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ABSTRACT
The paper reports on tests done on four commercial room temperature vulcanized
(RTV) silicone rubber high voltage insulator coatings aimed at achieving information
on the relative performance of the coatings with respect to aging. The initial
characterization of the coatings includes the identification of the primary filler type,
concentration of filler, the amount of free fluid, and the molecular species of the free
fluid. Soxhlet extraction and gas chromatography tests show considerable depletion of
fluid after accelerated aging tests in acid-water and the associated changes to the
physical properties is assessed by standard mechanical tests on coupon size specimens.
The effect of acid-water aging on the hydrophobicity is assessed by measurements of
the static contact angle and the onset of leakage current in an incline plane test.
Several field aged coatings are assessed for residual LMW fluid which is compared to
accelerated aging tests.
Index Terms - RTV silicone rubber coating, HVIC, accelerated aging, depletion of
fluid, hydrophobicity, de-polymerization, Soxhlet extraction, lifetime, gas
chromatography, LMW fluid.
1 INTRODUCTION emphasis has been on the degree at which the various fillers
are capable of reducing the mass loss during dry band arcing.
OF the concerns that users have today in using room Of course this assumes that the temporary loss of
temperature vulcanized (RTV) silicone rubber coatings for
hydrophobicity inevitably leads to the development of leakage
high voltage insulators, surely the life expectancy of the
current and dry band arcing on insulators in the field. After
coatings has been the main one. Lifetime is not easy to
many years of HVIC use, this observation has yet to be
assess as many factors play a role in the life of a coating.
reported. What has been observed by users is a loss of
However, it is generally considered that the end of life is
hydrophobicity but only on the unprotected parts of the
associated with the depletion of the low molecular weight
leakage path., for example on the upper surfaces of
fluid resulting in permanent changes to the hydrophobicity
insulators as evident in Figure 1. Flashover has also been
of the surface layer. More specifically, a loss of fluid leads
reported without the usual dry band activity that is normally
to a greatly reduced rate of return of hydrophobicity after
associated with uncoated insulators. This type of flashover
experiencing a temporary loss for example, during rain
is somewhat analogous to a wet flashover of a non-ceramic
washing. Ultimately, a permanent loss of hydrophobicity
insulator but at normal line-to-ground voltage and the
may occur but this has not yet been observed in the field.
mechanism has been referred to as a “sudden flashover”
Considerable research has been reported on the
which has been previously discussed by Gorur et al [2].
performance of high voltage insulator coatings (HVIC)
The loss of hydrophobicity of a RTV coating occurs with
dealing with the type and amount of inorganic fillers as time through natural washing and this process takes a very
documented in a review article by Hackam [1]. These long time before the coating performance is affected. In
studies have generally been performed in the laboratory by addition, as fluid diffuses into surface contaminant, the
exposing samples to salt-fog or in an inclined plane test. removal of contaminant speeds up the depletion of the fluid
The time in which a temporary loss of hydrophobicity as responsible for hydrophobicity. Furthermore, in coastal
gauged by the onset of leakage current and the ensuing regions where wetting is often constant, the loss of
physical erosion due to dry band arcing of the various coatings hydrophobicity occurs very rapidly. In other regions the
have been compared. However, in all of this work, the main loss of hydrophobicity is accelerated by acid-rain which
often causes depolymerization of the RTV coatings [3, 4].
Manuscript received on 10 January 2007, in final form 24 April 2007.
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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 15, No. 2; April 2008 445
2 CHARACTERISTICS OF COATINGS
EVALUATED
Considerable variation in viscosity, skin-over and cure
times, and specific gravity of the four commercial coatings
was observed in the as-received condition. Therefore, all
samples were made under the same conditions after
thorough mixing and left to air cure for 7 days prior to
characterization and acid-water immersion. The specific
gravity, primary filler type and concentration, porosity, the
amount of free fluid available, were the main properties
used in the characterization of the coatings. The method by
which each property was determined is briefly outlined
below. Table 1 summarizes sample composition and the
data obtained in the initial characterization.
