IEEE Transactions on Dielectrics and Electrical Insulation Vol. 16, No.

6; December 2009 1655

Corrosive Sulfur Effects in Transformer Oils

and Remedial Procedures
R. Maina, V. Tumiatti
Sea Marconi Technologies s.a.s.
Via Ungheria, 20
10093 Collegno (TO), Italy

M. Pompili
Department of Electrical Engineering of University of Roma La Sapienza
00184 Roma (Italy)

and R. Bartnikas
Institut de Recherche dHydro Quebec,
Varennes, Quebec, J3X 1S1, Canada

ABSTRACT
The behavior of corrosive sulfur in mineral oils is examined in terms of the failures
observed in transformers, the surfaces of the copper sulfide covered conductors and
degraded paper insulating tapes. The role of Dissolved Gas Analysis (DGA) in the
evaluation of the risk of copper sulfide formation is described. The degree of
corrosiveness of some sulfur compounds is examined and compared using a Kraft
paper wrapped-copper test (Standard IEC 62535). The occurrence of DBDS as the
most relevant corrosive compound is compared with the presence of other corrosive
species in insulating mineral oils. A number of mitigation techniques for corrosive
sulfur are described and evaluated.
Index Terms Corrosive sulfur, transformer failures, mineral oils, corrosion
mechanism, dielectric losses, corrosive sulfur mitigation.

1 INTRODUCTION transformer windings, Method IEC 62535 was

OVER the past decade there has been increased interest in
the effects of corrosive sulfur in mineral insulating oils,
which has been determined to be the main culprit for the
recent failures recorded in shunt reactors and power
transformers [1-4]. The mechanism of failure has been
demonstrated to involve conducting particles of copper
sulfide, which is formed on the copper conductors and
deposited upon the paper insulating tapes, rendering them
partially conductive. This gives rise to enhanced dielectric
losses within the affected paper tapes, leading to thermal
instability and finally to a thermo-electric breakdown of the
insulating system [4].
The exposed copper conductor surfaces have been
observed to become covered with copper sulfide films,
as are also the copper conductors themselves. In an
effort to simulate the actual conditions within
Manuscript received on 22 June 2009, in final form 29 September 2009.
developed in which the specimens consist of copper
conductors upon which a single paper tape layer is
retained. In this test procedure, it has been found that
the presence of corrosive sulfur in the oil may manifest
itself either by copper sulfide deposits on the copper
conductor or upon the paper tape contiguous with it or
on both. One of the objectives of this investigation is to
examine the causes for this peculiar behavior.
Particular attention is given to the characteristics of the
corrosive sulfur degradation mechanism on both the
copper conductors and paper tapes and its overall
effects on transformer and shunt reactor insulating
systems. An additional intent is also to consider the
passivation of the oils for protection of the copper
conductors against corrosive sulfur as well as the
extraction procedures of corrosive sulfur from the oils.
Whilst partial discharges may be contemplated to play
some role in the breakdown process, their occurrence is
unlikely. The conductive and semi-conductive deposits
of copper and copper sulfide in the oil-paper insulation

1070-9878/09/$25.00 2009 IEEE

1656 R. Maina et al.: Corrosive Sulfur Effects in Transformer Oilsand Remedial Procedures

forming the walls of the occluded cavities would tend
to reduce the voltage gradients across the cavities that
are necessary to initiate and sustain the partial
discharge process.
decomposition point. Moreover, low temperature thermal
faults usually affect a larger portion of the power apparatus,
thereby leading to a more diffused deposition of conducting
copper sulfide within the overall insulating system
structure.

