are suspected to remain in the case of the homocharge is easier to be injected into filled XLPE than to
heat treatment at 60 C for a week, unfilled XLPE. In the latter case, charge compensation takes
place when nano filler is added. Charge packet appears at the
9.1 PERMITTIVITY AND DIELECTRIC LOSS extremely high electric field near breakdown. This can be
There are some effect cross-linking residues on permittivity suppressed by nano filler, but no nano filler effect is clarified
and dielectric loss in the case of the heat treatment at 60 C, in this experiment.
while no such effects are recognizable in the case of the heat 9.4 DIELECTRIC BREAKDOWN STRENGTH
treatment at 80 C. This observation is in a good agreement
with the results obtained by DSC and CG/Mass spectroscopy It was found that there is no significantly positive effect of
measurement. Permittivity and dielectric loss can be analyzed nano filler on the change of ac and impulse breakdown
in two distinct frequency regions, i.e. the low frequency region strength. But the highest ac and impulse breakdown strengths
and the high frequency region. Permittivity and dielectric loss were obtained for filled XLPE with surface-modified nano
in the low frequency region is mainly related to electrical filler, although the difference is not so marked.
conduction and slow-orientation components of dipoles, and 9.5 PD RESISTANCE
those in the high frequency correspond to electronic
polarization and fast-orientation components of dipoles. It was found that PD resistance of XLPE can be significantly
improved by nano filler addition. The surface modification
As for permittivity, the following conclusions are derived. In nano filler particles will further improve PD resistance.
the high frequency region, there is not much difference in
permittivity among unfilled XLPE, filled XLPE with and 9.6 CROSS ANALYSIS
without surface modification. On the contrary, in the low
Cross-linking residues were first evaluated by material
frequency region, there is a significant difference in
characterization with DSC and GC/Mass Spectrometry. Heat
permittivity among the above three kinds of samples. In both
treatment at 80 C for a week is appropriate enough to
cases, nano filler particles are considered to reduce the
measure dielectric properties. This was verified by a series of
permittivity. Apparent increase of the permittivity by nano
dielectric property measurement. SEM observation clarified
filler addition may be caused by cross-linking residues.
that prepared filled XLPE samples include 5 wt% nano silica
As for dielectric loss, the following conclusions are derived. particles ranging 300 nm to 30 Pm in size with their
In the low frequency region, it is not decisive which is less macroscopic homogeneous dispersion. Even if size
lossy, unfilled XLPE or filled XLPE. But the dielectric loss of distribution is relatively large, nano filler included in XLPE
unfilled XLPE seems to be smaller than that of filled XLPE. are effective for some of dielectric performances. Surface
In the high frequency region, it is possible to postulate that modification of nano filler particles also adds a further
nano particles will reduce the loss, although the residues will improvement in dielectric properties, although the state of
increase it. Furthermore, the functionalized nano filler will interfaces between nano filler particles and XLPE matrices
work to reduce the dielectric loss in the both low and high cannot be investigated by the present characterization
frequency regions. In the low frequency region, the dielectric techniques.
loss must be sensitive to the amount of the residues, even if
Permittivity and dielectric loss, dc conductivity, space charge,
they are small in content. Values of the loss might be
dielectric BD strength and PD resistance were evaluated for
determined by a balance of roles between nano filler particles
unfilled XLPE and filled XLPE. It is difficult to discuss them
and cross-linking residues.
with data of material characterization in this research, because
9.2 DC CONDUCTIVITY only limited information is available. We just know that we
used filled XLPE samples include 5 wt% nano silica particles
Nano filler acts to significantly reduce dc conductivity in
ranging 300 nm to 30 Pm in size with homogeneous
XLPE. Surface modified nano filler additionally reduces dc
dispersion as nanocomposites for evaluation, and that cross-
conductivity. Since dc conductivity corresponds to the
linking by-products can be removed by a proper heat treatment.
dielectric loss at very low frequency, then performance of dc
conductivity should be correlated with that of the low Permittivity and dielectric loss, dc conductivity, space charge,
frequency dielectric loss. But unfortunately they are not in dielectric BD strength and PD resistance are not
good agreement. It is because the performance might be interdependent. Dielectric permittivity (real and imaginary) at
sensitively affected by a balance of roles between nano filler very low frequency must be related to dc conductivity. But no
particles and cross-linking residues. similar dependence was obtained as nano filler effects.
