and Effect of Fillers
Yukihiro Koshino:, Itsuki Umeda* and Michio Ishiwan**
* Polymer Insulator Division, Power Business Group, NGK Insulators, LTD.
"NGK High Voltage Laboratory, Power Business Group, NGK Insulators, LTD.
1155Tagami, Futaehri, Komaki, Aichi, 485-8566 JAPAN
Abstract
This paper describes deterioration phenomena and mechanisms
on silicone rubber housings of the polymer insulators by corona
discharges. The uxona discharge was observed on the hunk
portion the insulator tested in a fog chamber. Nitric acid and
ozone generated by the corona discharge were recognized on
that hunk portion, which was discolored and became whitish.
The discolored area was expanded with test period. Surface
conditions and mechanical properties of six kinds of the
silicone rubber containing A'FH (Alumina Tn-Hydrate) and
&CO3 (Calcium Carbonate) as fillers, were investigated after
immersion in 1N nitric acid for 96 hours.
As a result, weight loss of test pieces containing CaC03and
ATH fillers was more than those solely containing ATH.
Cracks were observed on the surface of two specimens
containing &CO3 filler, and not observed on that not
containing CaC03 filler. This shows the cracks on the
surface due to corona discharges are depending on the kind of
the filler. The careful survey on the deterioration of the
housing rubber due to the corona discharge should be done
when we select the housing materials for the polymer insulators.
1. Inhwluction
In recent years, the polymer insulators have been increasingly
U L for~ outdoor high voltage insulation since they have some
advantages comparing to the ceramic ones: such as light weight.
easy installation, contamination performance and so on. The
polymer insulators are consist of the housing rubber: such a
SIR (silicone rubber), or EPDM (ethylene propylene diene
monomer), and the core material. such as FRP rods.
Toe SIR hxs gcwcl wcathcrbility. thermal stability ;milalso
surface hydrophobicity. Surf;lcc hydrophobicity of the SiK is
0-7803-5035-9/'98/$10.0001998IEEE.
kept even after many years in service and depositing of
contaminants, by migration of LMW (Low Molecular Weight)
component fiom bulk portion[l-3].
Therefore the SiR has been widely used as housing material
of the polymer insulators for high voltage transmission lines.
But these housing rubbers will be deteriorated more or less by
environmental and electrical stresses such as acid rain, W, dry
band arc and corona discharge, because they are organic
compounds.
The tracking and erosion are caused by the dry band arc.
Effects of contaminants to the tracking and erosion resistance
performance[4-6], and mechanisms of the tracking [7] are
studied. And some fillers, for example ATH is generally
added to increase tracking and erosion resistance. The
trackmg and erosion resistance performance is evaluated by the
salt-fog test specified in IEC 61109, tracking wheel test
specified in CEA LWIWG-01 as design tests, and tracking
resistance test method with incline plane test pieces specified in
IEC 60587:dry arc resistance test specified in ASTM D495 as
test piece level tests, in many laboratories.
On the other hand, deterioration mechanisms by the corona
discharge and the effects of the filler to corona discharge
resistance have not been clarified in detail. Only relationship
between the corona discharge and the behavior of surface
hydrophobicity [8],and between the corona discharge and
discoloration of housing materials [9,10] are reported.
Generation of the corona discharge on the polymer insulators is
considered asfollows;
Potential distributions of the long rod type polymer insulator
in dry condition is almost same as that of the rod-rod gap. At
the both ends, especially at the line end, the electrical stress is
concentrated. The degree of the concentration at the end of
the polymer insulator is much higher than that of the ceramic
disc type insulators. Ekcauw the ceramic disc type insulator
hxi the capacitance bchvccn cap and pin hardware, which
 makes the potential distribution more even between the both under continuous fog condition. Dimensions of the plymer
ends of the insulator string. insulators used for the corona discharge test are shown in Fig.1.
In the case of the polymer insulator with the SiR housing,
potential distribution under water spray condition is equal to that Table 1 Fillers in silicone rubber swimens
of clean and dry condition, since water film can not be Specimen Fillers
--
continuously formed due to it’s hydrophobicity. Therefore the s1 Silica, ATH 1
electrical stress concentrates most at the line end of the polymer --s2 I
Silica, ATH2
insulator even under wetting oondition. Water drops on the s3 I silica A T H ~
surface of the polymer insulator are deformed along with the s4 I Silica, ATH3, QC03
direction of the electrical field and elehcal field at the edge of s.5 I silica A T H ~ . CXO,
the deformed water drops t m m e much higher [11,12]. -- Si6 1
Silica, ATH3, CaCO,
Corona discharges are tend to be generated around the ATH 1,P X H 2, and ATH 3 are different in kinds
deformed water drops. Nitric acid is generated by the corona &CO3 contained in SI,S5, and S6 is the same kind.
discharge. These phenomena become more remarkable when Order of the amount of GC03is SI>S5>S6.
the system voltage becomes higher. It is reported that the
elecfrical stress of the central p t i o n of the polymer insulator
for 735 kV line is about 30 kV/m and that of the line side I 2 0 0 m n 7
reaches 200-300 kV/m [13].
This paper describes changa of alppearance of the rubber of
the polymer insulator by cnrona discharges which was
generated under high electrical stress under fog condition.
Some kinds of silicone rubber :sheets containing different types
I--
of fillers were immersed in nitric acid solution, and changes of
Leakage distance : 560”
their mechanical properties were studied to confirm the effects
of nitric acid generated by the corona discharge. Fig.1 Polymeric insulator uxd for the corona discharge test.

