Copper Dissolution and Deposition Tendency of Insulating Mineral Oils Related to Dielectric Properties of Liquid and Solid Insulation

R. Maina, V. Tumiatti
Sea Marconi Technologies s.a.s. Collegno (TO), Italy info@seamarconi.com

M.C. Bruzzoniti, R.M. De Carlo

Department of Analytical Chemistry University of Torino Torino, Italy mariaconcetta.bruzzoniti@unito.it

J. Luki, D. Naumovi-Vukovi
Laboratory for testing and calibration Elektrotehniki institut "Nikola Tesla" Belgrade, Serbia info@ieent.org

Abstract Mineral oils may react with the copper conductors in oil impregnated transformers, leading both to the formation of dissolved and suspended copper in the oil and to the deposition of copper onto the paper surface of the solid insulation. Available standard methods for copper detection in mineral oil may not be fully effective in assessing the total copper content. Dissolved and suspended copper species in the oil are shown to affect oils losses to a different extent. Unused oils are investigated to elucidate their tendency to dissolve copper in the oil and to deposit it onto the paper surface. Oils inherent properties, the presence of additives and the reaction conditions may significantly vary the magnitude of the copper dissolution, as well as the transfer of copper to the paper tapes. A tentative relationship between the deposited copper and the papers dielectric properties is described. Keywords-Oil losses, Copper in Oil, Paper Dielectric Properties

compounds [4,7]. The capability of different insulating oils to dissolve copper has not been intensively investigated, yet. In the first part of this study the influence of different copper forms on oils losses is elucidated, investigating a set of real oils in service in power transformers. The second aim of this work is to explore the copper dissolution phenomena and the deposition tendency of some unused mineral transformer oils available in the market, and to evaluate the relationship with dielectric properties of copper contaminated solid insulation. II. TEST METHODS APPLIED

I.

INTRODUCTION

The formation of conductive deposits within the solid insulation has been reported as the culprit for a number of failures in power transformers and reactors in the last decade. A significant deterioration of the dielectric properties of insulating Kraft paper was found in units having undergone a failure involving the formation of copper sulfide due to the presence of corrosive sulfur in the insulating oil [1-5]. The capability of oil to transfer copper onto the insulating paper tapes has been found also in oils where corrosive sulfur tests are negative. The same nature of copper deposits may differ case to case: either copper sulfide and copper oxide have been identified on contaminated paper tapes. Whilst copper sulfide contamination on the solid insulation has been shown to adversely affect its dielectric properties [3], dissolved or suspended copper in insulating mineral oils was reported to influence oils dielectric losses. In majority of the cases, a direct relationship between copper content and tan was found for oils in service [6]. The mechanism of copper dissolution in the oil, as reported in literature, is conducted throughout the formation of oil soluble metal hydro-peroxides and association into complex compounds with other oil species, like sulfur

ASTM D 7151 is the unique standard method currently available for the determination of copper content in oil. With this method, large suspended particles containing copper are not detected. Conversely, small particles (diameter < 2 m) are detected together with dissolved copper species, and therefore the method doesnt allow the separation between these two forms of copper. For the above mentioned reasons, it was necessary to develop methods for the detection of soluble copper species and to detect the actual total copper content, including large particles. The former aim was obtained by filtering the oil before submitting it to ICP analysis. PTFE filters (0.45 m) were preferred to other materials (such as polyamide) in order to avoid side effects of retention by the filter. 5 ml of filtered oil was analyzed by ICP after dilution 1:1 with a suitable solvent. Total copper content was determined after microwaveassisted mineralization of the oil, in an acid-oxidative reagent. The mineralization procedure, after optimization, was the following: 0.15 g of oil is added with 2.5 ml of a mixture of nitric acid (35%) and hydrogen peroxide (130 vv.) 4:1 (v/v). The sample is then treated under microwaves in a rotating digester, for 5 minutes. The digested solution is finally diluted up to 5 ml, and analyzed by ICP-OES. In order to estimate the tendency of unused oils to dissolve copper and to deposit copper on paper, two independent simulation test method (CDT, Copper Deposition and Dissolution Tendency Test) were developed and compared. In procedure A, 12 g of oil are put in contact with a total copper