Measurement techniques for permittivity should be
9.3 SPACE CHARGE
coordinated through information exchange. Nano filler effect
It was found that heterocharge is formed for unfilled XLPE. is visible for space charge, and it will be more marked at
It is considered to originate from some remains of cross- higher electric field at which a packet charge appears. Short
linking residues and natural impurities. It was also confirmed time BD strength is not much affected by nano filler addition,
that nano filler acts to reduce such heterocharge. Nano filler while PD resistance as long term performance is much
particles are characteritic of adsorbance of impurities. This improved by this technique.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1511

10 CONCLUSIONS (11)Short time ac BD strength and impulse BD strength


are both unaffected by nano filler addition. But data
Round robin-like tests were carried out on XLPE and scatter is significantly reduced. A longer time
XLPE/nano silica nanocomposites with and without nano filler performance such as treeing lifetime must be nano
surface modification. This research is unique for two reasons. filler sensitive.
First, the materials were manufactured and provided by one
source only. This is extremely important, because nominally (12)PD resistance is markedly improved by nano filler
the same nanocomposites prepared by different investigators, addition, as expected. From this, we may expect
nominally with the same techniques, often show different improvements in the (long-term) voltage endurance
characteristics. Second, experienced participants carried out qualities of nano-SiO 2/XLPE formulations.
tests by their respective expertise. Nevertheless, differences in Overall, several important improvements in key
data were found. dielectric and insulation properties over unfilled XLPE
Following conclusions are derived from the present are confirmed by these cooperative tests. We suggest this
cooperative experiments: augurs well for the potential application to MV and HV
extruded cables.
(1) SEM, DSC, GC/MS and Raman techniques are useful
to characterize XLPE nanocomposites.
ACKNOWLEDGMENT
(2) Nano filler interacts with XLPE matrices to reduce a This work was performed as one of the activities of CIGRE
melting point by 2 degree C of temperature. WG D1.24 (Nanocomposites) under the guidance of CIGRE
(3) Extrinsic impurities such as cross-linking by-products SC D1. The authors are indebted to the persons of their
can be removed to permissible level by a proper heat institutes and companies who supported their CIGRE work.
treatment in vacuum. This was clarified by DSC and They are also thankful for the former Chairman Professor E.
GC/Mass techniques. But some of the properties are Gockenbach, the present Chairman Professor J. Kindersberger,
sensitive to the residues. and Secretary Professor J. Holboell, AG 06 Convenor Dr. J.
Densley and all related persons in charge for their unwavering
(4) SEM observation exhibited that samples prepared for encouragement. They appreciate also the rest of the WG
evaluation are XLPE filled with nano silica particles D1.24 members who joined discussion to result in this fruitful
of 300 nm to 30 Pm in size with their macroscopic outcome.
homogeneous dispersion.
(5) Raman spectroscopy did not detect any significant REFERENCES
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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1515

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[128]K. J. Kingma, and R. J. Hemsley, Raman Spectroscopic Study of Toshikatsu Tanaka (SM95-F00) was born in
Microcrystalline Silica, American Mineralogist, Vol. 79, pp. 269-273, Tokyo, Japan in 1939. He is presently a Research
1994 Fellow at IPS Research Center of Waseda University.
[129]D. I. Bower and W. F. Maddams, The Vibrational Spectroscopy of He obtained the Ph.D. degree from Osaka University.
Polymers, Cambridge University Press, Cambridge, 1989. He worked until 2009 as Professor at IPS Graduate
[130]A. M. Macdonald, A. S. Vaughan and P. Wyeth, Application of School, Waseda University. He worked for CRIEPI for
Confocal Raman Spectroscopy to Thin Polymer Layers on highly 38 years and ended as Vice President for the last 6
scattering substrates: a case study of synthetic adhesives on historic years, and temporarily for Salford University in UK
textiles, J. Raman Spectrosc., Vol. 36, pp. 185191, 2005. (1970-1972), Rensselaer Polytechnic Institute and
[131]L. Wang, A. Cavallini, G. C. Montanari, A. S. Vaughan and N.A. General Electric in the USA (1975-76), and Kyushu
Freebody, PD-induced surface degradation of Insulation-embedded University in Japan (1993-1997). He is a recipient of the Ministry of Science
Cavities: Microscopic Investigation, submitted to Intl. Sympos. Electr. and Technology Prize in 2000, IEEJ Technology Progress Award in 1988, and
Insulating Materials (ISEIM), 2011. IEEE Dakin Award in 2002. He is active in IEEJ, IEEE, and CIGRE. He is an
[132]N. A. Freebody and A.S. Vaughan, Surface Ageing of Dielectric Associate Editor of the IEEE Transactions on Dielectrics and Electrical
Materials in a Controlled Atmosphere: a Raman Microprobe Study, Insulation and an IEEJ Life Fellow.
