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Dielectric Loss Characteristics of CopperContaminated Transformer Oils

R. Maina, V. Tumiatti, Associate Member, IEEE, M. Pompili, Senior Member, IEEE, and R. Bartnikas, Life Fellow, IEEE
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, [1]. It has been established that within the normal operating temperature range, the product of the equivalent conductance, , and the viscosity, , varies between 0.5 and 1.0 [3] and for electrical insulating oils, its value is normally found to approximate 0.5 within the temperature range from 30 C to 80 C [5]. This relationship shows that both the and, hence, values, can effectively be employed to gain insight into the dielectric loss behavior of oils, since by denition the equivalent conductance, , is equal to the ratio of the conductivity, , to the ion concentration, , expressed in gram equivalent weight per cubic centimeter. The conductive ions in the transformer oils originate with polar compounds, acids produced by oil aging, sludge formation, and metals (in both soluble and suspended species). The most common metal found in used transformer oil is that of copper. It is thus the intent of the present paper to examine the dielectric loss behavior due to the effects of copper on the transformer oils and to determine the attributes, which distinguish it from those normally associated with the presence of corrosive sulfur [5] and the induced failures observed in power transformers [5]. At this stage, it is not clear what the nature of the copper ion complexes may be in the oils; however, if the presvalues, an ionic ence of copper enhances the magnitude of conduction process is implicated in the oil. II. PRELIMINARY CONSIDERATIONS

AbstractThe relationships between the total copper content, both in dissolved and suspended form, and the dielectric loss characteristics were examined in transformer-type oils. It was established that the dielectric losses in the oils are a function of the total copper content. However, no measurable inuence of the sulfur corrosivity of the oils was detected upon the magnitude of the dielectric losses in the oils, notwithstanding that the conductive copper sulde deposits on the paper tapes impregnated with corrosive sulfur oils resulted in the tapes having highly augmented dielectric losses. It was demonstrated that oil chemical treatment processes that are capable of reducing copper content in the oil, result in a signicant improvement of the dielectric losses of the oil. Index TermsCopper, dielectric losses, transformer oil, transformers.

I. INTRODUCTION

T POWER frequencies, the electrical conductivity, , and dissipation factor, tan , characteristics of transformer oils are determined by the charge carriers within the oil. Over the usual range of operating temperature of transformer oils, the magnitude of the conductive and dielectric loss in the insulating liquid is a function of the type, concentration and mobility of the charge carriers as well as the magnitude of the externally applied electrical eld. Space charge losses predominate below room temperature, while dipole orientation losses occur over the higher frequency spectrum ( 1 MHz) at room temperaturewith their absorption peaks shifting to higher frequencies at the more elevated temperature and to lower frequencies with decreasing temperature. Over the power frequency rgime, a rise in temperature causes simultaneously a reduction in the frictional resistance to the movement of ions due to a reduction of the viscosity of the oil as well as an increase in the number of ions and, hence their concentration, arising from an enhanced dissociation rate of the ionizable constituents. Since the conductivity loss in the oils results from the movement of ions in a viscous medium,

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Manuscript received December 23, 2008 Paper no. TPWRD-XXXX. R. Maina and V. Tumiatti are with SEA Marconi TechnologiesTurin , Italy (e-mail: maina@seamarconi.it). M. Pompili is with the Department of Electrical Engineering of University of Roma La Sapienza, Rome

R. Bartnikas is with the Institut de Recherche dHydroQuebec, Varennes QC J3X 1S1 Canada . Digital Object Identier 10.1109/TPWRD.2010.2043693

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0885-8977/$26.00 2010 IEEE

The reactivity between copper conductors and transformer oils may result in two observed phenomena: while corrosive and potentially corrosive sulfur compounds can transfer copper onto insulating paper surfaces in the form of electrically conductive copper sulde, copper may also enter into the bulk of the oil in dissolved and suspended form. Contamination of the oil with copper and polar constituents augments the conductivity of the oils, hence it will render the impregnated paper tape and pressboard transformer insulation more lossy. In the presence of mercaptans and other organic suldes and disuldes, copper exhibits a high afnity for the sulfur compounds and forms a layer of copper sulde upon the surface of the copper conductors and paper tapes of the transformer insulation. This sulde is thermodynamically highly stable. However, its solubility in the transformer oils is extremely low (the 48.5, and product of solubility of copper sulde in water is even a lower value can be assumed in a hydrocarbon liquid, due to the lower solvability of inorganic salts in non-polar solvents). This infers essentially that while the copper conductor and the paper insulating the turns will become coated by the conductive

