2005 Annual Report Conference on Electrical Insulation and Dielectric Phenomena

Effect of Acid Immersion on RTV Silicone Rubber Coatings in Inclined Plane Tests
Shesha H. Jayaram 1 All Naderian Jahromi 1,2 Ayman H. El-Hag 1 Edward A. Cherney 1 2 Hosein Mohseni2 Majid Sanaye-Pasand 1 ECE Department, University of Waterloo, Ontario, Canada 2ECE Department, University of Tehran, Iran

Abstract: The paper presents the results of an investigation into the effect of acid immersion on the aging of room temperature vulcanized (RTV) silicone rubber coatings in inclined plane tests (INP). Two commercial coatings, RTV-A filled with ATH (aluminum tri-hydrate) and RTV-B filled with silica, are compared before and after acid immersion. Acid aging consists of immersing the samples in 3.9 pH nitric acid at a temperature of 90C for 2 weeks. The relative comparison between the two samples is based on the development of the fundamental and third harmonic of the leakage current during IPT tests, eroded area, the time to failure and SEM microphotographs. All of these observations show that acid rain damages RTV-A more severely than RTV-B. However virgin ATH filled sample showed a better performance compared to the silica filled material.

physical change in material properties such as a complete loss of hardness. The most severe influence of acid rain on dielectric materials is the de-polymerization at high acidity, i.e. low pH [4].
Room temperature vulcanized (RTV) silicone rubber coatings have been used to improve the flashover performance of ceramic insulators for more than 30 years. In addition, inorganic fillers are used in silicone rubber coatings to improve certain physical properties and to impart suitable erosion and tracking resistance to the material. These coatings are applied as a film with a thickness about 0.5 mm to porcelain and glass insulators. The anticipated life of present coatings is about 15 years [6] and guidelines for the evaluation of aging are published in JEC and IEEE guides. Aging in these guides considers only the loss of hydrophobicity which is normally brought through the loss of silicone fluid from the bulk of the coating, but none have considered the effect due to acid rain. There are primarily two types of fillers that are used in preparing coatings, namely alumina tri-hydrate (ATH) and ground quartz or silica. As yet, there has not been a performance evaluation between these two fillers in acid rain. This paper presents an investigation into the effect of acid on the aging of RTV coatings on two commercial coatings, one filled with ATH and the other is filled with silica. The inclined plane test, salt fog test, tracking wheel and voltage breakdown are some of the commonly used test methods to evaluate the aged polymeric insulators and coatings. Parameters like the leakage current, contact angle, SEM, TGA, FTIR, WAXD, gas chromatography, mass spectrometry and tan 6 have been used in analyzing results of aging [212]. But, the most common method for simulation of acidic aging is soaking of the coated samples in acid [410]. Nitric acid was selected as the main acid for aging process in this study. Different accelerating rates for aging have been reported. A wide variety of pH between 2 and 5.6 has been used for this propose. According to a field

Introduction
The effects of acid rain have been recorded in parts of the United States, Germany, Netherlands, Switzerland and Australia. It is also becoming a significant problem in Japan, China and in Southeast Asia [1-5]. The definition of acid rain is not very clear, but generally rainwater with a pH below 5.6 is called acid rain and the main acids in the rain are sulfuric and nitric acids [4]. The root cause of acid rain largely stems from the burning of coal and hydrocarbon fuels. When the atmosphere is polluted with sulfur oxide (SO2) and oxides of nitrogen (NOx), the rain goes through oxidation with ozone (03) or hydrogen peroxide (H202) which forms H2S04 and HN03 before failing to the ground. Various studies have shown nitrous oxides are the main constituent of acid rain [1].

The degradation of polymeric materials in acid rain is an electrochemical process of de-polymerization that is more severe in the presence of voltage [2-12].
Acid de-polymerization occurs when OH radicals begin to sever polymer chains resulting in shorter chains in which the manifestation is a drastic

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measurement in the Connecticut coast, the acid rain has pH=3.9[3]. It was estimated that one month of immersion in acid water of pH=3.9 at 90 C in the laboratory is equivalent to 90 months of aging in the field. This is based on measurements on 345 kV post insulators of a substation, which used a commercial RTV coating [3]. This is realized by monitoring the change of weight loss of bulk RTV of laboratory soaked samples compared with field coatings using thermogravimetric analysis (TGA). But the electrical stress aging was not considered in that aging rate. In this paper, this rate (pH=3.9, T=90 C ) is used to evaluate the RTV silicone rubber coatings as an artificial aging rate, which simulates a natural aging in the field Assuming a linear relationship between laboratory aging and natural aging, an aging time of 2 weeks is equal to about 4 years in the field.