2. Experiments Thc SiR specimens were subjected to nitric acid immersion

2-1 Specimens
Table 1shows the details ofthe filllerj in the SIR hotsing of
the specimen insulator. All the SIR specimens are HTV (High
Temperature Vulcanizing) type. The specimens, S1, S2 and
S3 contain silica as reinforcing filler, and ATH which is most
commonly used for outdoor insulat.ing materials to increase
tracking and erosion resistance performance. The specimens,
S4, S5 and S6 contain silica, ATBH and &CO3. Three
differcnt types of ATH are used in S1, S2 and (S3-S6)
respectively. These ATH are different from each other in
production processes and particle size. The specimens, S4, S5
and S6 contain the same t y F of CaC03, and the order of the
amount of &CO3 is S4S5SC. Tc~talamount of these fillers
in the rubber is almost q u a l for all the specimens. This
amount of the fillers is enough to pass the tracking resistance
performance test specified in E C 60587 (Method 1, Class 1)
and flammabilitytest specifid in IEC 60707 (level F W ) .
Three polymer insulators using SIR, S1. S2 ancl Sii a<
housing materials are cxamincct by a corona discharge test
tests. Test specimens of S1S6 were prepared by punching
out of sheets in 2mm thickness having No.3 dumbbell shape
specified in JIS K 6251. All the specimens were c u r d at
170’c under high pressure.
2-2 Corona discharge test
The polymer insulator samples were arranged in vertical
position in a test chamber (6.5 m X 0.9 m X 2.7 m) and were
energized 30 k.V from the lower end-fitting. Artificial fog
(water conductivity about 100 M S/m) was generated honi
.some nozzles, and fog injection rate wac 3-51/min. The tinic
up to when corona discharges appear and surface changes
during test duration were obsewed.
2-3 Nitric acid immersion test
The dumbbell shape specimens described in the section 2- 1
were immc&l in 1N-nitric acid solution for 24, 43, and 96
hours. Immersed specimens were taken out of the nitric x i c l
solution? and kcpt in exces of cleionized water to rcmo\c
residual nitric acid, thcn dried for 48houn at 35% in a ~ ~ ~ ~ c t ~ t i i i i

