21, rue dArtois, F-75008 PARIS http : //www.cigre.

org

A2-206 6 characters, 9 for joint meetings (to be centred)

CIGRE 2008

Failure modes of oil-immersed transformers due to static electrification and copper sulphide generation, and suppressive effect of BTA

T. Kawamura, Tokyo University

T. Kobayashi, Tokyo Electric Power Company

T. Amimoto, H. Murakami Mitsubishi Electric Corporation Y. Ebisawa Toshiba Corporation

Y. Shirasaka, Japan AE Power Systems Japan

SUMMARY Since suppression effect of 1,2,3-benzotriazole (BTA) against static electrification was experimentally confirmed and addition of BTA to insulating oil was standardized in Japan, it has been applied to many high-voltage transformers and sufficient practical results have been obtained. Through accelerated aging tests with a system in which insulating paper and copper material are placed in some insulating oils, generation of copper sulphide on insulating paper was confirmed. Effect of temperature and small amounts of chemical compounds in insulating oil were also clarified. It was confirmed that BTA suppresses not only static electrification but also copper sulphide generation. Evaluation of long-term reliability for the suppression effect of BTA against also copper sulphide phenomena should be investigated in the future.

KEYWORDS Transformer, Insulating oil, Insulating paper, Static electrification, Electrostatic charging tendency, ECT, Electrification potential, Copper sulphide, 1,2,3-benzotriazole and BTA Murakami.Hiroshi@dr.MitsubishiElectric.co.jp

1. Introduction Two fault modes of oil-immersed transformers caused by static electrification and copper sulphide generation on insulating paper have recently been reported. Both phenomena have the following features in common; the fault was caused by deterioration of insulating oil even under the normal service conditions of transformers, and was strongly influenced by the type of insulating oil. This paper reports the investigation results of suppression effect of 1,2,3-benzotriazole (BTA) against static electrification and copper sulphide generation on insulating paper. 2. Experience of BTA as static electrification passivator in Japan After initial failure with static electrification of power transformers in the 1970s, at the beginning of the introduction of 500kV transformers, the insulating oil characteristics have been improved by progress in insulating oil refining technology, application of insulating oil processing technology using clay, etc. Furthermore, after the suppression effect of BTA was experimentally confirmed, addition of BTA to insulating oil was standardized in Japan in the 1980s. Since then, BTA has been widely added to insulating oil for high-voltage transformers. [1] 2.1 Suppression of increase of electrostatic charging tendency (ECT) on insulating oil by BTA addition Various characteristics of insulating oil deteriorate with aging due to heat, oxygen, etc. while the transformer is operating. It has recently been found that sulfur compounds contained in the mineral insulating oil have the effect of increasing the electrostatic charging tendency (ECT) of the insulating oil. The sulfur compound with the highest content in mineral insulating oil is thiophene compound, and the second highest is sulphide compound. To confirm the effect of trace components contained in the insulating oil on the increase of ECT of the insulating oil, we prepared sample oil by adding various components to alkylbenzene which is a pure hydrocarbon compound without any impurities, and investigated changes in the ECT by accelerated aging tests. In addition, to confirm the effect of BTA to suppress increases of ECT of the insulating oil, we executed accelerated aging tests using sample oil in which components that cause increase of ECT were mixed together with BTA. Table 1 shows the accelerated aging test conditions. In the accelerated aging test, the sample oil put in a stainless steel container was heated with oxygen or with copper catalyst. Figure 1 shows the results of the accelerated deterioration test using only alkylbenzene. Increase of ECT was not detected under any test condition while only alkylbenzene was present. Figure 2 shows the results of the accelerated aging test using alkylbenzene with dodecyl sulphide (1,000 ppm) with or without addition of BTA (34 ppm). Figure 2 shows the test results under the conditions in which oxygen and copper catalyst were added. The ECT of alkylbenzene with dodecyl sulphide without addition of BTA increased with aging, and exceeded 1000 pC/ml. On the other hand, the ECT of alkylbenzene with dodecyl sulphide with addition of BTA increased transiently at the point of 100 hours but decreased after that. We confirmed the effect of addition of BTA in this way. The same trend was detected under other test conditions. We performed the same accelerated aging tests using alkylbenzene with thiophene compound added, but increase of ECT was not detected.