IEEE Conf. Electr. Insul Dielectr. Phenomena (CEIDP), pp. 54-57, 2004.
[133]A. S. Vaughan, I L Hosier, S J Dodd and S J Sutton, On the Structure Alexander Bulinski (F'95) received the Ph.D. degree
and Chemistry of Electrical Trees in Polyethylene, J. Phys. D: Appl. (1976) in electrical engineering from the Wroclaw
Phys., Vol. 39, pp. 962978, 2006. University of Technology, Poland. He joined the
4. Permittivity National Research Council of Canada in 1977 and has
[134]IEE Monograph Series 14, Electrical Insulating Materials and their been associated with it ever since. His research
Application, Edited by R. W. Sillars, Peter Peregrinus Ltd on behalf of interests include aging processes in high voltage
IEEE, p. 144, 1973. insulation, insulation system design and testing, high
6 Space Charge voltage measurements and the development of
[135]CIGRE Task Force D1.12.01, Space Charge Measurement in diagnostic measurement techniques and
Dielectrics and Insulating Materials - PEA, PWP (PIPWP & LIPP) and instrumentation for assessing the operating conditions
TSM methods, CIGRE Technical Brochure No. 288, pp.50, 2006. of different types of high voltage insulation. He is a recipient of the IEEE-
6.1 TSM Principle and Mathematical Treatment (Castellon) DEIS Eric O. Forster Award (2007).
[136]A. Toureille, P. Notingher jr, N. Vella, S. Malrieu, J. Castellon and S.
Agnel, The Thermal Step Technique : an Advanced Method for
Studying the Properties and Testing the Quality of Polymers, Polymer Jerome Castellon (M08) was born in Lodve,
Intl., Vol. 46, pp. 81-92, 1998. France, in 1970. He received the Ph.D. degree in
[137]P. Notingher jr, A. Toureille, S. Agnel and J. Castellon, Determination electronic, optronic and systems from the University
of electric field and space charge in the insulation of power cables with of Montpellier 2 "UM2", France, in 1997. He has been
the thermal step method and a new mathematical processing, IEEE the technical manager of Advanced metrology for
Trans. Industr. Appl., Vol. 45, pp. 67-74, 2009. electrical engineering "Am2e" Company until 2003.
6.3 Space Charge (Bulinski) Since then, he is an assistant professor at the UM2. He
[138]Y. Li and T. Takada, Experimental Observation of Charge Transport is working with the Energy and Materials Group
and Injection in XLPE at Polarity Reversals, J. Phys. D: Appl. Phys. "GEM" of the Southern Institute of Electronics "IES"
Vol. 25, pp. 704-716, 1992. (joint facility of the UM2 and French National
[139]K.S. Suh, S.J. Hwang, J.S. Noh and T. Takada, Effects of Constituents Council for Scientific Research "CNRS"). He has been involved in various
of XLPE on the Formation of Space Charge, IEEE Trans. Dielectr. research fields related to insulating materials and system for electrical
Electr. Insul., Vol. 1, pp. 1077-1083, 1994. engineering. His major research activities concern electrical characterization,
[140]M. Fu, G. Chen, L.A. Dissado and J.C. Fothergill, Influence of Thermal dielectric phenomena and diagnostic techniques development. He is a member
Treatment and Residues on Space Charge Accumulation in XLPE for of the IEEE Dielectrics and Electrical Insulation Society, of the CIGRE SC-
DC Power Cable Application, IEEE Trans. Dielectr. Electr. Insul., Vol. D1 Materials and Emerging Technologies, of the French Society of
14, pp. 53-64, 2007. Electrostatics and of the Socit des Electriciens et Electroniciens.