73
oven. Weight loss, appearance changes, hardness, elongation
and tensile strength were investigated.
3. Test results and discussion
3-1 Corona discharge test
Observation results of the corona discharges and the
changes of appearance of the insulators by the corona discharge
test are summarized in Table 2. After 24 hours, the corona
dixharges due to water drops were observed visually at the 1'
shed from the earth side of the S2 insulator. After 72 hours,
the corona discharges were observed on the trunk portion
between the 2d and 3"' shed from the earth side of the S2
insulator. The trunk portion of the S2 insulator on which the
corona discharges were observed slightly discolored whitish.
This phenomenon was considered to agree with the previous
ones reported by Cash et a1 [9]. After 250 hours, the corona
discharges were observed at around the end-fitting of the earth
side, and the trunk portion between the 1"and 3' sheds from the
earth side of the S2 insulator. The discoloration area of the S2
insulator was spread, and a small amount of deposition of white
powder-like material was observed on the discolored trunk
portion. After 400 hours, the corona discharges were
continuously observed, on the S2 insulator, at all around of the
trunk portion between the l*and 2d sheds from the earth side.
The area of the corona discharges observed on the S2
insulator was spread as about 3 times as the area of after 2.50
hours. However the corona discharges could not be observed
on the S1 and S4 insulators. This reason was considered that
the S1 and S4 insulators kept good hydrophobicity even after
400 hours test duration. Photographs of the trunk portion of
the S2 insulator where the corona discharges were observed are
shown in Fig.2. Leakage current was measured by less than
3mA on all three insulators. However dfierences of the
behavior of generation of the corona dkharges were
considered as due to the differences of the behavior of surface
hydrophobicity. Further researches should be needed to
understand these behavior.
The concentration of hydrogen ion in water drops on the
shed surface under the discolored trunk portion was pH0-2.0
by measuring with pH testing paper. We consider this high
concentration of hydrogen ion is due to the corona discharges.
Analytical results of anions in the water drops are shown in
Table 3. Nitride ion concentration was 700 in giml which was
much higher than that of chloride ion and sulfate ion. The
nitride ion concentration in the water drops around area
subjected no corona discharges was only 40 U giml. These
results show the acid generated by the corona discharges is
mainly nitric acid.
Ozone was generated in the test chamber. Concentration
of the ozone was 0.1-lppm by measuring with gas detector tube,
of which sensitivity ranges from 0.025 to 3 p.p.m. Since
solubility of ozone to water is much lower than nitride ion and it
easily disperses in the air, the phenomenon of discoloration to
white and depositing of the white powder-like material, which
were observed at the trunk portion was suggested to be taken
place by nitric acid.

Table 2 Appearance of corona activity and surface changes during corona discharge test

edge edge
72 No corona discharge -
Corona discharge on the hunk portion. - No corona discharge
Slight discoloration on the trunk portion.
t
250 No corona discharge Corona discharges on the trunk portion, between shcds No corona discharge
and around the end-fitting at he earth side.