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Fig. 1. Tapes of Kraft paper from a power transformer contaminated with copper sulde. Fig. 3. Correlation between the copper content and the tan  value (at 90 C) of transformer oils as a function of service time of a eet of four distribution transformers. The copper concentrations range from 0.65 to 87.3 mg/kg, and the tan  values are from 0.01 to 1.73.

Fig. 2. Total and dissolved copper content and tan  value (at 90 C) of a set of four transformer oils.

copper sulde (Fig. 1), the effect on the conductivity of the oil will be minimal. value of the impregnating oil will be inHowever, the creased by other contaminants, such as dissolved or suspended polar compounds, which may include moisture, acids and organic salts. Copper may be detected in the transformer oil as a sum of dissolved and suspended forms by means of method ASTM D 1581, modied by reducing the dilution of the sample to reach a lower detection limit. As will be described subsequently, the presence of copper can readily enhance the oils conductivity and have detrimental effects on its dielectric loss. Charge carriers affecting dielectric loss must be in ionic, non neutral state, so that it is probable that the total copper content includes compounds, micelles or complexes where copper is present in soluble ionic forms. Fig. 2 delineates the total copper and soluble copper contents obtained on four transformer oils with different contamination levels. It can be seen that a portion of the detected copper is still measurable after oil ltration (PTFE lters of 0.22 m size were used in this study). This suggests the presence of soluble, ionic forms of copper. However, the nature and species of dissolved and suspended copper are still relatively undened and will require further investigation. From Fig. 2, it can be perceived that the remnant dissolved and suspended copper in the contaminated oil after ltration still

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III. COPPER ION EFFECTS

cause the oil to retain unusually high 0.3 to 3.5.

values ranging from

Dissolved and suspended metals can increase markedly the values of mineral ionic content of mineral oils, causing the oils to rise very signicantly to as high as 3 or even higher as has been made apparent already in Fig. 2. Fig. 3 substantiates yet once more another relationship between copper content and value in a mineral oil of distribution transformers as a the function of time. are norThe values of the Cu ion concentration and malized to delineate more lucidly the relationship between the two values over the lifetime of the transformers. No relationship was found to exist between the total acidity number and the dissolved or suspended amount of metal; similarly no correlation was evinced with the corrosive sulfur. According to the denition of acidity number, all compounds exhibiting an acid-like behavior in an hydrocarbon contribute to the value of the acidity number. Since the neutral point is dependant upon the properties of the solvent and its dielectric constant, the total acidity number is comprehensive of a large known and unknown number of compounds. It is thus essentially a parameter that is related to aging and oxidation of the oil, promoted by the presence of oxygen and increased temperature. It should be emphasized that the absence of correlation between metal content and acidity cannot account for the recorded concentrations of copper in transformer oils found in service. Evidently, the mechanism of the oils to dissolve copper is not fully understood. It is conceivable that the copper in the oil acts as an oxidation catalyzer with some assistance from the moisture present in the oil. Oxidation increases the polarity of the oil and the solubility of polar metallic compounds. The concentration of copper is signicantly lower in oils, which contain corrosive sulfur as is apparent from Fig. 4. The curves in Fig. 4 represent a sampling of 50 transformers, which contain corrosive sulfur, and 50 transformers which are free of corrosive sulfur. Both samples of statistical data are arranged in

MAINA et al.: DIELECTRIC LOSS CHARACTERISTICS OF COPPER-CONTAMINATED TRANSFORMER OILS

Fig. 4. Typical concentrations of copper in transformers oils with and without corrosive sulfur compounds.

Fig. 6. Distribution of copper concentration as a function of tan  (at 90 C) in 20 000 transformer oil specimens.