surface of 15 cm2 (obtained by cutting in small pieces a copper wire of known diameter) into a 20 ml test tube, in presence of a total surface of 30 cm2 of Kraft paper. The test tube is sealed with a PTFE/butyl rubber septum, and heated under continuous stirring, for 72 h at different temperatures, described in the following chapters. In procedure B, 25 ml of oil were aged using modified method IEC 61125 B and C at 120 C, during 164 h, with additional 6 pieces of paper wrapped copper conductors, length of 6 cm and other dimensions as described in IEC 62535. The additional copper pieces were inserted inside the copper coil, in order to increase the available surface of copper in the reaction. After ageing, the copper in oil content was detected following ASTM D 7151 procedure, and copper content in the paper was determined after mineralization of the cellulose in an acidic-oxidative aqueous solution. Determination of insulating paper surface resistivity was based on resistance measurement by a megaohmmeter, with a particular system of electrodes that consists of center electrode e1, ring electrode e2 and guard (shield) electrode e3. Electrodes were brass-made, and their dimensions were adjusted to fit the size of tested insulating paper sample.. III. COPPER IN OIL CONTENT RELATED TO OILS DIELECTRIC PROPERTIES

presence of suspended copper containing particles in the oil. These results indicate that method ASTM D 7151 may be partially ineffective for the determination of total copper content in mineral oils, due to its inherent limitation in detecting copper (as well as other metals) in particle form.
Copper concentration, mg/kg
45,00 40,00 35,00 30,00 25,00 20,00 15,00 10,00 5,00 0,00 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Oil # After Filtration ASTM D 7151 After mineralization

Figure 1. Copper concentrations in oil determined by different procedures; error bars are also indicated (>10 replicates).

Mineral insulating oils may react with the copper conductors surface, forming copper compounds that can be detected in the oil itself. This phenomenon is commonly observed in transformers impregnated with mineral oil, and it may result in an enhancement of the oils dielectric losses [5,6]. Nevertheless, it is not clear, yet, which forms of copper compounds are more capable to influence the dielectric dissipation factor (DDF) of the oil. Methods described in chapter II were applied in this study to investigate whether soluble or suspended copper-containing species are present in mineral oils in service, and how they differently influence oils losses, expressed as DDF measured at 90C. A set of 16 mineral oils in service was selected, collecting samples from transformers in service where presence of dissolved copper was historically detected by ASTM D 7151 method. On these oils, numbered 1 to 16 in the following tables and graphs, copper content was measured with different methods: ASTM D 7151 (reference method), ICP-OES after filtration, ICP-OES after microwave mineralization. Results are depicted in Fig. 1. In some oils (#4, #13, #14, #16), a relevant percentage of the copper detectable in the conditions of Method ASTM D 7151 is lost after filtration, indicating that they have a considerable copper content in particle form. Moreover, the copper concentration detected after mineralization, which gives account for the total dissolved and suspended copper content, is in all cases higher than the one detected by direct ICP analysis. Oil # 8 is particularly interesting, because the majority of its copper content cannot be detected without mineralization of the sample. As it can be perceived from the standard deviation bars in Fig. 1, method ASTM D 7151 shows the highest standard deviation among the applied methods. This behavior has been attributed to the poor reproducibility of the nebulization efficiency of the ICP spray chamber at the increasing of the

The contribution of copper species to oil losses (expressed as DDF at 90C, measured accordingly with method IEC 60247) has been investigated by testing the DDF before and after filtration; results are reported in Fig. 2. As it can be perceived from the graph, significant variations in the DDF value were observed in few cases (oil # 2 and oil # 4), considering the reproducibility of the test (plotted in the figure as error bars). Observing the copper concentrations reported in fig. 1, oil # 4 is among the ones having the largest percentage of filterable copper species, and this may explain the difference encountered in DDF values after filtration. Nevertheless, other oils (# 6, #13, #14, #16) show a similar variation in copper content, without giving appreciable decrease in DDF after filtration.
DDF @ 90C
0,6000 Before filtration 0,5000 0,4000 0,3000 0,2000 0,1000 0,0000 After filtration

10

11

12

13

14

15

Oil #

Figure 2. DDF of 16 mineral oils before and after filtration through .45 m PTFE filter.