2 TRANSFORMER FAILURES
One of the most common types of corrosive sulfur
related transformer failure in the field are found to be
due to high temperatures in the windings, commonly Evidence of general
resulting from inadequate cooling of the windings or overheating in the
design defects. The occurrence of copper sulfide on the faulty winding.
copper conductors and the Kraft paper tapes adjacent to
them represents possible sites of overheating in either an
otherwise healthy winding or an additional source of
overheating in an already faulty winding. Examination of
failed transformer windings provides evidence that many
failures occur either in close vicinity to the top portion of
the winding where the temperature is highest, or in zones
of the winding where insufficient cooling results in a
higher degree of cellulose chain scission than what can
be anticipated on the basis of longevity of the unit in
service. These high temperature hot spots frequently
reveal copper sulfide deposits (cf. Figures 1 and 2),
strongly suggesting that in these failures, corrosive sulfur Copper sulfide found
is either the main cause of the fault or in the least an on conductors
important contributing factor.
Tables 1 and 2 refer respectively to DGA (Dissolved
Gas Analysis) data obtained prior to failure for the units,
whose failures are depicted in Figures 1 and 2. The
Figure 1. Copper sulfide deposit on a copper conductor at a failure site on
dissolved gas analysis data clearly implies overheating the winding of an industrial distribution transformer (23 kV / 4 MVA)
(fault type T1-T2 according to Guidance IEC 60599); this
would suggest that DGA, even if it is not capable to
intercept the electrical fault that leads to the failure of the
unit (probably due to the rapid development of the fault in
its final stages), can be an effective technique to assess
the risk of dangerous formation of copper sulfide in units
impregnated with corrosive sulfur containing oils. A
condition of overheating detected in transformers or shunt
reactors in service, whose oil has been found to be
corrosive according to Method IEC 62535 or Method
ASTM D 1275 B, should thus be considered as a
symptom of possible copper sulfide formation either on
bare copper surfaces or on the paper tapes wrapped onto
the conductors.
Thermal faults at lower temperatures (T1 according to
Guidance IEC 60599, i.e. T< 300 C), that are usually
deemed less dangerous than thermal faults at medium and Conductors meltdown in a
high temperatures for the safety of the unit, should be taken failed winding

more seriously in cases where the transformer oils contain

significant amounts of corrosive sulfur. In fact, the most
commonly occurring corrosive sulfur compound, DBDS,
(cf. chapter 4 of this paper), decomposes at 270 C; thus its
reactivity against copper, even if enhanced by temperature,
Figure 2. Evidence of failure in a copper sulfide contaminated winding of
is likely reduced when the temperature exceeds its a network distribution transformer (130 kV / 130 MVA).
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 16, No. 6; December 2009 1657
Table 1. DGA data prior to a corrosive sulfur related failure (see Figure 1); 1 layer - contact
the high ethane, methane and O2/N2 ratios indicate an overheating with copper
condition (fault type: T2, 300 < T < 700 C according to IEC 60599).
Cu content: 100000 mg/kg (10% by weight)
3 years 4 years
8 months before 2 layer 4 individual
Gas before the before the
the failure (l/l) layers on
failure (l/l) failure (l/l)
each
Oxygen 87 0 355 3 layer
conductor
Nitrogen 72216 60994 64844
Carbon dioxide 8673 3301 3068 4 layer
Carbon monoxide 1068 98 152
Hydrogen 84 75 46 1 layer of common 1 of 12
Methane 198 36 75 wrapping common
Ethane 239 393 390 layers on twin
Ethylene 32 23 31 conductors
Acetylene <1 <1 <1 Figure 3. Papers contaminated with copper sulfide deposits, with the
contamination progressing from the innermost to outer layers.