1516 T. Tanaka et al.: Dielectric Properties of XLPE/SiO2 Nanocomposites Based on CIGRE WG D1.24 Cooperative Test Results

Michel Frchette (SM95) has a graduate Peter Morshuis (M95) was born in The Hague, The
background in physics. He joined Hydro- Netherlands, in 1959. Between 1986 and 1988, he was
Qubecs research institute (IREQ) in 1981. involved in studies for NKF Kabel on the effects of
Since then, he has been involved in applied defects on the lifetime of high voltage cables and in
basic research in various fields related to studies on new cable concepts. Since 1988, he has been
electrical insulation and insulating materials. a staff member of the High Voltage Group at Delft
His major contributions concern discharge University of Technology where he was awarded the
physics, dielectric phenomena, and most Ph.D. degree in electrical engineering in 1993 on the
recently nanodielectrics. topic of ultra wide-band electrical and optical studies of
partial discharges in solid dielectrics. In 1998, he was a visiting Professor at
the University of Bologna. Since 1999, he is an Associate Professor in High
Stanislaw M. Gubanski (M'89-SM'90-F'01) received the M.Sc. (high voltage Voltage Engineering at Delft University of Technology. His most important
engineering) and Ph.D. degrees (material science) from fields of interest are HVDC (materials and systems), nanodielectrics, space
the Technical University of Wroclaw, Poland, in 1973 charge, partial discharge, smart grid and aging of electrical insulation. He is
and 1976, respectively. He was a Research Fellow at involved in a number of CIGR and IEEE activities and he is an Associate
the University College of North Wales Bangor, U.K Editor of the IEEE Transactions on Dielectrics and Electrical Insulation.
from 1976 to 1977, a senior lecturer at the Technical
University of Wroclaw, Wroclaw, Poland, from 1977 Yasuhiro Tanaka (M99) was born in Fukuoka, Japan
to 1988. Afterwards he was an associate professor at in 1961. He received the B.E., M.E. and Ph.D. degrees
the Royal Institute of Technology, Stockholm, Sweden. in electrical engineering from Waseda University, Japan,
Currently, he is professor of High Voltage Engineering in 1986, 1988 and 1991, respectively. He became a
at the Department of Manufacturing and Materials Lecturer, an Associate Professor and a Professor at
Technology, Chalmers University of Technology. He currently is Vice Musashi Institute of Technology, in 1992, 1998 and
President Administrative of IEEE-DEIS and a Senior Associate Editor of the 2004, respectively. He was a Visiting Scientist at
IEEE Transactions on Dielectrics and Electrical Insulation. University of Southampton from 1999 to 2000.
Currently, he is developing a measurement system for
Josef Kindersberger (M87). He received the Dipl.-Ing. space charge distribution in various solid dielectric
and the Dr.-Ing. materials at high temperatures, under ultra-high electric field or under
degrees from the Technische Universitaet Muenchen in irradiation of gamma-ray or electron-beam in vacuum. (Musashi Institute of
1979 and 1986, respectively. From 1986 to 1995 he was Technology was renamed Tokyo City University.)
with the High Voltage Insulator Group of Hoechst
CeramTec AG. In 1995 he became full professor at the Serge Plissou (M77-SM96) was born in Castres,
Technische Universitaet Dresden. Since 2001 he has France, in 1951. He received the B.Sc.A., M.Sc.A.
been Head of the Institute of High Voltage Technology and Ph.D. degrees in engineering physics from the
and Power Transmission of Technische Universitaet cole Polytechnique, University of Montral,
Muenchen, Germany. He is active in IEC (chairman of Qubec, Canada, in 1976, 1979 and 1986,
TC 36), CIGRE (Chairman SC D1), IEEE and VDE/ETG. respectively. Since 1982, he joined the Institut de
recherche dHydro-Qubec (IREQ) as a member of
Gian Carlo Montanari (M87-SM90-F00) was the scientific staff. His research interests are
born on 8 November 1955. He is currently Full materials for cables, including dielectric properties of
Professor of Electrical Technology at the Department polymers, extruded dielectric cable performance, physico-chemical
of Electrical Engineering of the University of characterization of insulations and diagnostic techniques for underground
Bologna, and teaches courses of Technology, lines. He is a registered engineer in the province of Qubec, a senior member
Reliability and Asset management. He has worked of IEEE/PES, involved in several activities of the ICC/PES, and in CIGRE
since 1979 in the field of aging and endurance of SC-D1 Materials and Emerging Technologies.
solid insulating materials and systems, of diagnostics
of electrical systems and innovative electrical Alun Vaughan (M06-SM07) has a B.Sc.