Figure 1. Photograph of the top end of a RTV coated 500 kV station post
insulator taken at night showing corona discharge from wetted parts of the Table 1. Characteristics of cured coatings.
insulator without dry band arcing. RTV Primary Filler Specific Water Fluid
Coating Filler Wt % Gravity Absorption Wt %
Wt %
The definition of acid rain is not very clear; generally
rainwater having a pH below 5.6 is called acid-rain. The A ATH 54 1.48 13.6 2.26
main acids in rain are sulfuric and nitric acids [5] and the B ATH 51 1.54 4.20 1.13
C ATH 47 1.45 17.4 3.47
root cause of acid rain stems from the burning of coal and
D Silica 40* 1.61 4.10 1.14
hydrocarbon fuels. When the atmosphere is polluted with
* Estimated from specific gravity
sulfur dioxide (SO2) or nitrogen oxides (NOX), rain-water
goes through oxidation with ozone (O3) or hydrogen
peroxide (H2O2) forming H2SO4 or HNO3 before reaching 2.1 SPECIFIC GRAVITY
the earth. The most severe influence of acid rain on RTV The specific gravity of each coating was measured before
coatings is depolymerization [4] and in the extreme cases and after curing by accurately measuring the weight and
reported, the coating becomes very soft somewhat similar volume of the specimens.
to a putty. Acid-depolymerization of RTV coatings occurs 2.2 PRIMARY FILLER TYPE
when OH radicals begin to sever polymer chains resulting
in shorter chains in which the manifestation is a drastic Specimens of the coatings were studied in a scanning
change in material physical properties such as a loss of electron microscope (SEM) with an energy dispersive X-
tensile strength, elongation, and hardness. Previous studies ray attachment (EDAX). The particles that were dispersed
have shown that nitrous oxides are more harmful and throughout the rubber matrix were scanned and X-ray
corrosive than sulfuric acid [6]. counts of the elements were noted. The presence of
aluminum (Al) or silicon (Si) X-ray counts from the
Various rates of aging have been reported in different particles are attributed to alumina and silica fillers,
types of acids and a variation in pH between 2 and 5.6 has respectively. Thermo-gravimetric analysis (TGA)
been used for this purpose [3-5, 7, 10, 11]. According to a confirmed that Al in three of the coatings was from alumina
field measurement in a 230 kV high voltage substation, the tri-hydrate (ATH).
acid rain has a pH of 3.9 [3]. By comparing the weight loss
of field aged RTV samples to laboratory aged samples, this 2.3 PRIMARY FILLER CONCENTRATION
study suggested that one month of immersion in nitric acid Thermo-gravimetric analysis was used to analyze the
of pH=3.9 at 90 0C in the laboratory is equivalent to 90 coatings thermally. In this measurement, the temperature
months of field aging. was increased at a rate of 20 0C/min from 100 to 800 0C.
In this work, four commercial RTV coatings are The weight loss versus temperature for the RTV coatings is
examined for performance characteristics with respect to shown in Figure 2. For coatings A, B and C, the curve
aging. The loss of hydrophobicity is assessed by the ease trend changes at around 200 0C which is correlated to the
in which leakage current develops in an inclined plane test, release of the water of hydration and confirms ATH as the
measurement of the static contact angle, loss of LMW fluid, primary filler type. The concentration of ATH in these
and the loss of LMW species. The associated effect of coatings can be calculated from the percentage weight loss
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446 A. Naderian et al.: Aging Characteristics of RTV Silicone Rubber Insulator Coatings
at 350 0C being due to the release of the water of hydration The average contact angle was calculated from ten droplets;
from the ATH filler. For coating D, the silica filled each having a volume of about 20 μL , and these results are
coating, the specific gravity is used to estimate the shown in Figures 3 and 4.
concentration of filler. The water immersion test indicates that the increment of
water absorption for RTV-D and RTV-B is an order of
magnitude smaller than RTV-A and RTV-C. RTV-C lost
hydropobicity after 15 days whereas the other coatings still
exhibited a static contact angle of 85 degrees. Scanning
electron microphotographs show considerable
agglomeration of micron size filler particles in RTV-A and
this may be the reason for increased voids while in RTV-C,
the relatively large particles give rise to large voids in the
silicone matrix and the microphotographs suggest poor
bonding between the particles and the matrix.
105 RTV-B
RTV RTV-C
Ti (oC) TATH (oC) T50 (oC) Tf (oC) RTV-D
Coating
A 250 343 410 560 95
B 222 350 463 600
C 240 349 490 560 85
D 345 - 523 570
Definition of Parameters [7]: Ti: Initial decomposition temperature, TATH:
Water released ending temperature, T50: 50% weight loss temperature, Tf: 75
Final decomposition temperature.