(a)

(b)

Experimental Setup and Test

The IPT setup is based on the ASTM D 2303 standard. Each sample has a 10 kQ, 200 W resistor to limit the short circuit current and the initial voltage was 2.0 kV. The contaminant was 0.1% ammonium chloride with a flow rate of 0.15 mLlmin for four hours. At each hour the voltage was increased by 250 V. The measurement instrumentation consisted of a National Instruments T PCI 6111 data acquisition card, shunt resistors to measure the current in the 6 channels and resistor dividers to monitor the applied voltage.

Figure 1: RTV-A samples after IPT test (a) non-aged sample, (b) acid aged sample.

The sampling rate was 10 kS/s for each channel. The fundamental and harmonic content of FFTI of leakage current of each of the 6 channels were recorded as well as applied voltage.
The samples were prepared by coating of materials A and B on ceramic slabs with dimensions of 50 mmX 120 mm. The thickness of coated material was about 1 mm. The test was done before and after acid aging for each sample.

I16Nu
(a)
Figure 2: RTV-B samples after IPT test (a) non-aged sample, (b) acid aged sample.

Analysis and Discussion of Results

Figure 1 shows samples of RTV-A at the end of the IPT, for aged and un-aged conditions.. The length and width of erosion area are highlighted in these figures. A large difference exists before and after aging for the two samples. Similar illustrations are shown in Fig 2 for RTV-B. These figures depict that although the damaged area for non-aged sample is higher for RTV-B, the surface degradation is more severe for RTV-A due to acid effect. Fig 3 shows the recorded FF1' of the fundamental harmonic of leakage current for RTV-A and RTV-B before and after aging.

The plots of the 3rd harmonic components are illustrated in Fig. 4. The difference in leakage current between aged and virgin samples is apparent. The increment of the third harmonic current, which is basically due to dry band arcing and chemical erosion for virgin and aged samples of RTV-B, is more or less similar to RTV-A. But the 3rd harmonic of current of the aged sample of RTV-B is not compatible to the virgin sample. In order to analyze the results and evaluate the effect of acid on RTV-A and RTV-B, the following factors were considered: average of fundamental and third harmonic of FFI' of leakage current, length of erosion, area of erosion, number of failures, time to failure based on IEC 587 and the SEM photographs.

314

-RTV-BArgin

RTV-A ag d

5o

40

80

120
Time, minutes

160

200

240

(a)
30

R1V-B irgin

RTV-A aged

E 4

2.5 1.5

2 RTV-B aged

80.5

40

80

Time, minutes

120

160

200

240

Figure3: Leakage current components measured during the IPT test, (a) Fundamental component, (b) Third harmonic component
Table 1: Comparative study of RTV-A and RTV-B before and after

(b)

acid aging.

A, virgin
Fundamental LC

ag,

B, virgin

LC (mA) Failed Samples Length of erosion

Erosion area

rd(mA) harmonic

3.0
1.0
I 19.8
95

4.74
1.68

4.0
1.4

B, aged 3.66
1.56 4 26.3
195

1 19.75
170

3 22.7
160

Timetofailure

(mm2)
(min)

190

95

136

125

The comparative results are summarized in Table. 1. It is depicted in Table 1 that just 1 sample of RTV-A failed during the IPT. The time-to-failure of virgin samples of RTV-A is longer than RTV-B and the level of the fundamental and 3rd harmonic of leakage current is also higher for RTV-B. So, it can be concluded that RTV-A has a better performance in IPT, neglecting acid aging. On the other hand, the 3rd harmonic of RTV-B increased by 11% due to acid aging but the fundamental and 3rd harmonic of leakage current of aged samples of RTV-A is increased 58% and 68% respectively.

Figure 4: SEM imaged for different RTV samples, (a) Virgin sample of RTV-A, (b) Acid aged sample of RTV-A, (c) Virgin sample of RTV-A, (d) Acid aged sample of RTV-A.

The increment of the 3rd harmonic of current is an indicator of dry band arcing on the surface of the samples. The erosion area, leakage current and time to

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failure of RTV-A has been seen to be dramatically increased due to acid immersion.
The erosion area of RTV-B increased by around 21.8% after aging but the increase was 79% for RTV-A. Time to failure for the failed sample of RTV-A changed to half compared with the virgin coating. This time is longer for RTV-B compared with RTV-A after aging, which shows that acid rain has a serious effect on RTV-A samples.

bonding affinity to main polymer which causes more resistive on chemical erosion effect of acid rain.