We have estimated from these test results that sulphide compounds contained in small amounts in new oil has the effect of increasing ECT of the mineral insulating oil, and that increase of ECT is promoted by deterioration of sulphide. We have confirmed also that BTA offers the suppressive effect on ECT even while sulphide is present.
Table 1: Conditions of accelerated aging tests
Item Amount of oil Conditions 500ml Oxygen: Air with 10ml oxygen (Amount of oxygen in oil: 20,000ppm) Copper catalyst:Polished copper wire (1mm, surface area: 298cm2) Combinations of oxygen and copper catalyst: Without oxygen, without copper catalyst With oxygen, without copper catalyst Without oxygen, with copper catalyst With oxygen, with copper catalyst 120 degrees C 450 hours maximum Electrostatic charging tendency (ECT) by mini-static tester

Oxygen, copper catalyst

Heating temperature Heating time Measurement item

10000

1000 ECT [pC/ml]

Without oxygen, without copper catalyst With oxygen, without copper catalyst Without oxygen, with copper catalyst With oxygen, with copper catalyst

10000

1000 ECT [pC/ml]

100

100

10

10

1 0 100 200 300 400 Heating time [hrs] 500

Without BTA Not added BTA not added With BTA Added BTA added

1 0 100 200 300 Heating tine [hrs] 400 500

Figure 1: Aging characteristics of electrostatic charging tendency of alkylbenzene

Figure 2: Aging characteristics of electrostatic charging tendency of alkylbenzene with dodecylsulphide and effect of BTA addition

2.2 Suppression of the accumulated charge on pressboard by addition of BTA to insulating oil Recently, we experienced increases of static electrification due to deterioration of not only the insulating oil but also of the pressboard in an aged transformer. To evaluate static electrification due to aging of the pressboard, we measured the electrification potential on the insulator to determine the accumulated charge density. Figures 3 and 4 show the structure of the test system for electrification potential measurement. In this test system, an oil duct to simulate the oil flow inside the transformer was made of pressboard, and the electrification potential was measured on the pressboard inside the duct so that the accumulated charge density on the pressboard could be evaluated. A measuring wire insulated with Teflon was taken out of the electrode inside the pressboard located in the center of the oil duct, and the potential of the measuring wire was measured using a surface electrometer by a non-contact method. 2

Figure 5 shows a comparison of the flow velocity characteristics of the electrification potential measured using combinations of insulating oil and pressboard at an oil temperature of 30 degrees C. New oil 1 and new oil 2 were insulating oils of different brands. The measured electrification potential levels for the combinations of insulating oil and pressboard were: Aged pressboard & aged oil > New pressboard & aged oil > New pressboard & new oil. In this way, we confirmed that the increase of electrification potential is affected not only by the increase of ECT of insulating oil but also electrification of the pressboard. As countermeasures against static electrification in aged transformers, the effects of replacement with new oil and addition of BTA were investigated by measuring the electrification potential. The aged pressboard shown in Figure 5 was used as the generation area for static electrification. Figure 6 shows the electrification potential measurement results using new oil without BTA added and new oil with BTA added. The electrification potential levels realized by the differences in the insulating oil were: Aged oil > New oil without BTA added > New oil with BTA added. In this way, we confirmed that replacement with new oil gives a positive effect to decrease the electrification potential. New oil without BTA added, however, does not provide a sufficient electrification potential decrease effect. We found that addition of BTA offers a larger decrease effect.