65
2.4 WATER ABSORPTION 0 5 10 15
Water absorption of a RTV coating is an indicator of Number of Days
porosity and in filled materials this is normally associated
with poor bonding between the filler particles and the Figure 4. Static contact angle measured as a function of immersion time
silicone matrix and spaces between the particles. Moreover, in water.
soaking in water has been used previously to evaluate the
loss of hydrophobicity of polymer surfaces [8]. In these 2.5 LMW FLUID CONCENTRATION
tests, two samples of each coating were immersed in 80 0C The fluid content of the silicone rubber was measured
tap water, of 350 μS/cm conductivity, for 15 days. At 5 using the Soxhlet extraction technique with analytical grade
day intervals, the samples were removed, air dried, and the n-hexane [9]. Extraction was carried out for 72 hours on
weight gain was recorded using a microbalance having a two specimens of each coating. The dimensions of
sensitivity of 0.1 mg. The static contact angle, as recorded specimens were 2 cm x 2 cm, and 4 cm x 2 cm respectively.
with a digital camera from which the angle was measured. A vacuum oven was employed to dry the samples for 10
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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 15, No. 2; April 2008 447
hours at 80 oC and at 0.1 kPa pressure. The difference in 3.1 LOSS OF HYDROPHOBICITY
weight of the specimens before and after immersion in n- Contact angle is normally used as a means of estimating
hexane after drying in an oven is assumed to be a measure the loss of hydrophobicity after aging. However, as the
of the low molecular weight (LMW) content. A loss of hydrophobicity leads to the development of leakage
microbalance having a sensitivity of 0.1 mg was used in current and dry band arcing, a test such as the inclined
this measurement. RTV-C showed the highest percentage plane test provides a means of evaluating the effect of acid-
of free fluid while RTV-B and RTV-D had the lowest and water aging.
nearly the same percentage of free fluid.
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448 A. Naderian et al.: Aging Characteristics of RTV Silicone Rubber Insulator Coatings
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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 15, No. 2; April 2008 449
RTV-A and RTV-C exhibited the largest reductions in 3.4 GAS CHROMATOGRAPHS OF ACID-WATER
the tensile strength and elongation at break and after acid- AGED COATINGS
water aging. The degradation of RTV-C was visible even Gas chromatographs of the coatings after acid-water
without microscope (Figure 8). Such deep cracks aging were determined for the coatings according to the
resembling mud crack was not observed in the other method outlined in section 2.6, to observe the reduction in
coatings. polydimethylsiloxane cyclics as compared to new coatings.
All samples showed increased hardness with RTV-C These results are shown in Figure 9.
showing the greatest increase of 35% after 336 hours in
nitric acid. The brittleness of RTV-C is noted in the surface
cracks evident in Figure 8.
Table 4. Soxhlet extraction of LMW fluid in un-aged and acid-water All coatings showed a marked decrease in all cyclic
aged RTV coatings. groups after acid-water aging with RTV-C showing the
RTV Coating greatest decrease which corresponds to the Soxhlet
A B C D extraction results shown in Table 4. The least change
occurred in RTV-B followed by RTV-D. The reduction in
Un-aged, LMW fluid, % 2.26 1.13 3.47 1.14
the cyclic groups following acid-water aging is mainly due
Acid-water aged, LMW fluid,
%
1.11 1.03 1.25 0.97 to opening of the PDMS structure and reduction of
Loss of LMW fluid after acid- molecular weight allowing the LMW fluid to be easily
51 9 64 15
water aging, % extracted.