References
[1] D. Leduc, S. Fally, P. Vuyst, R. Wollast, "Acute Exposure to Realistic Acid Fog", Journal of Environmental Research, NO. 71, 1995, pp. 89-98 [2] X. Wang, S. Kumagai, N. Yoshimura, "Contamination Performances of Silicone Rubber Insulator Subjected to Acid Rain ", IEEE Transaction on Dielectrics and Electrical Insulation, Vol. 5, No. 6, December 1998, pp. 909-916 [3] H. Homma, C. L. Mirley, J. Ronzello, S. A. Boggs, "Field and Laboratory Aging of RTV Silicone Insulator Coatings", IEEE Trans. on Power Delivery, Vol. 15, No. 4, October 2000, pp. 1298-1303 [4] X Wang, L Chen and N Yoshimura, "Erosion by Acid Rain, Accelerating the Tracking of Polystyrene Insulating Material", Journal of Physics, Volume D: Applied Physics, No. 33, 2000, pp.117-1127. [5] J. Montesinos, R. S. Gorur, J. Goudie, "Electrical Performance of RTV Silicone Rubber Coatings After Exposure to an Acidic Environment", 1998, pp. [6] K Eldridge, J. Xu, W. Yin, A. Jeffery, J. Ronzello, S. A. Boggs, "Degradation of a Silicone-Based Coating in a Substation Application", IEEE Transactions on Power Delivery, Vol. 14, No. 1, January 1999, pp. 188- 193 [7] Nancy E. Frost, Paul B. McGrath, "Comparative Evaluation of Polymer Insulator Materials Subjected to Synthetic Rain", IEEE International Symposium on Electrical Insulation, Arlington, USA, June 1998, pp. 378-381 [8] Nancy E. Frost, G. Xu, B. McGrath, "A Examination of the Environments for Aging of Polymers", IEEE Conference on Electrical Insulation and Dielectric Phenomena, Minneapolis, USA, October 1997, pp. 354357 [9] R. Sarathi, "Investigations of Surface Degradation of High-Density Polyethylene Materials Resulting from Tracking, Using Physicochemical Analysis", Journal of Applied Polymer Science, Vol. 83, 2002, pp. 2843-2849 [10] R. Sarathi, U. M. Rao, "Analysis of Surface Degradation of Silicone Rubber Due to Tracking-A Physicochemical Approach", Journal of Applied Polymer Science, Vol. 88, 2003, pp. 2392-2399 [11] Nancy E. Frost, Paul B. McGrath, C. W. Burns, "Accelerated Aging of Insulators Under Acid Rain Conditions", IEEE International Symposium on Electrical Insulation, California, USA, April 2000, pp. 197-200 [12] Luiz H. Meyer, "A Study on the Role of Fillers in Silicone Rubber Compounds for Outdoor Insulation ", PhD thesis, Electrical and Computer Engineering, University of Waterloo, 2003

Aged coatings were also examined using scanning electron microscope (SEM). The resulting photographs are shown in Fig. 4. Comparing Figs 4-a and 4-c, there is no visible difference between virgin samples of ATH filled and silica filled coatings when the magnitude of SEM is OOX(lOO1n). However, it is evident from Fig. 4-b that a dramatic surface changes for RTV-A due to acid has occurred. One the other hand, no significant effect due to acid aging on RTV-B was found. This might be due to the strong bonding between silica filler and the polymeric matrix as opposed to ATH in these two types of samples. In other words silica shows a better performance compared with ATH in an acidic environment. However ATH has a better resistance to the discharge heat from dry band arcing in case of non-acid aged samples. This property of silica gives it an advantage over ATH filled coating to resist chemical erosion of acid. So for power plants, transmission lines and HV substations, which are placed in an acidic environment, silica based fillers might be recommended compared with ATH based fillers. The research will continue to study other important properties of silicone rubber like loss of hydrophobicity and mechanical properties of acid aged samples.

Conclusions
The IPT based experiments on two RTV silicone rubber coatings with different fillers (ATH and silica) show that ATH filler has a better performance compared with silica based coating in visual observation, fundamental and third harmonic of leakage current, length of erosion, area of erosion and time to failure. On the other hand, aging samples with nitric acid of pH=4 and T=85 C for two weeks shows that aging rate of ATH based coating is higher then silica based coating. In terms of 3rd harmonic leakage current, the aging of RTV-A is 6 times to RTV-B. Considering the percentage of erosion after and before aging as an aging factor, the ratio of this aging factor of RTV-A to RTV-B is 3.6 that show a large difference in aging due to acid. However ATH has a better resistance to the discharge heat from dry band arcing, silica has a higher

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