2009 Annual Report Conference on Electrical Insulation and Dielectric Phenomena
Evaluation of Dielectric Properties in
Polypropylene/clay Nanocomposites
N. Fuse1, T. Tanaka2, and Y. Ohki1
1
Department of Electrical Engineering and Bioscience, Waseda University, Shinjuku 169-8555, Japan
2
Information, Production, and Systems Research Center, Waseda University, Kita-kyusyu 808-0135, Japan
Abstract- Effects of nanofiller addition on four typical dielectric
properties, namely permittivity Hr’, dielectric loss factor Hr”,
space charge accumulation, and partial discharge (PD) resistance
were evaluated for polypropylene (PP) and its nanocomposites
(NCs) with nanoclay. While Hr’ and Hr” are almost independent
of temperature and frequency in the base unfilled PP, they are
highly dependent on the two parameters in the two NCs.
Namely, Hr’ increases significantly at temperatures above 20 °C
and the frequency spectrum of Hr” shows at least one
temperature-dependent peak. Furthermore, space charge
appears abundantly in the two NCs compared to the base PP.
These results indicate that plenty of mobile carriers and/or
dipoles, probably resulted from the manufacturing process,
remain in the two NCs. Notwithstanding the above-mentioned
‘inferior’ insulating properties, the two NCs have an improved
PD resistance compared with the base PP. Namely, the erosion
depth on the surface induced by PDs is the smallest in the NC
with the largest filler content, while it is the largest in the base
PP. Such differences in the effects of nanofillers on different
insulating properties are attributable to the fact that nanofillers
can improve the PD resistance simply by their presence, while the
chemicals needed for uniform dispersion of nanofillers may
sometimes increase the permittivity and abundance of charge
carriers.
I. INTRODUCTION
It is well-known that proper loading of nanofillers improves
certain dielectric properties of polymers significantly [1, 2].
However, a thorough understanding has not been achieved on
many points such as the most adequate filler for each
dielectric property. This is partly due to the lack of a
systematic study like the one in which a wide variety of
dielectric properties are extensively studied by many methods
in many institutes simultaneously using standardized model
samples. In this regard, an international project called the
Versailles Project on Advanced Materials and Standards
(VAMAS) has launched Technical Working Area (TWA) 33
to carry out a cooperative study on polymer nanocomposites
(NCs), for which 18 institutes are now working [3]. In this
scheme, the authors are evaluating the dielectric properties
such as space charge accumulation, complex permittivity, and
partial discharge (PD) resistance for isotactic polypropylene
(PP)/clay NCs.
II. EXPERIMENTAL
All the samples were supplied from the VAMAS-TWA 33
Project #2. They are unfilled base PP and its NCs containing
978-1-4244-4559-2/09/$25.00 © 2009 IEEE
507
2 and 6 wt% of clay nanofillers (Southern Clay Products,
Cloisite 20A), which are called PP-0, PP-2, and PP-6
according to their nanofiller contents. Note that PP homo-
polymer modified with maleic anhydride (Crompton,
Polybond 3150) was mixed as a dispersant in the two NC
samples. Chemicals remaining in the samples were investi-
gated by gas chromatography/mass spectrometry (GC-MS).
While space charge distribution profiles in the samples were
measured using the pulsed electroacoustic method at room
temperature, the relative dielectric constant Hr’ and loss factor
Hr” were measured by an impedance analyzer over a wide
temperature and frequency range from -80 to 140 °C and from
10-2 to 104 Hz.
Using the IEC (b) electrode system consisting of a pair of
stainless steel rod electrode and plane electrode, a 500-Hz ac
voltage of 5 kVrms was applied to the 200-Pm thick sample for
a fixed period ranging from 1 to 6 hours in order to investigate
the PD resistance. The sample surface was observed by a
mechanical surface profilometer to measure the eroded depth
by the PD degradation. Observations by scanning electron
microscopy (SEM) and energy dispersive X-ray spectroscopy
(EDX) were also carried out for the sample surface with
sputtered carbon.
III. RESULTS
It has been often reported that polar chemicals such as
maleic anhydride are used as a dispersant in PP composites to
mix inorganic fillers as homogeneously as possible and to
reinforce the resin/filler interfaces [4]. As mentioned above,
this is also the case for the present NC samples. To confirm
6
Cathode Sample Anode
4
Charge density (C/m )
3
2
0
-2
PP-0
-4 PP-2
PP-6
-6
-50 0 50 100 150 200
Thickness ( Pm)
Fig. 1. Space charge distributions observed right after the short-circuit
that followed the application of dc electric field of 10 kV/mm for 75 min.
 4 4

Relative Dielectric Constant Hr'

Relative Dielectric Constant Hr'

(a) (a)
3.5 3.5

3 3

2.5 2.5

10-2 10-1 100 101 102 103 104 -100 -50 0 50 100 150
Frequency (Hz) Temperature (°C)
0.15 0.15
(b) (b)
Dielectric Loss Factor Hr''