Measurements of DDF prior and after filtration indicate that oil losses are influenced mainly by the soluble fraction of copper. This result is better appreciated in Fig. 3, where the correlation between copper content and DDF is plotted for each of the three methods applied. The best correlation DDF vs copper content (R2 = 0,9883) is obtained for filtered samples. On the other hand, if the correlation between the copper content measured with method ASTM D 7151 and DDF is still acceptable (R2 = 0,9295), the same correlation between the copper content measured after mineralization and DDF is much

16

worse (R2 = 0,7378). It can be concluded that soluble copper species are the main responsible for the increase of DDF often encountered in real oils; suspended copper forms, or particles in which copper is trapped, do not affect oils losses appreciably. These conclusions are consistent with the principle that, at power frequencies, the electrical conductivity, , and dissipation factor, tan , characteristics of transformer oils are determined by the charge carriers within the oil. The conductivity loss in the oils results from the movement of ions in a viscous medium, the conductivity of an oil is necessarily directly proportional to the number of ionic charge carriers present and inversely proportional to the viscosity of the oil, [8,9]. Thus, ionic (soluble) forms of copper should be accounted for having an higher mobility within the oil, and for giving a contribution to oils losses larger than suspended particles, even if conductive.
DDF @ 90 C

The dependency of CDT from temperature (100, 120 and 140C) has been investigated. Data in Fig. 4 a) indicate that, under the experimental conditions described, uninhibited oils show a general decrease in the formation of copper in oil at increasing temperatures, while in case of inhibited oil copper content is lower than the detection limit for almost all tested temperatures. This behavior has been attributed to the increasing formation of sludge and deposits in uninhibited oil at higher temperatures, which may result in the precipitation of copper into insoluble forms. It is noteworthy that, among uninhibited oils, the amount of dissolved copper is related to the total aromatic content of the oil. Oil # 3, surprisingly, doesnt form measurable dissolved copper: this may be due to the presence of Irgamet30 as metal passivator (15 mg/kg detected in the oil). A more complicated trend is present in case of copper content in paper after ageing, depicted in Fig. 4 b). In fact, with the exclusion of Oil # 1, that deposits much more copper at 100C (1200 mg/kg), the other oils show a lower (350 mg/kg average value) and fairly constant copper concentration at increasing temperature.
1,4 1,2 1 0,8 0,6 0,4 0,2 0 -0,2 90 100 110 120 130 140 150 Temperature, C Oil # 1 Oil # 3 Oil # 5 Oil # 7 Oil # 2 Oil # 4 Oil # 6 Oil # 8
Copper content (mg/kg) in paper Copper content (mg/kg) in oil

0,6

0,5

[Cu] after filtration [Cu] ASTM D 7151 [Cu] after mineralization

0,4 R = 0,9883 0,3 R = 0,9295 R = 0,7378

1400 1200 1000 800 600 400 200 0 90 100 110

0,2

Oil # 1 Oil # 3 Oil # 5 Oil # 7

Oil # 2 Oil # 4 Oil # 6 Oil # 8

0,1

0 0,000

5,000

10,000

15,000

20,000

25,000

30,000

35,000

40,000

45,000

[Cu], mg/kg

Figure 3. Correlation between [Cu] and DDF of 16 mineral oils. Copper concentration was detected according to different methods. Correlation factors are expressed by the R2 value of a 2nd order linear regression.

120

130

140

150

Temperature, C

IV.