Fig. 5. Copper in oil content found after the contact of corrosive oil with either wrapped or bare copper conductors.

order of decreasing copper concentration; this representation assists in dening the contrast between the two cases more clearly.

In order to explain the results given in Fig. 4, tests were carried out on copper conductors tightly wrapped with one layer of Kraft paper and on exposed copper conductors in oil containing a corrosive sulfur compound (dibenzyl disulde, at a concentration of approximately 150 mg/kg). It was found that the corrosive oil specimens, which were exposed directly to bare copper, were characterized by a higher copper content than those that were exposed to copper conductors wrapped with the single sheet of paper. This result would infer that the paper layer enveloping the copper conductor, ltered out the copper, that presumably accumulated in the form of copper sulde (Fig. 1), thus reducing the amount of copper entering into the oil solution. This ltering action occurred as the copper sulde from the copper conductor diffused through the oil into paper due to the increased diffusion gradient from the high concentration on the copper surface. In addition, as a result of the dipole forces

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IV. COPPER REMOVAL AND ITS EFFECTS

in the cellulose structure of the paper, increasingly more of the semi-conducting copper sulde particles became trapped due to dipole bonding forces in the paper. , measurement has been freThe dissipation factor, quently shown to be effective in detecting charge carrier effects in oils, particularly in cases where only traces of copper are involved. When large numbers of oil specimens are available, cluster analysis techniques may be employed to determine variable dependencies. Fig. 6 depicts a plot of the copper convalue. It centration in a transformer oil as a function of the can be discerned that the point clusters indicate two tendencies values of the 20 000 transformer oil specimens of the tested. One cluster of the experimental points to a dependence value, while the of the copper concentration upon the value independent of the other indication indicates a copper concentration (i.e., an oil free of copper ions/particle complexes). It is evident from Fig. 6 that transformer oils with do not necessarily infer a high copper content; the high losses may equally well arise from other ionic contaminants.

It has been the experience that the conductive and dielectric losses of the oil may be reduced by means of removing copper from the oil. The removal of copper from transformer oil can be industrially accomplished by using a selective depolarization technique, which consists of an on-line chemical/physical treatment of the oil. The oil is forced under specic temperature, ow-rate and pressure conditions through a mixture of solid chemical reagents, in a close-circuit mode connecting the transformer with a treatment plant. This process has been already applied, with small modications, for the in-service removal of corrosive sulfur from mineral oils [11]. Also the Selective Depolarization technology has been industrially applied in a number of cases, to reduce the total copper content of the oil, thus restoring oil losses due to copper content. Tables I and II report two cases of copper removal from copper-contaminated transformer oils. In the rst case, described in Table I, a 130/15 kV, 30 MVA distribution transformer was subjected to Selective Depolarization to remove

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TABLE I FIRST ACTUAL CASE OF COPPER REMOVAL FROM A TRANSFORMER OIL. INITIAL OIL PARAMETERS AND FINAL OBTAINED RESULTS

Fig. 7. First actual case of copper removal. Copper content and tan  value as a function of the number of depolarization cycles.

TABLE II SECOND REAL CASE OF COPPER REMOVAL FROM A TRANSFORMER OIL. INITIAL OIL PARAMETERS AND FINAL OBTAINED RESULTS

copper. The transformer was manufactured in 1989 and lled with 21 tons of a parafnic uninhibited oil. The oil was treated by circulating it 15 times through the depolarization reagents. The total mass of reagents used was 5.2% by weight of the mass of oil. The process was concluded in 10 days, including the installation and the dismounting of the treatment plant. Fig. 7 illustrates the progressive removal of copper during the process, and the subsequent improvement of dielecdown to actric properties, indicated by the decrease of values are plotted against the ceptable levels. Copper and number of treatment cycles, where one cycle denotes the mass

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Fig. 8. Second actual case of copper removal. Copper content and tan d value as a function of the number of depolarization cycles.