Dielectric Loss Factor Hr''

0.1 0.1

0.05 0.05

0 -2 0
100 101 102 103 104
10 10-1 0 50 100 -100150 -50
Frequency (Hz) Temperature (°C)
Fig. 2. Relative dielectric constant (a) and loss factor (b) as a function of Fig. 3. Relative dielectric constant (a) and loss factor (b) as a function of
frequency observed for PP-0 (circles), PP-2 (triangles), and PP-6 (squares) at temperature observed for PP-0 (circles), PP-2 (triangles), and PP-6 (squares) at
–20 °C (solid symbols) and at 80 °C (open symbols). 10-2 Hz (open symbols) and at 104 Hz (solid symbols).

the effect caused by the presence of the dispersant and its 100
byproduct, the samples were analyzed by GC-MS. As a result, PP-0
Total PD Charge (mC)

alkane molecules were detected in the two NC samples, and 80 PP-2

not in PP-0. This indicates that a certain chemical reaction
that induces the alkane molecules is involved in the synthesis
process of the NC samples.
Fig. 1 shows space charge distribution profiles observed
right after the sample, biased by dc electric field of 10 kV/mm
for 75 min, was short-circuited. A positive homocharge layer
remains in the vicinity of the anode in all samples. In PP-6, a
large positive heterocharge layer also remains in the vicinity
of the cathode.
Although the complex permittivity was measured at various
temperatures over a wide frequency range as mentioned
above, only typical results are shown in Figs. 2 and 3 to save
space. Permittivity Hr’ increases with an increase in nanofiller
content. As shown in Fig. 2, both Hr’ and Hr” have fairly flat
frequency dependencies at -20 °C in all the samples, except
for the slight increase in Hr” with a decrease in frequency.
This flat tendency disappears at 80 °C, especially in the NC
samples. Namely, in the two NCs, Hr’ measured at 80 °C
shows a negative frequency dependence, while Hr” at 80 °C
shows at least one peak. This is partly due to the formation of
a heterocharge layer by the enhanced charge transport at high
temperatures [5].
The fact that Hr’ increases with an increase in filler content is
also obvious in Fig. 3 (a). One important fact is that Hr’ in the
NCs shows a sharp increase around the temperature at which
Hr” shows a peak, as typically shown in PP-6. This indicates
that the two NCs exhibit dielectric relaxation, whereas PP-0
does not. Therefore, it is assumed that some polar substances,
PP-6
60
40
20
0
0 1 2 3 4 5 6
Voltage Application Time (hour)
Fig. 4. Sample dependence of the total PD charge integrated for the whole
voltage application time in the PD test.
probably oligomers or molecules, which induce dielectric
relaxation and charge transport, were incorporated in the NC
samples by the nanofiller loading. On the other hand, the
temperature dependence of Hr’ observed in PP-0 and PP-2 at
104 Hz is negative. This is due to the fact that thermal
perturbation obstructs dielectric polarization, as is typically
observed in inorganic solid dielectrics.
A constant ac voltage of 5 kVrms was applied to the sample
sandwiched between a rod and a plane electrode in the IEC (b)
system in order to generate PDs around the periphery of the
rod electrode on the sample surface. As a result, the total PD
charge during the whole PD test period increases with an
increase in nanofiller content as shown in Fig. 4. This is
reasonable, since the electric field is enhanced around the
electrode periphery on the sample due to the high Hr’ values of
the NC samples.

508
 60
Erosion Depth (Pm) 50 PP-0
PP-2
40 PP-6

30
20
10
0
0 1 2 3 4 5 6
Voltage application time (hour)
Fig. 5. Erosion depth degraded by PDs as a function of voltage application
time, measured for each sample.

60
50 PP-0
Erosion Depth (Pm)

PP-2
40 PP-6

30
20
10
0
0 20 40 60 80 100 Fig. 7. Surface SEM images of PP-0 (a), PP-2 (b), and PP-6 (c). Figures
Total PD Charge (mC) (a1), (b1), and (c1) represent images before degradation, whereas (a2), (b2),
Fig. 6. Relation between PD charge and surface degradation depth induced and (c2) represent those after PD degradation for three hours.
by the PDs.