STUDY OF COPPER DEPOSITION AND DISSOLUTION TENDENCY (CDT) IN OIL AND ONTO PAPER.

A set of 8 unused oils available in the market have been collected and characterized (see Tab. I) to study their copper dissolution and deposition tendency (CDT), into oil and onto paper respectively. They differ for inhibitor content, total aromatics content and physical properties such as viscosity and flash point. Both optimized CDT conditions above described (section II), were applied in this study.
TABLE I. OILS
# Oil Name FP a

a) b) Figure 4. a) Correlation between copper in oil and temperature applied. Three replicates for each condition, RSD% 0 26.4. b) Correlation between copper in paper (after wet digestion) and working temperature. 3 replicates for each condition; RSD% 9.1 23.2

CHARACTERIZATION OF THE SELECTED UNUSED OILS Parameters of characterization

b AC c d DBPC e

1 2 3 4 5 6 7 8

Ergon Hyvolt II Ergon Hyvolt III Agip ITE360 Shell Diala B Shell Diala D Shell Diala DX Nynas Libra Nynas Gemini X

140,5 130,5 142,5 148,5 140,5 140,5 150,5 146,5

0,876 0,866 0,880 0,875 0,873 0,871 0,872 0,877

9,37 3,12 12,14 5,73 9,29 4,59 8,47 7,49

9,51 8,63 9,64 11,08 8,23 8,24 9,79 8,70

0,207 0,279 < 0,01 < 0,01 < 0,01 0,255 < 0,01 0,272

a. Flash Point PMCC, C; b. Density, kg/l; c. Aromatic Content, % m/m; d. kinematic viscosity @ 40C, cSt; e. Inhibitor content (Di-tert-Butyl-Para-Cresol), % m/m

Oil # 1 (inhibited) and oil # 5 (uninhibited) were selected to evaluate the influence of oxygen availability in the reaction; temperature was fixed at 100 C to maximize the rate of copper dissolution, on the base of the results previously reported. To keep under control the atmosphere, a continuous and constant oxygen (oxidative conditions) or argon (inert conditions) flow rate was applied during the 72 hours of ageing. Fig. 5 a) illustrates how copper dissolution is strongly depending on the presence or absence of inhibitor in oxidative atmosphere. This may be attributed to the anti-oxidant role of DBPC, which reduces the sludge formation and the subsequent precipitation of the copper. If the oil is adequately protected from oxidation (inhibited oil) the oxygen seems to accelerate the copper dissolution. As above described, uninhibited oils are markedly prone to dissolve copper, more than inhibited oil, but this effect may be masked by an excess of oxygen, which may cause the formation of conductive sludge instead of dissolved copper. Absorption of copper in the paper was augmented with the increase of oxygen availability, as depicted in Fig. 5 b),

especially in the case of inhibited oil. This might be explained by assuming that oxygen promotes the copper oxidation.
Copper content (mg/kg) in oil Copper content (mg/kg) in paper
4,5 4 3,5 3 2,5 2 1,5 1 0,5 0 Oil # 1 (inhibited) Oil # 5 (uninhibited) Oil type Inert atmosphere (Argon) Oxidative atmosphere (Oxygen) 700,00 600,00 500,00 400,00 300,00 200,00 100,00 0,00 Inert atmosphere (Argon) Oxidative atmosphere (Oxygen)

copper concentration tends to decrease at higher passivator contents, coherently with the shielding effect of Irgamet39 towards the conductor (Fig. 7). Moreover, Oil # 1 always dissolves less copper than Oil # 5, so confirming the correlation between presence of inhibitor and copper in oil described above. This result is opposite to what has been obtained in case of copper deposited on paper. A general decreasing trend of copper content at increasing Irgamet39 concentration is perceivable from fig. 7 b), and can be explained by interference of Irgamet39 absorbed in the paper [4]. In case of inhibited oil (# 1) copper deposited on paper resulted to be higher than in case of uninhibited oil (# 5). This confirms the role of inhibitor in facilitating the transfer of copper from conductor to the solid insulation.
Conpper content (mg/kg) in oil
Oil # 5 1,0 0,5 0,0 0,00 Oil # 1