of oil circulated in the treatment unit corresponding to the total mass of oil in the transformer. The second case, described in Table II, is related to another distribution transformer, similar to the one described before. The oil was treated by circulating it 11.2 times through the depolarization reagents. The total mass of reagents used corresponded to 6% by weight of the mass of oil, and the process was concluded in eight days. Fig. 8 delineates the progressive removal of copper during the depolarization of this second trans. former and the accompanying decrease of It is interesting to note that in both cases the removal of copper takes place quite rapidly, within the rst few treatment cycles. value requires a few Though the progressive restoration of more cycles of treatment, the nal acceptable level is reached after at least 8 cycles. A possible explanation for this phenomvalue is directly reenon may be that, even if the high lated to copper content, copper is not the only parameter responsible for the dielectric degradation of the oil, as we had already pointed out, and other polar compounds play a role, perhaps marginal but not negligible, in contributing to the enhancement of oil losses. This explanation is partially supported by the fact, that the depolarization process removes also other polar compounds from the oil (i.e., acids) and this contributes to an additional reduction of the losses.

MAINA et al.: DIELECTRIC LOSS CHARACTERISTICS OF COPPER-CONTAMINATED TRANSFORMER OILS

Here, it is perhaps appropriate to indicate that between the rst and the second case described, IEC 60422 and IEC 60296 standards were both revised, and this explains why some of the quantities and some analytical methods differ in Tables I and II. The removal of copper has a further, very important, consequence on the characteristics of the oil. Copper ions and copper particles act as oil oxidation catalyzers, and the results of oxidation stability before and after the process, reported in Tables I and II, clearly demonstrate that the removal of copper allowed a signicant improvement in the oil residual oxidation stability. V. CONCLUDING REMARKS It has been demonstrated that the metal content in transformer oils may compromise the dielectric losses of transformer insulating oils. Copper, as one of the most important materials present in a transformer, is statistically the major component (but not a unique one) responsible for dielectric loss increases in insulating mineral oils. The phenomenon of dispersion of copper into the bulk of the oil, both in dissolved and suspended forms, remains yet to be investigated in terms of the mechanism of copper oxidation and type of chemical complexes involved. Nevertheless, it is quite evident, from eld observations, that the effects of copper are not in any way connected to the presence of corrosive or potentially corrosive sulfur, which can form highly stable copper sulde on the insulating paper surfaces, but forms negligible amounts of dissolved and suspended copper into the bulk oil. The copper dissolution mechanism will be a matter for further research. The removal of copper from the oil by means of an industrial process, named Selective Depolarization, has been found to be capable of efciently reducing the total copper amount in transformer oils. This represents a virtual restoration of the oils dielectric properties, and in a signicant improvement of the oils oxidation stability. REFERENCES

[11] V. Tumiatti, R. Maina, F. Scatiggio, M. Pompili, and R. Bartnikas, In service reduction of corrosive sulfur compounds in insulating mineral oils, presented at the IEEE Int. Symp. Electrical Insulation, Vancouver, BC, Canada, Jun. 811, 2008. [12] F. Scatiggio, V. Tumiatti, R. Maina, M. Tumiatti, M. Pompili, and R. Bartnikas, Corrosive sulfur induced failures in oil-lled electrical power transformers and shunt reactors, IEEE Trans. Power Del,, vol. 24, no. 3, pp. 12401248, Jul. 2009. R. Maina was born in Torino, Italy, in 1971. He received the degree in pure chemistry from the University of Turin, Turin, Italy, in 1996. After a brief experience in R&D in the eld of surface coatings, he has been Laboratory Manager with SEA MARCONI Technologies since 2001. His work deals with oil analyses and diagnoses of the degradation of transformers and insulating uids. Mr. Maina is a member of CIGRE and IEC and is active in numerous working and research groups.