Relaxation Tank (100L)

Pump

Internal Electrode Oil Duct t3.2mm Sample Tank Flow Meter

To Potential Measuring Terminal

Grounded Electrode Pressboard t3.2mm

Bypass

Potential Measuring Electrode

70mm

Figure 3: Structure of Test System for Electrification Potential Measurement

Figure 4: Cross-Section of Test Sample for Electrification Potential Measurement

500

Measured Potential (V)

2000 0 -2000 -4000 -6000 -8000 -10000 0 0.5 1 1.5 2 2.5

Aged PB Aged Oil New PB Aged Oil New New Oil 1 New PB New Oil 2 Oil Flow Velocity (m/s)

Measured Potential (V)

0 -500 -1000 -1500 -2000 0 0.5 1 1.5 2 2.5

New oil with BTA New oil without BTA aged oil

Oil Flow Velocity (m/s)

Figure 5: Effect of aging on flow velocity dependence of electrification potential

Figure 6: Electrification potential suppression effect of replacement with new oil and addition of BTA

2.3 Decrease of BTA content in oil under service condition BTA added to transformer oil is gradually adsorbed to the insulating paper during transformer operation, and therefore BTA content in oil decreases during service operation. Figure 7 shows an example of the trend of decreasing BTA content in transformer oil. In one case involving a transformer to which BTA had been added more than 10 years earlier, no BTA was detected in the transformer oil but the BTA content measured in pressboard sampled from the transformer was comparable to the BTA amount originally added to the transformer oil.

ECT BTA Content ECT BTA Content Oil 1 year rest Filling Service Operation

Years

Figure 7: Decrease of BTA content in oil

3. Copper sulphide generation on insulating paper Failure of an operating transformer due to generation of copper sulphide was reported recently. [2] Even though the insulating oil passed the corrosive sulphur test, copper sulphide was generated on the insulating paper. New test methods and generation mechanisms, etc. have been investigated. It is reported that some sulfur compounds have considerable effect on copper sulphide generation on the insulating paper, but the phenomenon details including the mechanism have not been made clear. It is necessary to examine the details in the future. It has been known that the oil type (type and amount of sulphur compound in insulation oil), temperature, aging time, atmosphere, etc. affect sulphur corrosion characteristics and solubility of copper material. The same factors are assumed for copper sulphide generation on insulating paper. We investigated the factors for copper sulphide generation on the insulating paper, and examined the effects of BTA addition as a suppressive measure against copper sulphide generation through two types of accelerated aging tests. We examined the effects of acceleration factors (type of sulfur compounds in oil, heating temperature, and atmosphere) using test method A, and examined the effects of BTA addition using test method B. Table 2 shows the test conditions of each test method. Test method B is currently being examined by CIGRE.
Table 2: Test methods
Item Amount of sample oil Copper Shape of wrapped copper Bare copper plate Insulating paper Wrapping Condition Test case A 100ml Plate: Thickness: 0.2mm,Width :15mm, Length: 40mm Kraft paper Two fold wrapping Coexistent 15mm Flat wire conductor 30mm7.5mm1.5mm Kraft paper One layer Nonexistent Test case B

3.1 Investigation of factors related to copper sulphide generation on insulating paper To examine the effects of sulfur compounds in oil on copper sulphide generation on insulating paper, we prepared sample oils with various sulfur compounds, and examined the effects using test method A. To prepare the sample oil, we added sulfur compounds whose sulfur element concentration was 86 ppm to alkylbenzene, a pure hydrocarbon compound not containing any impurities. We placed a copper plate wrapped with paper and a bare copper plate together in this sample oil, and heated the sample oil inside an oven at 140 or 150C for 72 hours. Sulfur and copper elements on the insulating paper, which was measured by X-ray microanalyser (XMA), are shown in Figure 8. Sulfur and copper elements were detected in every test case. The amount of sulfur was greater than that of copper. In the detected amount of sulfur, adsorbed sulfuric compounds were also included. In the test cases where both sulfur and copper elements were remarkably detected, a metallic shine was locally observed, which was thought to be a symptom of generation of copper sulphide. It is thought that generation of copper sulphide will be promoted, if the heating time is extended. Benzyl sulphide and octyl sulphide showed high amounts of sulfur elements compared with other sulfur compounds but they did not show remarkable copper element detection. Test temperature and atmosphere did not show strong influence on the amount of sulfur and copper elements. Dibenzyl disulphide (DBDS) has been reported recently as a substance causing copper sulphide generation. [3] Symptoms of copper sulphide generation were detected for some sulfur compounds in this test. It seems necessary to continue research on causative compounds other than DBDS.
20000 Sulfur and copper element on surface of paper [Count Per Second by XMA]

