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Generation of hydrogen from oils with the addition of passivators such as 1, 2, 3-benzotriazole (BTA) and Irgamet® 39 for suppressing copper sulfide deposition was investigated by heating tests. Large amounts of hydrogen were generated from the oils with the addition of Irgamet® 39 compared to the oils with the addition of BTA. BTA is suitable in terms of less generation of hydrogen. For Irgamet® 39 added oils, the amounts of hydrogen increase with an increase in oxygen concentration. Irgamet® 39 was consumed by thermal decomposition and oxidation. Consumption by oxidation of Irgamet® 39 is considered to be affected to the hydrogen generation. Amounts of hydrogen increase with increase in heating temperature for a certain period of time. After conducting heating test, Irgamet® 39 was remained in oil. Total amount of hydrogen, which is defined by sum of the amount of hydrogen generated by consumed Irgamet® 39 and the amount of hydrogen generated by residual Irgamet® 39, are considered to be independent of heating temperature. Effects of additives such as dibenzyl disulfide, which is one of the prime compounds that cause the copper sulfide deposition, and 2, 6 ditertiary-butyl paracresol as antioxidant on hydrogen generation were significant. Consequently, in case of adding Irgamet® 39 for the purpose of suppressing copper sulfide deposition, installation of a conservator system and rubber bag which reduces the dissolution of oxygen into the oil is effective to minimize the amount of hydrogen. [ABSTRACT FROM PUBLISHER]

The suppressive effect of triazole-based passivators such as 1,2,3-benzotriazole (BTA) and Irgamet 39 and duration of the suppressive effect on copper sulfide deposition are investigated by changing the time when passivators are added to oil. All corrosive sulfur tests were performed by the method stipulated by IEC 62535. In order to simulate the timing for adding passivators into actual transformers, preheated and non-preheated oils were used for corrosive sulfur test. Adding a passivator into preheated oil simulates the condition where a passivator is added into the transformer after a period of operation, and adding a passivator into non-preheated oil simulates the condition where a passivator is added before operation. Although the deposition rate of copper sulfide in preheated oil with the addition of passivator was lower in preheated oil without passivator, copper sulfide deposition still continued even while the passivator was detected in the oil. The result suggests that the precursors of copper sulfide have been already generated in preheated oil before adding a passivator. After the passivator was depleted in the oil, the period until onset of copper sulfide deposition in the preheated oil was shorter than in non-preheated oil since a protective complex layer was created on the copper surface and reaction with the passivator continued to prevent the deposition of copper sulfide precursors. [ABSTRACT FROM AUTHOR]

Copper sulfide deposition on cellulosic insulating materials in oil-immersed transformers was investigated by heating tests stipulated by IEC 62535 with controlled atmospheres to which mineral insulating oils were exposed. Both oxygen in the atmosphere and 2,6-di-tert-butyl-p-cresol (DBPC) in the oil were found to accelerate the copper sulfide deposition on the insulating paper when the oil contains dibenzyl disulfide (DBDS). The weight of copper sulfide deposition on the insulating paper was found to increase when the oxygen concentration was increased up to 20 volume %. X-ray absorption near edge structure (XANES) analysis was applied to study the chemical bonding state of copper atoms in copper deposits on the insulating paper for the first time. It can be clarified the copper deposits on the insulating paper are mainly Cu2S and small amounts of CuO are contained. [ABSTRACT FROM PUBLISHER]

Copper-sulfide deposition on coil insulating paper used for power transformer insulation is investigated with the aim of obtaining the concentration dependence of corrosive sulfur. Several mineral insulating oils containing dibenzyl disulfide (DBDS), which is typical corrosive sulfur causing the copper sulfide deposition, are used as sample oils. Thermal aging tests are done at 140 °C with an air atmosphere up to 1296 h with Kraft paper-wrapped and bare copper plates. The test results indicate that the deposition rate is proportional to the DBDS concentration and the incubation period before onset of the copper-sulfide deposition is inversely proportional to the DBDS concentration. These concentration dependences can be derived by considering equilibrium between three compounds such as dissolved DBDS-Cu complexes in the oil, adsorbed DBDS-Cu complexes and deposited copper-sulfide on the insulating paper. [ABSTRACT FROM AUTHOR]