Table 2. DGA data obtained prior to a corrosive sulfur related failure (see The accepted scale of corrosiveness places elemental sulfur
Figure 2); the ethane, methane and O2/N2 ratios indicate an overheating as being the most corrosive element against copper; this is
condition (fault type: T1, T < 300 C according to IEC 60599). followed in descending order by hydrogen sulfide,
4 months before the 10 months before the mercaptans, sulfides and disulfides. Whilst sulfur organic
Gas
failure (l/l) failure (l/l)
compounds, wherein the sulfur atom is part of the aromatic
Oxygen 384 468
Nitrogen 67293 67440 structure (e.g. thiophenes and related compounds) are
Carbon dioxide 4993 4223 normally considered as non-reactive. Standard IEC 62535 [5],
Carbon monoxide 704 479 which is intended to test for corrosive sulfur and take into
Hydrogen 154 205 account the effect of the paper tapes (as opposed to ASTM
Methane 89 103
Method D 1275B [6] that excludes the involvement of the
Ethane 216 204
Ethylene 95 131
paper insulating tapes), has been found not to respect the
Acetylene <1 <1 conventionally accepted scale of corrosive sulfur reactivity.
This test, in which the specimen consists of a piece of copper
conductor covered with a single turn of paper tape insulation,
3 CORROSIVE SULFUR EFFECTS would indicate, as is substantiated in Figure 5, that alkyl
Corrosive sulfur leads to the formation of substances that mercaptans produce either no or negligible indication for
are insoluble in oil, precipitate as sludge or form copper corrosive sulfur.
sulfide deposits on the copper conductors and paper insulating
tapes. In transformer and shunt reactor windings, copper
sulfide growth is accompanied by its migration within the
layers of the insulating paper. In most of the observed cases,
the copper sulfide concentration tends to be highest within the
inner tape layers adjacent to the copper conductors, with a
tendency to diffuse outwards; this process is strikingly in
evidence in Figure 3, which was obtained on Kraft paper tapes
retrieved from an actual transformer.
A plausible explanation for the observed decrease in the
concentration of copper sulfide towards the outer layers is that
it is due to the higher concentration gradient of copper sulfide
at the surface of the copper conductor. In addition, there is
also an increased temperature gradient effect at the copper
conductor surface or in its vicinity, as a result of the high
currents carried by the copper conductor, which will augment
the reaction rate of the corrosive sulfur with the copper to
form copper sulfide. It can be normally anticipated that the
Kraft paper will tend to be darkened more at elevated
temperatures as a consequence of the oxidation of cellulose
papers (c.f. Figure 4). Yet, it is also frequently observed that Figure 4. Copper sulfide deposits on a conductor and the adjacent paper
the outer layer tapes may became even more darkened due to tape of a winding in a 130 kV/130 MVA transformer, where symptoms of
the oxidation of the oil itself. overheating are also substantiated by DGA measurements.
1658 R. Maina et al.: Corrosive Sulfur Effects in Transformer Oilsand Remedial Procedures
Figure 5. IEC 62535 test applied on sulfur free oils with different
intentionally added sulfur compounds (the equivalent elemental sulfur
content is equal to 75 mg/kg for all compounds).
In contradistinction, dibenzothiophene, which is normally
taken as being inert, produces a corrosive indication. As to be
anticipated, the IEC test is an effective test for sulfides and
disulfides for which it was intentionally devised. Evidently,
the apparent and partially unexpected changes in the scale of
reactivity obtained with the IEC test are to be attributed to its
intended scope, i.e., to identify oils that are capable to transfer
copper sulfide onto the insulating papers and not to assess the
reactivity of the oil on copper. This provides important test
data, because the deposited semiconducting copper sulfide
enhances the conductivity and dielectric loss of the paper
tapes, thereby creating the possibility of thermally unstable
regions and hot spots along the paper tapes that eventually
may lead to thermally induced dielectric breakdown of the
insulating systems in transformers and shunt reactors [3, 4].
One can hypothesize that most likely the chemical reaction
of sulfur with copper cannot per se account entirely for the
capability of the oils to transfer copper sulfide into the
cellulose fibers of the paper tapes. There have been
suggestions that certain specific corrosive sulfur compounds
may play a significant role in the transfer of copper in the form
of complex from the copper conductor surface unto the paper
[7, 8]. Our own studies have indicated that the movement of
copper particles in this elemental form can occur within the
oil. This would infer that copper particles may enter and
become trapped between the interstices of the paper fibers and
at its surface. When in contact with corrosive sulfur oil, these
particles would combine with the corrosive sulfur to form
copper sulfide [9]. These copper particles may occur in
mineral oils in neutral or ionic state in the form of large
micelle-like structures [10]. In neutral form, movement of
copper particles through the relatively open fibre structure of
Kraft paper could result from Brownian movements and from
their concentration gradient at the copper surface.
In addition to the density and thermal gradients and the
Brownian motion effects, the transport behavior of the
macroscopic conducting copper and semiconducting copper
sulfide particles is most markedly determined by the external
electrical field. Both types of particles become charged when
they come into contact with the energized copper conductors.
The imparted electric surface charge renders the copper and
copper sulfide particles mobile in the presence of the ac field,
[10]. The force causing the motion of the charged
macroscopic particles is determined by the product of the
electrical field and the charge on the particles, whilst the force
restraining their motion is that due to the viscous drag which is
proportional to the viscosity of the oil and the equivalent radii
of the particles. It is primarily the mobility of these large
charged macroscopic particles in the presence of external
electrical field that accounts for the migration and
simultaneous presence of both copper and copper sulfide
particles in the oilimpregnated paper tapes of the transformer
winding insulation.
4 CORROSION MECHANISM
Among corrosive sulfur compounds, dibenzyl disulfide
(DBDS) appears to play a predominant role in the corrosion
process. Identified as a major sulfur compound in several
insulting oils [11], it is present in approximately 90% of the
insulating oils employed within the European market.
Considering 20 mg/kg of DBDS as the threshold to render an
oil corrosive, 89.7% of the oils in this population derive their
corrosiveness from DBDS (cf. Figure 6). Hence it is not
surprising, that most of the investigative efforts on the
corrosiveness of the mineral insulating oils have been carried
out on DBDS.
It has been postulated that a more reactive corrosive species
can result when DBDS is reduced to benzyl mercaptan [11]
with a consumption of a stoichiometric hydrogen.
Alternatively, it has been suggested the copper sulfide may be
formed directly upon the surface of the Kraft paper, whereby
the copper is transported as a complex of DBDS, resulting in
by-products such as bis-benzyl and dibenzyl sulfide [7].
Traces of the by-products identified in [7] and [11] have been
detected in mineral oils that are currently in service.
It is interesting that a minor portion of the insulating oils are
found to be corrosive independently of the presence of DBDS.
These oils exhibit a propensity to form the copper sulfide
observed on the surface of the Kraft paper tapes; yet the
compounds responsible for this corrosion process remain to be
identified, though some studies indicate that they should be
sought among the disulfides [12]. Figure 7 delineates the total
disulfide content in given corrosive oil observed in our
laboratory in which the oil has been exposed to a wrapped
copper conductor (conditions are the same as those in Method
IEC 62535) at 150 C for increasing amounts of time. The
resulting deposition of copper sulfide is readily discernible
upon the Kraft paper tapes as portrayed in Figure 8. The
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 16, No. 6; December 2009 1659