[1] R. Bartnikas, Dielectric loss in insulating liquids, IEEE Trans. Elect. Insul., vol. EI-2, no. 1, pp. 3354, Apr. 1967. [2] R. Bartnikas, Engineering Dielectrics, vol. III, Electrical Insulating Liquids vol. III, 1999. [Online]. Available: www.astm.org/digitallibrary, Monograph 2, ASTM, Philadelphia/West Conshohocken, PA [3] J. B. Whitehead, Impregnated Paper Insulation. New York: Wiley, 1935. [4] J. D. Piper, Liquid Dielectrics, in Dielectrics Materials and Applications, H. Von Hippel, Ed. New York: Wiley/MIT Press, 1954. [5] J. Dunkley and R. W. Sillars, Effects of humid air in power loss in pure and impure parafn oil, Proc. Inst. Elect. Eng. IIA, pp. 8993, 1954. [6] F. M. Clark, Insulating Materials for Design and Engineering Practice. New York: Wiley, 1962. [7] A. H. Rocha, Faults in a 500 kV shunt reactor by corrosive sulfur in insulating oil, presented at the 68th Int. Conf. Doble Clients, Boston, MA, 2001. [8] L. R. Lewand, Corrosive sulfur in transformer insulation, Doble Engineering Company/NETA World, 2003. [9] L. R. Lewand, Negative effects of corrosive sulfur on transformer components, Doble Engineering Company/NETA World, 2004. [10] F. Scatiggio, V. Tumiatti, R. Maina, M. Pompili, and R. Bartnikas, Corrosive sulfur in insulating oils: Its detection and correlated power apparatus failures, IEEE Trans. Power Del., vol. 23, no. 1, pp. 508509, Jan. 2008.

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V. Tumiatti (A09) was born in Ariano nel Polesine, Italy, in 1946. He is the Founder and Owner of SEA MARCONI Technologies, Torino, Italy, an international company that is involved in research, technologies, products, and services for decontamination and diagnosis of energy and environment management. He has more than 40 international patents and is the author of many international technical and scientic publications. Mr. Tumiatti has been the Assistant Secretary of IEC TC10 since 1990. He is also a member of several international groups, with major participation in technical normative activities (CEN, IEC, CIGRE).

M. Pompili (SM04) was born in Rome, Italy, on September 16, 1956. He received the Dr.Ing. degree and the Ph.D. degree in electrical engineering from the University of Roma La Sapienza in 1981 and 1985, respectively. He joined the same university as Researcher in 1989 and since 1993, has been an Associate Professor of Components and Electrical Technologies. Since 1987, he has been the Chairman of TC10 Fluids for electrotechnical application of the Italian CEI, and since 1988, he has been the Secretary of the same IEC Technical Committee. His main interests concern electrical technology with particular reference to dielectric uids and the characterization of new materials to be employed in electrical power components. He is the author of many papers, presented at international conferences or published in the permanent Italian and international scientic literature. In 2007 he was honored with the IEEE Hans Tropper Memorial Lecture, presented at the ICDL, Poitiers, France. He is Associate Editor of the IEEE TRANSACTIONS ON DIELECTRIC AND ELECTRICAL INSULATION.

R. Bartnikas (S56M58SM69F77LF97) received the B.A.Sc. degree from the University of Toronto, Toronto, ON, Canada, in 1958, and the M.Eng. and Ph.D. degrees in electrical engineering from McGill University, Montreal, QC,. Canada, in 1962 and 1964, respectively, and the D.Eng. degree (Hons.) from the University of Waterloo, Waterloo, ON, Canada, in 2002. In 1958, he joined the Northern Electric Co., Lachine, Canada, where he worked on power and communication cables. In 1963, he joined the Northern Electric R&D Laborories (now Nortel) in Ottawa, where he continued his research work on cable dielectrics, gas discharges, thin-lm dielectrics, and integrated circuits. In 1968, he joined the Institut de Recherche dHydro Quebec, Varennes, QC, where he was engaged in dielectrics and discharge research on

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high-power apparatus and cables. Currently, he is an Adjunct Professor at the Ecole Polytechnique of Montreal, Montreal; University of Waterloo; and McGill University. He is a Visiting Professor at the University of Roma La Sapienza (from 1995 to present). He is the Editor of the ASTM monograph series on Engineering Dielectrics and several other books, including Power and Communication Cables.

Prof. Bartnikas is a Life Fellow of ASTM, the Institute of Physics (U.K.), the Royal Society of Canada (Academy of Science), and the Canadian Academy of Engineering. He is the Chairman of the IEC TC10. He has been active in various ASTM, IEEE, IEC, and CIGRE committees.

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