74
 After 72 hours After400hours
Fig2 Photographs of the trunk portion of the S2insulator,
which was subjected to corona discharges
Table 3 Analytical results of water droplets around corona
discharge
Measuring Ions
-
Ion Concentmtions( ,U g/d)
NO; 700 (4)
Cl- 50 (30)
so,” ~~ ~~~ ~~~
Values in parenthcses show concentrations of each component
of water drops around the m a without lthe corona discharges.
The white powder-like material was scratchdoff and
analyzed by diffraction-refraction FT-R (Fourier Transform
Infra-red Spectroscopy). Spat” of the silicone rubber
housing surface beforc tested (a), and that of the white powder- studied a$ d w n i in the section 2-3, that is the acid
like material @) are shown in Fig. 3. Assignments of major
peak are also given in the figure. Since the peaks of spectrum
(b) at 1370 cm-’and 1630 cm-’ indicate nitride compounds,
this proves generation of nitric acid by corona discharges.
Although four peaks were obsewed based on ATH around
about 3400 m-’in spcctrum (a), only one peak was observed
at same portion in spectrum (b). This peak was assigned to
AI(?IO,), (Aluminum nitride). The Feaks at about 1350 cm-’
and 1650 m-’of spectnrm (b) are also assigned to AI(N03);.
The peak at 1250 mi’ based on Si-C silicone side chain in
spectrum (a) was disappeared in s p w m @). The peaks
around 1100cm-’based on Si-0-Si, silicone back-bom chain in
spectrum (a) became broad and one peak in spectrum @).
This means the white powder-like material contains silica..
These results suggests that white powder-like material
deposited on the surface of the insulator by decomposition and
oxidation of siliconc polymer of housing rubber, and that
dissolution and nitration of ATE3 were taken place with nitric
acid generated by the corona discharges.
75
4000 2’000 1500 1000 650
Wavenumber (cm-‘)
Fig3 hh-red spectra of the silicone rubber
housing before the corona discharge test, (a)
and the deposited material at the trunk
portion oE the S2 specimen, @).
teriomtion of ,&cone rubber by nitric acid
It is clarified that nitric acid generated by corona discharges
in humid condition c a m deterioration of the housing rubber
surface as discoloration and deposition of the powder-like
material. Therefore the deterioration behaviors of the silicone
rubbers used for the polymer insulators by nitric acid wa5
immersion test. Nitric acid concentration for the immersion
test w z specified as 1 N, because the lowest pH of the water
drops on the shtd surface subjected to the corona discharges
was zero. This concentration of nitric acid was considered very
high, since the nitric acid may be immediately disperxd and
diluted by rain and wind in the actual field.
The specimens immersed in 1N-nitric acid solution for 24
to 96 hours were taken out of it and continuously they were
immersed in deionized water for 24 hours to stop the progress
of deterioration by the residual nitric acid. Then the specimens
were dried in a vacuum oven at 35c for 48 hours. This
drying removes the absorbed water , and eliminates the errors
due to the weight of the residual water. Then the weight loss
and mechanical properties of the immersed rubber specimens
were measured.
3-2-1 Weight IQSS of the specimens by immersion in nitric
acid
Weight loss ratio of the spccimens by immersion in the 1N-
nitric acid solution for 24,@ and 96 hours wcre shown in Fig.4.
Tbe weights of the spccimens arc reduced lincarlv with
immcrsion period. The wcighk of the s4, S5 and SO
containing both ATH and CaC03 were remarkably reduced.
Especially 17% of weight loss was observed on the specimen,
S5 after 96 hours immersion. Weight loss ratio of the S1, S2
and S3, not containing CaCQ were smaller comparing to the
specimens containing CaCQ. The weight loss of the S1 after
96 hours immersion was only 7%. The amount of A I and Ca
in the IN-nitric acid solution which was used for immersion of
the specimen, S4 for 96 hours were measured by Inductively
Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES).
As a result, the concentration of A
I and Ca in the solution were
180 and 2700 ,U dml, respectively. This results showed
CaCO, is more easily dissolved than ATH with nitric acid.
-20 '
0 20 40 60 80 100

3-2-2 Changes of the appearance of the specimens by Immersion duration (hrs)

immersion in nihic acid
Discoloration from gray to whitish on the surfaces of the Fig.4 Weight loss ratio of shmne rubber specimens
specimens were observed after immersion in the 1N-nitric acid after immersion in 1N-nitric acid.
solution. However discoloration of the specimen, S1 after 96
hours immersion was most slight among the other specimens.
Other five specimens were discolored almost completely to
white. A number of cracks were obsewed on the surfaces of
the specimens, S4 and S5 immersed for 96 hours.
Microscopic photognpls of the surfam of the specimens, S1,
S4 and S5 after 96 hours immersion were shown in Fig.5.
The S4 and S5 are the specimens containing CaC03. These
two showed the largest weight loss ratio as shown in Fig.4.
Further microscopic photograph of cross section of the
specimen, S4 after 96 h o m immersion is shown in Fig.6.
Sponge like discolored layer in about 0.7" thickness from the
surface is observed. Also the similar discolored layer was s1 s4 s5
obsewed on the specimen S5. It was suggested that surface Fig5 Microscopic photographs of the surface of
cracks of the specimens S4 and S5 were generated by specimens after immersion in IN-nitric
dissolution of large amount of fillers into the nitric acid. Since acid for 96 hours
the nitric acid dissolves &CO3 more easily than ATH, the
QCO, filler near the surface was almost dissolved and flew
away from the rubber. These results indicate that QCO; Surf ace
should not be used as the filler for the housing rubber of
polymer insulatons without careful survey, even if CaCO,
improves mold processability or lowers costs. It is suBested
from these tests the surface cracks are the results of the attack of
nitric acid generated by corona discharge in the actual field.