16000

12000

8000

4000

0 140 150 140 150 140 150 140 150 140 150 140 150 140 150 140 150 140 150 140 150 140 150 140 150 140 150 140 150 140 150 140 150

N2

Air

N2

Air

N2

Air

N2

Air

N2

Air

N2

Air

N2

Air

N2

Air

Octyl sulfide

Benzyl sulfide

Octanethiol

Octyl sulfoxide Octyl sulfide Test condition

Benzyl sulfide

Octanethiol

Octyl sulfoxide

Sulfur element

Copper element

Figure 8: Comparison of sulfur and copper elements on surface of insulating paper

3.2 Effect of BTA addition on copper sulphide generation on insulating paper We examined the suppressive effect of BTA addition against copper sulphide generation using test method B. To prepare the sample oil, we added a specified quantity of DBDS and BTA to two types of domestically produced oil (sample oil A and sample oil B). Because copper sulphide generation was not detected in either domestically produced oil in blank tests, we added 400 ppm DBDS to accelerate copper sulphide generation and 0 to 100 ppm BTA. 5

Table 3 shows the test results for each sample oil. When DBDS was added, copper sulphide was generated on the insulating paper and conductor in both sample oil A and the sample oil B. We confirmed that copper sulphide generation was accelerated by addition of DBDS. Addition of BTA suppressed copper sulphide generation on the copper plate and insulating paper inside the oil with DBDS added. When 30 ppm or more BTA was added, absence of copper sulphide generation was confirmed on both the copper plate and insulating paper. We confirmed in this test that BTA addition provides a copper sulphide generation suppressive effect to both the copper plate and the insulating paper. But it is necessary in the future to determine long-term reliability of BTA against copper sulphide generation in the same way as for static electrification.
Table 3: Test results on suppressive effect of BTA Test Results BTA Oil A Oil B [ppm] Copper Paper Copper 0 Negative Negative Negative 0 Positive Positive Positive 10 Positive Positive Positive 15 Positive Positive Positive 30 Negative Negative Negative 50 Negative Negative Negative 100 Negative Negative Negative

DBDS [ppm] 0 400 400 400 400 400 400

Paper Negative Positive Positive Positive Negative Negative Negative

4. Conclusion Since suppression effect of BTA against static electrification was experimentally confirmed and BTA addition to insulating oil was standardized in Japan in the 1980s, it has been applied to many high-voltage transformers and sufficient experience has been obtained, and BTA addition also gives suppressive effect to recently-reported increase of static electrification of insulators. We performed accelerated aging tests using a system where the insulating oil, copper materials and insulating paper existed together (instead of the conventional accelerated aging test using only the insulating oil and copper materials), confirmed copper sulphide generation on the insulating paper, and confirmed the effect of trace components contained in the mineral insulation oil. We also confirmed that BTA suppressed not only static electrification and copper sulphide generation on copper materials but also copper sulphide generation on the insulating paper. Accompanied by increasingly aged transformers, evaluation of long-term reliability for the suppression effect of BTA against copper sulphide phenomena should be investigated in the future.

BIBLIOGRAPHY [1] G. Touchard, P. Mas, T.Paillat and O. Moreau: Static Electrification in Power Transformers: Correlation between Charge Generation and ECT-tan Parameters for Different Oil-Pressboard Couples, Proceedings of 13th ICDL, p.396, 1999 [2] J. Hajek, G. Bennstam, et al. ABB Review, No-3 pp61 (2004) [3] Riccado Maina, etc: Dibenzyl disulfide (DBDS) as corrosive sulfur contaminant in used and unused mineral insulating oils,: CIGRE A2 documents