Oil # 1 (inhibited)

Oil # 5 (uninhibited) Oil type

Conpper content (mg/kg) in paper

1,5

1500,0 Oil # 5 1000,0 500,0 0,0 0,00 0,10 0,20 0,30 0,40 Irgamet 39 (mg/kg) Oil # 1

a) b) Figure 5. a) Effect of atmosphere on copper content in oil. b) Effect of atmosphere on copper content in paper

The influence of inhibitor content in the CDT was studied by fortifying two originally uninhibited oils (#3 and #5) with DBPC at increasing concentrations. The effect of DBPC on copper in oil concentration, depicted in Fig. 6 a) indicates that increasing inhibitor content does not influence significantly the metal concentration. Oil # 3 did not form measurable amount of copper in oil, probably due to the presence of a passivator, as previously reported. Otherwise, it's very interesting the effect on copper deposited onto paper, reported in Fig. 6 b). In fact, at increasing DBPC concentrations, the augmentation of copper deposited on paper may be observed, indicating that inhibitor causes an increase in copper deposition tendency. As already suggested by other researchers [10], this may be interpreted by postulating the formation of organo-metallic copper-DBPC compounds, which increases the solubility and mobility of copper in the oil, favoring its transfer onto the paper surface. It is not clear, yet, why oil # 3 did not form dissolved copper, while it deposited copper on paper in the same conditions.
Conpper content (mg/kg) in oil Conpper content (mg/kg) in paper

0,20 0,40 Irgamet 39 (mg/kg)

a) b) Figure 7. a) Effect of passivator on copper content in oil. b) Effect of passivator on copper content in paper

1,5 1,0 0,5 0,0 0,00 Oil # 5 Oil # 3 0,20 0,40 % DBPC

600,0 500,0 400,0 300,0 200,0 100,0 Oil # 5 Oil # 3

0,0 0,00 0,10 0,20 0,30 0,40 % DBPC

a) b) Figure 6. a) Effect of inhibitor content on copper dissolution. b) Effect of inhibitor content on copper deposition onto paper

Modified IEC 61125 B and C methods have been also applied, with the aim to increase the ratio between copper surface and the oil volume, and to enhance the copper transfer to oil and paper. Each analysis has been carry out in four replicates on two inhibited (# 1 and # 2) and on two uninhibited (# 4 and # 5) oils. The results of dissolved copper and deposited copper give an higher repeatability in case of modified IEC 61125 C method. As shown in Fig. 8 a), in case of uninhibited oils (# 1 and # 2) higher copper in oil content was obtained with modified IEC 61125 C (air flow 0.15 L/h), than with modified IEC 61125 B (oxygen flow of 1 L/h). The opposite trend is present in case of oil containing DBPC, where dissolved copper increases in presence of high oxygen availability (method B; oil # 1 was heavily degraded, with marked sludge precipitation, and copper in oil analysis was not possible). This is in agreement with the above illustrated results (Fig. 5) in controlled atmosphere: also in that case, in fact, in oxidizing conditions the inhibited oils dissolved more copper than the uninhibited one. As postulated before, this can be ascribed to a complexing role of DBPC towards copper, effect that favors the dissolution of the metal into the oil. On the contrary, in the same oxidizing conditions absence of the inhibitor dramatically reduces copper in oil concentration, as an effect of the metal precipitation. Parallel considerations can be made about copper deposited on paper, reported in Fig. 8 b): also in this case the presence of the inhibitor favors the transfer of metal onto paper, especially in oxygen saturated conditions (method IEC 61125 B). It is noteworthy the large difference obtained for oil # 1, which was highly degraded after IEC 61125 B modified test (copper in oil measurements were not performed). The decrease of copper deposited on paper observed in case of method IEC 61125 B for uninhibited oils must be probably was attributed to the