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450 A. Naderian et al.: Aging Characteristics of RTV Silicone Rubber Insulator Coatings
4 FIELD AGED COATINGS The return of hydrophobicity, after a temporary loss, was
investigated by measuring the static contact angle as a function
Field aged coatings of known length of time in service of time. This was done on new and field aged specimens of
and type is always difficult to obtain with any certainty as RTV-A and RTV-C. Before the test, the samples were washed
record keeping is not always reliable. However, two field in water, which simulates a heavy rain condition, to temporarily
aged coatings RTV-A and RTV-C were obtained from destroy the hydrophobicity. Then, the contact angle was
insulators having 6 and 10 years of exposure, respectively, measured at intervals over a 36 hour period by averaging the
and are identified as RTV-AFA and RTV-CFA. RTV-AFA contact angle of 10 drops, each about 20 μL volume, of distilled
was exposed to industrial contaminant in a region where water and these results are shown plotted in Figure 10.
natural rain washing occurs infrequently while RTV-CFA According to Figure 10, field aged RTV-C, identified as
was exposed to a coastal environment. Both were covered RTV-CFA, showed an initial contact angle more than 30
with a light deposit and the ESDD was not estimated. degrees lower than the un-aged sample, and again, this assumes
Soxhlet extraction tests were done on the samples with and the manufacturer has not changed the formulation over this time.
without surface contaminant following the procedure Also, the sample did not show hydrophobicity recovery in the
outlined above in section 2.5. The samples were in the 36 hour test period. But in the case of RTV-A, RTV-AFA
weight range of ~ 2.5 grams to reduce possible error. The showed a similar trend of recovery of hydrophobicity compared
samples without contaminant were cleaned using distilled with a new sample of RTV-A.
water and a soft brush. These results are shown in Table 5. There is a notable difference on the amount of low and
medium molecular weight of polydimethylsiloxane cyclics of
Table 5. Soxhlet extraction of LMW fluid in field aged RTV coatings.
field aged samples: RTV-AFA and RTV-CFA, according to
Fig.11. To quantify the difference, Table 6 compares the relative
Sample RTV-AFA RTV-CFA abundance of PDMS cyclics for new, acid-water and field aged
With contaminant, % 1.18 1.73 samples of RTV-A and RTV-C. Once again it must be assumed
Without contaminant, % 1.05 1.22 that the coating formulations have not changed and under this
assumption, the field aged samples show a marked reduction in
In the case of RTV-A, that was in the field for 6 years, the D6 to D12 cyclic groups. Inconsistencies in the relative
the LMW of the sample, RTV-AFA, is very close to the abundance of the cyclic groups below and above this range are
loss of LMW of the laboratory acid-water aged sample believed to be due to error in the detected values. In addition,
the relative abundance of cyclic groups in field aged samples are
shown in Table 4. Un-aged RTV-C has a 3.47% LMW free
similar to those detected in laboratory acid-water aged samples
fluid according to Table 4 and this value is 1.73% based on
although with only two samples, one can only speculate on the
Table 5. Therefore, RTV that was in the field for 10 years, effect of field exposure.
showed a loss of about 50 % of the LMW fluid. Of course
this assumes that no changes in the coating formulations
occurred over this time. As evident in Table 5, a part of the
LMW is trapped in the contaminant layer which may not
participate effectively to help the recovery of
hydrophobicity.
Figure 10. Return of hydrophobicity after a temporary loss as determined Figure 11. Gas chromatographs of field aged coatings, RTV-AFA and
by measurement of the static contact angle on new and field-aged samples RTV-CFA.
of RTV-A and RTV-C.
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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 15, No. 2; April 2008 451
Table 6. Comparison of the relative abundance of cyclic groups for new, rate of return of hydrophobicity that constitutes the end of
acid-water and filed aged coatings.
useful life on an insulator.
There were no field aged samples of RTV-B and RTV-D
Coatings
RTV-A RTV-C
available for this study, but it may be possible to extend the
Cyclic Acid- Field Acid- Field conclusion that the acid-water laboratory aged samples
group New water aged New water aged shows a similar loss of LMW % as the field aged samples.
aged 6y aged 10 y Based on this observation and assumption, and considering
D3 12 11 8.5 Table 4, it is predicted that RTV-B and RTV-D show a
D4 5 7 6.5 5 8 6 better performance in the field and have longer life
D5 6 6.5 9 27 2 1.5
D6 30 22 17 94 12.5 7.5 ACKNOWLEDGEMENT
D7 25 19.5 19 70 13 15 The financial support provided by Natural Sciences and
D8 13 11 9 40 8.5 10 Research Council of Canada is appreciated. The authors
D9 16 8 6.5 28 6.6 8 gratefully acknowledge Dr. Ayman El-Hag for helping in
D10 8 5.4 4.5 22 5 9 the TGA work.
D11 6 9 5 18 4.8 6
D12 10 6 6 16 6 8
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