50
Fig. 5 shows the maximum depth eroded by PDs, which
indicates that the depth in each sample becomes deeper almost 40
before degradation
in proportion to the total PD charge, since a good propor- degraded by PDs
Count (a.u.)

tionality between the total PD charge and voltage application 30

time is seen in Fig. 4. However, the relationship between the
depth and the total PD charge differs among the samples. 20

Namely, the depth is shallower in the NC samples than in PP- 10

0, although the total PD charge is larger in NCs. Fig. 6 shows
this relationship, with approximation lines drawn to pass
through the origin of the coordinates. The slope of each line
decreases with an increase in nanofiller content, indicating that
the PD resistance to a unit charge is improved by the
nanofiller loading. Since the slope is 1.26, 0.33, and 0.14
mm/C for PP-0, PP-2, PP-6, respectively, it turns out that the
nanoclay loading of 6 wt% improves the PD resistance by 9
times. It is worth noting that a similar result was also obtained
using a different ‘rod to plane’ electrode system [6], indicating
high reproducibility of the present result.
Fig. 7 shows the surface images observed by SEM before
and after the PD degradation. Many cavities with diameters of
several Pm to several-ten-Pm are seen on the surface of PP-0
after three hours of PD degradation as shown in (a2), while the
diameter becomes smaller by adding 2 wt% of clay nanofillers
as shown in (b2), and is too small to measure in PP-6 as
shown in (c2).
Although not shown due to the space limit, EDX analyses
were also carried out simultaneously with SEM measure-
0
Al Si Al Si
PP-2 PP-6
Fig. 8. EDX intensities of Al and Si on the surfaces of PP-2 and PP-6,
observed before and after PD degradation for three hours. The intensity is
normalized for each sample by that of carbon.
ments. As a result, only signals of C and O were observed in
PP-0, whereas those of Al and Si were also observed in the
NC samples. The signal intensities of Al and Si normalized
by the intensity of C that should originate in PP are shown for
PP-2 and PP-6 in Fig. 8. The intensity becomes larger for
both Al and Si in the two NC samples after the samples were
exposed to PDs, indicating that volatilization of polymer resin
induced by PDs results in the deposition of clay nanofillers on
the surface.

509
 IV. DISCUSSION
It has been already reported in much literature that nanofiller
loading decreases Hr’ [1, 2, 7]. However, in the present
research, loading of clay nanofillers increases Hr’ as shown in
Figs. 2 and 3. Moreover, Hr’ shows an abrupt increase in the
two NC samples at temperatures higher than 20 °C. This is
due to the occurrence of dielectric relaxation, which also
induces a large peak in Hr”. This dielectric relaxation seems to
be ascribable to polar groups in maleic anhydride or those
induced by the chemical reaction that resulted in the oligomers
detected by the GC-MS analysis.
It is quite natural for nonpolar polymers like polyethylene
and PP with excellent insulating properties to have very few
mobile carriers and polarizable dipoles. Therefore, their
dielectric properties such as permittivity, loss factor, and space
charge accumulation would be significantly affected by any
treatment like the one to disperse nanofillers that would bear
polar and/or charged chemical moieties. In this regard, the
accumulation of heterocharge in PP-6 shown in Fig. 1 seems
to be due to ionic moieties induced in the dispersion process of
nanofillers. Similar results, namely, appearance of new
dielectric relaxation and heterocharge accumulation, have also
been reported for NCs of insulating polymers such as PP,
ethylene-vinyl acetate copolymer, low-density polyethylene,
and epoxy resin [8-11]. However, it has been also reported for
low-density poly-ethylene NCs that loading of nanofillers
suppresses space charge accumulation [12]. In this regard, an
adequate post-treatment such as degassing the sample in
vacuum to remove the causal chemical would be necessary for
the present NCs to exhibit excellent insulating performance.
On the other hand, the above-mentioned results show clearly
that the PD resistance is improved by the addition of
nanofillers. Such good PD resistance is assumed to be
induced by the following three mechanisms [7]; hindrance of
cavity growth mentioned in relation to Fig. 7, deposition of
clay nanofillers with far more resistivity against PDs on the
sample surface mentioned in relation to Fig. 8, and restriction
of gas diffusion and the resultant oxidation [13]. In other
words, the presence of uniformly dispersed nanofillers
improves the PD resistance. In this regard, any dispersion
process of nanofillers may be beneficial to improve PD
resistance as long as it can disperse the fillers uniformly.
However, it is important to note that the dispersion process
may exert some unexpected influence to other dielectric
properties such as permittivity and conductivity.
V. CONCLUSIONS
Several dielectric properties such as complex permittivity,
space charge accumulation, and PD resistance in PP/clay NCs
were evaluated. As a result, the following conclusions were
obtained.
(1) Loading of clay nanofillers increases Hr’ and induces an
Hr” peak around 20 °C. This is partly due to the
occurrence of dielectric relaxation, resulting form polar
moieties such as maleic anhydride incorporated in the
510
filler dispersion process. The enhancement of space
charge accumulation by the nanofiller loading seems to
be due to ionic moieties induced in the filler dispersion
process. In this regard, an adequate post-treatment to
remove the causal moieties would be necessary to
realize excellent insulating performance.
(2) The erosion depth induced by PDs becomes shallower
by the nanofiller loading, notwithstanding the high Hr’
values of NCs, indicating that simple presence of clay
nanofillers plays a significant role in the improvement
of PD resistance.
ACKNOWLEDGMENT
The present work was partly supported by a Grant-in-Aid for
Young Scientists (Start-up) from the Japan Society for the
Promotion of Science and by a Grant for Special Research
Project from Waseda University.
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