As underlined in literature [4], presence of passivators dissolved in the oil and absorbed in the paper interferes with copper dissolution in the oil and deposition process in paper insulation. Known amounts of passivator was added to an inhibited (# 1) and an uninhibited (# 5) oil. It is possible to observe that both for inhibited and uninhibited oil dissolved

copper precipitation as oxidized species, before deposition on the paper, leading to lower concentration of detectable dissolved copper and accordingly to lower concentrations of absorbed copper in the paper.
Copper content (mg/kg) in oil
1,80 1,60 1,40 1,20 1,00 0,60 0,40 0,20 0,00 Oil # 4 Oil # 5 Oil # 1 Oil # 2 Type of oil 0,80

Copper content (mg/kg) in paper

61125 B 61125 C

18000 16000 14000 12000 10000 8000 6000 4000 2000 0

61125 B 61125 C

Measured values of insulating paper resistance between electrodes e1 and e2 were in the range from 1 T to 1000 T, and surface resistivity is in the range from 10 T to 10000 T. For surface resistivity values less than 100 T evaluated uncertainty of measurement was better than 5%. For surface resistivity values in the range from 100 T to 1000 T evaluated uncertainty of measurement was about 10%. Uncertainty of measurement for surface resistivity values great than 1000 T was hard to evaluate for the reason that external influences are extremely high. No significant difference between resistivity values for inner and outer surface of the paper were observed. This results if further indicating that copper species absorbed in the paper are not influencing decrease of insulating properties of the copper enriched papers, and no direct relationship of copper content in the paper to paper surface resistivity was observed.
Log Rin Rin = 74 - 1000103 G
10000 1000 100 10 1 100 1000 10000 Log [Cu] in paper [Cu] = 269 - 30800 mg/kg Oil # 4 Oil # 1 Oil # 5 Oil # 2

missing value

Oil # 4 Oil # 5 Oil # 1 Oil # 2 Type of oil

a) b) Figure 8. Copper in oil (a) and in paper (b) after modified IEC 61125 B and C method

V.

EFFECT OF COPPER ON PAPER INSULATING PROPERTIES.

Modified IEC 61125 B and C test were used to enrich paper with copper in order to determine effects of absorbed copper on electrical properties of the paper. Paper surface resistivity results of copper enriched papers (described in Fig. 9 and Fig. 10) indicated that good paper insulating properties were preserved, regardless of copper content in the paper.
Log Rin Rin = 210 - 1490103 G
1000

a)
Log Rout Rout = 160 - 10000103 G
10000 1000 100 10 1 100 1000 10000 Log [Cu] in paper [Cu] = 269 - 30800 mg/kg Oil # 4 Oil # 1 Oil # 5 Oil # 2

100 Oil # 4 Oil # 1 Oil # 5 Oil # 2

10

1 800 900 1000 1100 1200 1300 Copper content (mg/kg) in paper

b) Figure 10. Application of IEC 61125 B method; a) Copper content vs. mean surface resistivity on the inner paper surface; b) Copper content vs. mean surface resistivity on the outer paper surface

a)
Log Rout Rout = 190 - 1340103 G
1000

VI.

CONCLUSION.

100 Oil # 4 Oil # 1 Oil # 5 Oil # 2

10

1 800 900 1000 1100 1200 1300 Copper content (mg/kg) in paper

Standard methods available for the detection of copper in oil do not take into account the copper dispersed in particle form. Methods to determine total copper content (after sample mineralization) and to separate the soluble fraction (after sample filtration) have been optimized to fully investigate the copper content in oil. The detrimental influence of the presence of copper in transformer insulting oils is related to the increase of oils losses. This effect has been demonstrated to be mostly depending on the copper in dissolved form rather than on copper containing particles suspended in the oil.

b) Figure 9. Application of IEC 61125 C method; a) Copper content vs. mean surface resistivity on the inner paper surface; b) Copper content vs. mean surface resistivity on the outer paper surface