[discolored

Fig6 Microscopic photographs of cross secbon

of the specimen. S4aker immersion in
IN-nitric acid for 96 hours

76
3-23Changes of hardness OS the spechemby
immersion in nittic acid
Although the fillers in the housing rubber is dissolved by
nitric acid generated by the moria discharges, it may be
predicted that surface hardness of the specimens increase by
oxidation with nitric acid. Therefore changes of hardness of
the specimens were measured by the micro durometer which
can detect the hardness up to 0.5mm ffom the surfaces. The
measurement results are shown in Fig.7. Hardness of the
specimens, S1, S2 and S3 not containing CaCO?increased with
immersion period. Increase of harclness of the S1, S2 and S3
specimenswere 10,12, and 4 pints respectively after 96 hours -15 L
immersion. Especially, hardness of the specimen, S2 0 20 40 60 80 100
increased about by 90 as absolute value after 96 hours immersion duration (hrs)
immersion. As a result, the S2 lost elasticity and became
brittle. Hardness of the specimens, M, S5 and S6 containing Fig.7 Clangis of hardness of silicone rubber specimen during
&CO3 filler decreased after 24 hours immersion once, but after immersion in IN-nitric acid
96 hours immersion the hardness increased to 0,2, and 5 points
respectively. This behaviors are considered due to the
formation of the sponge-like layer by dissolving of the almost +s1
amount of CaCO, filler in the bulk of the Sa.

3-24 Change of elongation, and tensile strength of the

"\
specimens by im"ion in niitiic acid
Typical mechanical properties, that is, elongation and tensile
strength of the specimens were measured after immersion in
1N-nitric acid for from 0 to 96 hours. Residual elongation
ratio and residual tensile strength raltio of the specimens with
immersion period are shown in Fig.8 and Fig9 respectively.
Although the residual elongaition ratio of the S1 decreased to
32% after 96 hours immersion, cracks were not observed on the 0 20 40 60 80 100
S1 surface by folding up the test piece. Residual elongation Immersion duration (hrs)
ratio of the specimens, S4, S5 and S6, which containing CaCO,
filler, decreased to 11, 7, and 4% respectively after 96 hours
immersion. Decreasing ratios of the specimens, S4, S5 and S6 Fig.8 Residu,alelongation ratio of silicone rubber specimen
at 24, and 48 hours immersion were less than those of the after immersion in 1N-nitricacid
specimens, S2 and the S3.
Residual tensile strength ratio of the specimen, S1 decreased
to 40% of the initial value with 96 lhours immersion, and the
ratios of the specimens, S2-S6 were lower than 25% of the
initial values. These behavior related with the residual
elongation of the specimen, that is the cracks apt to be generated
by slight stress on the specimen which has a small residual
elongation.

77

0 20 40 60 80 100
immersion duration (hrs)
Fig9 Residual tensile strength ratio of silicone rubber
specimen after immersion in 1N nitric acid
4. Conclusions
From these test results, we conclude as followings;
Discoloration of the silicone rubber housing surfaces of the
polymer insulator is suggested to be caused by mainly nitric
acid generated, even though both of nitric acid and ozone are
generated by the corona discharges.
- It is clarified that the ATH and CaCO, fillers added in the
silicone rubber dissolved into the 1N-initric acid during the
immersion test.
After the nitric acid immersion test for 96 hours, the thickness
of discolored layer of the test specimens containing &CO3 filler
was between 0.5 and 0.7mm, and bulk portion (the deeper part
than this) was not discolored. This means the nitric acid
attacks and dissolves the fillers at the surface layer. Then the
nitric acid penetrates (not diffuses) into the bulk portion through
the vacancies of the fillers.
* The surfaces of the specimens, S4 and S5 containing CaCO,
are cracked, since the nitric acid solves large amount of &CO3
as much ay ten times of ATH. The silicone rubber specimens
which are not containing CaCO; filler show different behaviors
on their properties during the nitric acid immersion test.
Therefore it should be considered that the perfomlances of
the silicone rubbers depend upon kinds and amount of the base
polymer and fillers. Moreover, further studies are needed to
clarify the relation between the discoloration phenomena in
actual field and thc stresses, deterioration factors and
detcrioration phenomena.
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79