nature of the shiny surface deposits was identified by means of well as the shape of the tank. In addition, prior to changing
SEM/EDX (Scanning Emission Microscopy/Energy the oil, a test of corrosive sulfur on a suitable mixture of the
Dispersion X-Ray) technique; the results are shown in Figure old and new oils should be made to ascertain whether the
9, where the peaks of copper and sulfur can be readily mitigation effort is adequate to provide a non corrosive oil.
recognized. As we have pointed out earlier, it is these deposits Corrosive sulfur may be removed from the oil by means of
of semiconducting copper sulfide that augment significantly chemical treatment. There are four common methods
the dielectric losses of the tapes [4]. available, namely: oil depolarization, traditional oil
reclamation, solid/liquid (S/L) extraction, and liquid/liquid
(L/L) extraction. Oil depolarization has been employed
5 CORROSIVE SULFUR MITIGATION both off-load and on-load to reduce the corrosive sulfur
Several mitigation techniques may be employed to reduce content in transformers. It uses a combination of solid
the impact of corrosive sulfur in transformers and reactors. reagents, chemicals and sorbents and is capable of reducing
The most obvious approach is to use metal surface passivators the DBDS content down to a level of < 5 mg/kg. Figure 12
to provide a film cover over the copper conductor to protect its depicts the rate of decrease of corrosive sulfur as a function
surface. A common metal passivator in use is that of of the number of the treatment cycles.
toluitrazole-dialkyl-ammine (commercially available as
Irgamet39) that is usually added to new and used transformer
oils in concentration levels of approximately 100 mg/kg. The
purpose of the metal passivator is to protect the copper
conductor by forming a molecular layer onto the copper
surface; however, it does not remove the corrosive compounds
from the oil and it evinces some unexpected and undesired
collateral effects, such as the release of hydrogen and carbon
oxides. This often leads to erroneous gas evolution test results.
Figure 10 portrays hydrogen gas evolution in a transformer
prior to and following metal passivation; the introduction of a
metal passivator is seen to lead to a very marked increase in
gas generation.
Perhaps one of the most adverse effects of thermal stress
and oxidation by-products of the oil is the ensuing
instability of the metal passivator. Metal passivator
depletion during service is observed in highly loaded power
transformer units, containing oils where the oxidation
process has already commenced. An initial depletion of the
metal passivator is to be anticipated in 10-15% of the units Figure 6. Occurrence of DBDS in 242 corrosive oils.
passivated during the service; on the other hand,
transformers initially impregnated with a passivated oil
appears not to be affected by problems of abnormal
passivator consumption. A disconcerting effect of metal
passivator depletion is illustrated in Figure 11, where it can
be perceived that a reduction below a concentration of 25-
30 mg/kg can cause the insulating oil to revert back to a
corrosive state; surface discoloration of the copper
specimens demonstrates the growth of the copper sulfide
films on the copper conductor specimens.
One obvious mitigation technique, that is commonly
used, consists of simply replacing the existing oil in a
transformer or shunt reactor unit by a new, non corrosive
oil. Evidently in this approach, the corrosive compound
content is reduced by diluting the existing oil according to
the ratio between the volume of the new oil added and the
remnant volume of the old oil (i.e., the existing remaining
oil at the bottom of the tank and windings of the specimen
unit). The latter ratio may vary from 5 to 12% depending Figure 7. Decay of total disulfides during exposure of a corrosive oil to
on the amount of paper and other absorbing materials as copper and paper at 150 C.
1660 R. Maina et al.: Corrosive Sulfur Effects in Transformer Oilsand Remedial Procedures