Two different methods to estimate the copper dissolution and deposition tendency (CDT) were proposed. Preliminary results obtained from a set of unused oils selected from the market indicates that: - copper in oil dissolution is limited at high temperatures, especially for uninhibited oils, which are prone to oxidation; - copper in paper transfer and deposition is favored by the increase of oxygen and inhibitor (DBPC); it is advisable that a Cu-DBPC complex participate to this mechanism; - increasing amount of oxygen influences both reaction of dissolution and deposition, but its effects are strongly dependant on the presence of antioxidants in the oil; - when significant amount of sludge from the oil is formed, under conditions of excess of oxygen, as it is the case with uninhibited oils, copper species may precipitate and, as a consequence, the transfer of copper onto the paper is hampered; - passivators reduce both copper dissolution in oil and copper deposition onto the paper; - increasing amounts of copper absorbed in the paper do not affect paper surface resistivity, implicating that good insulating properties of the paper are preserved. ACKNOWLEDGMENT The Authors would like to acknowledge prof. C. Sarzanini (University of Torino), M. Facciotti, V. Trento, M. Pittavino, S. Skundric and D. Nikolic for the valuable efforts dedicated to the work presented in this paper. This work has been performed under the Project n 31 Life Cycle Assessment study of metal contaminated large power electrical apparata, co-financed by MISE-ICE-CRUI. One of the author RMDC is

indebted for the fellowship granted under this project. MIUR (Ministero dell'Istruzione, dell'Universit e della Ricerca, Italy) is also gratefully acknowledged. REFERENCES
F. Scatiggio, V. Tumiatti, R. Maina, M. Tumiatti, M. Pompili and R. Bartnikas, Corrosive sulfur in insulating oils: its detection and correlated apparatus failures, IEEE Trans. on Power Delivery, Vol. 23, pp. 508-509, 2008. [2] S. Toyama, J. Tanimura, N. Yamada, E. Nagao and T. Amimoto, Highly sensitive detection method of dibenzyl disulfide and the elucidation of the mechanism, IEEE Trans. on Dielectrics and Electrical Insulation, vol. 16, N. 2, pp. 509-515, 2009 [3] F. Scatiggio, V. Tumiatti, R. Maina, M. Tumiatti, M. Pompili and R. Bartnikas, Corrosive Sulfur Induced Failures in Oil-Filled Electrical Power Transformers and Shunt Reactors, IEEE Trans. on Power Delivery, Vol. 24, pp. 1240-1248, 2009. [4] Jelena Lukia, Sran Milosavljevi a, Aleksandar Orlovib, Degradation of Insulating Systems of Power Transformers by Copper Sulfide Deposition: Influence of Oil Oxidation and Presence of Metal Passivators, Ind.Eng.Chem.Res. 2010, 49, 9600-9608. [5] R. Maina, Corrosion Phenomena, Proc. MyTransfo Meeting, Turin, 2008, pp. 69-84 [6] R. Maina, V. Tumiatti, M. Pompili and R. Batnikas, Dielectric Loss Characteristics of Copper-Contaminated Transformer Oils, IEEE Trans. On Power Delivery, vol. 25, N. 3, pp. 16731677, July 2010 [7] J.Lukic, Oil Oxidation and Role of Oil Inhibitors , Proc. My Transfo Meeting, Turin, 2008, p. 122. [8] R. Bartnikas, Dielectric Loss in Insulating Liquids, IEEE Transactions on Electrical Insulation, Volume EI-2, Issue 1, pp. 33-54, 1967 [9] R. Bartnikas, Engineering Dielectrics, Vol. III, Electrical Insulating Liquids, Vol. III, Monograph 2, ASTM, Philadelphia/West Conshohocken, 1999 (see also www.astm.org/digitallibrary) [10] J. Tanimura, T. Amimoto: Influential Factors of Copper Sulpide Formation on Insulating Paper in Transformers, Cigre A2.40 IWD 41, Venice, 2011. [1]