materials (magnetics, nanomaterials, electrets, degree in chemical physics and a Ph.D. degree in
superconductors). He has been also engaged in the fields of power quality and polymer physics. After working at the UKs
energy market, power electronics, reliability and statistics of electrical Central Electricity Research Laboratories and
systems. He is a member of AEI and Institute of Physics. He is a member of spending a period as an academic at The
the AdCom of the IEEE DEIS. Since 1996 he is President of the Italian University of Reading, he is now Professor in
Chapter of the IEEE DEIS. He is an Associate Editor of IEEE Transactions on Electronics and Computer Science at the
Dielectrics and Electrical Insulation. He is founder and President of the spin- University of Southampton. He is an EPSRC
off TechImp, established on 1999. He is author or coauthor of about 600 College member, Chair of The Dielectrics Group
scientific papers. He is an Associate Editor of the IEEE Transactions on of the Institute of Physics, a Fellow of the
Dielectrics and Electrical Insulation. Institute of Physics, and a member of the IET.

Masayuki Nagao (M90) was born in Gifu, Japan in Yoshimichi Ohki (M76-SM98-F00) received the B.
1950. He received the B.Eng., M.Eng. and D.Eng. Eng., M. Eng. and Dr. Eng. degrees in 1973, 1975 and
degrees from the Nagoya University, Japan in 1973, 1978, respectively, all from Waseda University, Japan.
1975 and 1978, respectively. He became a Lecturer in He joined the teaching staff of the Department of EE,
1980, an Associate Professor in 1985 and a full Waseda University in 1976 and is presently a
Professor in 1998 in the Department of Electrical and Professor. He was a Visiting Scientist at the
Electronics Engineering of Toyohashi University of Massachusetts Institute of Technology from 1982 to
Technology, Japan. He is engaged primarily in research 1984. He is a recipient of the Forster, Whitehead, and
on high-field electrical properties of polymers and insulation degradation Ieda Awards from IEEE-DEIS, Outstanding
phenomena. He received a Paper Awards from IEEJ in 1991 and from Achievement Award and two Best Paper Awards from
Japanese National Committee of CIGRE in 2006 and 2010, and Technical IEE Japan, and other awards. His major research interests cover various
Committee Award from CIGRE in 2005. He is a member of the IEE Japan, organic and inorganic dielectrics, e.g., those used in optical fibers and power
Japan Society of Applied Physics, CIGRE and presently a chair of IEEE DEIS cables. He is an Associate Editor of the IEEE Transactions on Dielectrics and
Japan Chapter. Electrical Insulation.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 5; October 2011 1517

Clive W. Reed (M80) graduated from the University Suh Joon Han (M '98) is a Senior R&D Specialist
of Bristol, England in 1956 with a First Class Special for the Wire and Cable buisness of The Dow
Honors B.Sc. degree in organic chemistry and with a Chemical Company. He holds a Ph.D. degree in
PhD. Degree in physical chemistry in 1960. After a polymer science and engineering from Lehigh
postdoctoral fellowship in low temperature physics at University of Bethlehem, Pennsylvania. Since 1998,
the National Research Council of Canada in Ottawa, in he has been involved in research and development
1963 he joined GE Corporate Research and projects for semiconductive shields compounds and
Development, Schenectady, NY, where he worked on insulation materials in power cable applications, and
high voltage insulation material and design and dielectric fluids for transformer applications. He is a
dielectric phenomena for numerous commercial member of IEEE Dielectrics and Insulation Society,
applications until retirement in 2002. He is past and Society of Plastics Engineers. He is an author of more than 36 technical
chairman of CEIDP, past member of NAS-NRCs Committee on Dielectrics, papers and presentations, and holds 10 patents.
past chairman of CIGREs Study Committee on Materials for
Electrotechnology, and has served in many capacities for these and other
professional organizations and on NIST, US Government, and industrial
review and advisory committees. Presently, he is an independent consultant on
dielectrics and high voltage insulation materials and design.

Simon Sutton has a B.Sc. degree in physics with


subsidiary mathematics and a Ph.D. degree in
polymer physics both from the University of
Reading. After holding several postdoctoral
positions, including a Royal Society fellowship, he
spent more than 10 years with National Grid in the
UK working on cables research before leading teams
on Cables Policy, Condition Monitoring and Asset
Management. In 2007 he joined Dow Wire and
Cable a market facing business of The Dow
Chemical Company as European End Use Marketing Manager. He is a
Member of the Institute of Physics and an active member of CIGRE.