Highly sensitive detection method of dibenzyl disulfide (DBDS) in insulation oil was realized using solid phase extraction (SPE) with active alumina adsorbent followed by gas chromatography equipped with a mass spectrometry (GC-MS). The detection limit of DBDS is around 0.1 ppm. This method is also useful for detecting bibenzyl (BiBZ) and dibenzyl sulfide (DBS). The good relationship between the weight change of copper strip and BiBZ IDBS formation was obtained under heating with insulating oil containing DBDS and copper strip, so it was clarified that BiBZ and DBS are the by-products of the copper sulfide generation with the chemical reaction between DBDS and copper. The chemical reaction formula between DBDS and copper was proposed based on the assumption that copper sulfide should be generated via Cu-DBDS complex. The temperature dependence of the weight change of copper strip before and after the heating in the insulating oil containing DBDS was quantitatively explained with the chemical reaction formula. [ABSTRACT FROM AUTHOR]

Effects of oil brand, temperature and atmosphere conditions on copper sulfide deposition on insulating paper were investigated by thermal aging test. copper sulfide deposition occurred in a certain oil brand and dibenzyl disulfide (DBDS) was found in the oil. There was an incubation period observed before copper sulfide deposition occurred. Copper sulfide deposition was accelerated by temperature. The deposition rate after the incubation period became twice when the heating temperature was increased by approximately 10 °C. The incubation period and the deposition rate were the same at 140 °C whether the thermal aging test was done in air or nitrogen atmosphere. On the other hand, the incubation period in air was shorter than that in nitrogen at 120 °C. The deposition rate was not affected by atmosphere condition at 120 °C. Intermediate substances due to copper dissolution into oil are introduced to explain the incubation period and the atmosphere dependence of incubation period observed at 120 °C. [ABSTRACT FROM AUTHOR]

The suppressive effect of triazole-based passivators such as 1,2,3-benzotriazole (BTA) and Irgamet 39TM (CIBA Specialty, Basel, Switzerland) on the deposition of copper sulfide on insulating paper in transformers and reactors was investigated by heating test with bare and paper-wrapped copper plates. Commercially available mineral oil meeting the specification of IEC 60296 was used. This oil contained 136 ppm wt./wt. of dibenzyl disulfide (DBDS). The deposition of copper sulfide occurred after 144 h of heating at 140 °C without these passivators. However, little deposition of copper sulfide occurred even after 432 h of heating when either of these passivators was added to the oil. The concentration of dissolved copper significantly decreased when either of these passivators was added to the oil, which reflects the formation of complex layers on the copper surface caused by the reaction between these passivators and copper. The complex layers were confirmed by time-of-flight secondary ion mass spectrometer (TOF-SIMS). The suppressive effect was derived from retarding copper from dissolving into: the oil due to the reaction inhibition between DBDS and copper by the complex layers. The duration of these passivators can be determined by the durability of the complex layers. [ABSTRACT FROM AUTHOR]

Copper sulfide is found to be more likely formed on Kraft paper in oil-immersed transformers with an increase in either dibenzyl disulfide (DBDS) concentration or heating duration, which is verified by heating tests stipulated by IEC 62535. Two effects of DBDS concentration on the formation rates of copper sulfide were obtained. The formation rates of investigated oils are proportional to the DBDS concentration when the concentration is low. However, the amounts of copper on the Kraft papers are constant when the DBDS concentrations are more than certain values, which is considered to reflect the saturation of dissolving DBDS-Cu complex in the oil. These concentrations depend on oil brand. Copper sulfide begins to form after some duration of heating and the duration decreases with an increase in the DBDS concentration. Copper sulfide formed on the Kraft paper is a portion of the total copper reacted with DBDS by comparing the amount of copper formed on the Kraft paper with the total amount of reacted copper calculated from the amount of consumed DBDS. [ABSTRACT FROM PUBLISHER]

Copper sulfide deposition on Kraft paper in oil-immersed transformers is found to be accelerated by di-tert-butyl p-cresol (DBPC), which is widely used as an antioxidant, and paraffinic hydrocarbons in their oils, which is verified in laboratory experiments. DBPC can prolong the lifetime of precursors of the copper sulfide deposition by reacting decomposition products of copper dibenzyl disulfide (Cu-DBDS) complex and by creating the Cu-DBPC complex. Because the lifetime of the Cu-DBPC complex is far longer than that of the Cu-DBDS complex, considerable amounts of copper sulfide are deposited on Kraft paper instead of being formed on the surface of copper. A good correlation is obtained between the concentration of paraffinic hydrocarbons and the amount of copper sulfide deposited on Kraft paper in the three commercial oils. [ABSTRACT FROM PUBLISHER]