140

Irgamet39 conc. (mg/kg)

120
100 Borderline

80
60 Corrosive
Non Corrosive
40
20
Non Corrosive
0

24/03/06

13/05/06

02/07/06

21/08/06

10/10/06

29/11/06

18/01/07
Sampling date

Figure 11. Decay of the metal passivator and its effect on corrosiveness of
Figure 8. Increasing deposition of copper sulfide on copper conductors
the oil.
(left side specimen) and kraft paper tapes (right side specimen) as a
function of time.

160

Concentration (mg/kg)
140 DBDS
Irgamet 39
Copper 120

100

80
Sulfur
60

40

20

0
0 1 2 3 4 5 6 7 8 9 10
Number of treatment cycles
Figure 9. SEM/EDX spectrum of deposits formed on Kraft paper by a
corrosive oil not containing DBDS. Figure 12. Removal of DBDS by depolarization of the oil
Gas evolution (ml/l)

(l/l)
Hydrogen As concerns the reduction of corrosive sulfur compounds
Passivation

trend
in oils, it should be borne in mind, that in the case of DBDS
containing oils, the reduction also involves necessarily the
residual oxidation stability of the oil. It has been
demonstrated that DBDS acts as an oxidation inhibitor, i.e.,
as a secondary antioxidant, with the consequence that its
Date of measurement (month/year)
removal may require the necessity to re-inhibit the oil with
Figure 10. Example of stray gassing following the passivation with
Irgamet39. a classical cresolic antioxidant, such as di-tert-butyl-para-
cresol (DBPC). Table 3 provides some typical values of
oxidation stability prior to and following depolarization as
The traditional on-line method has been originally well as those obtained after re-inhibition.
developed to reduce the polar compound concentration in
mineral oils, using fuller earths and clays. However, it was
also found to be effective in reducing the corrosive sulfur Table 3. Oxidation stability of depolarised oil before and after the re-
content. The solid/liquid method involves the forcing of inhibition with di-tert-Butyl-para-Cresol (DBPC)
oils through a suitable sorbent to reduce the corrosive
Oxidation After re-
sulfur content, whilst the liquid/liquid corrosive sulfur After on-Load IEC 60296
stability inhibition with
depolarization reference
extraction method is based on the selectivity of certain oil- parameters,
(test duration:
DBPC 0.3%
values (for
immiscible solvents, which are placed in contact with the according to (test duration:
164 h) unused oil)
IEC 61125 500 h)
oil in a separate cistern to extract the corrosive sulfur
sludge (%) 0,91% 0,76 < 0,80
compounds. However, this system of corrosive sulfur
extraction has not been validated in industry. TAN (mg/g) 1,55 0,78 < 1,2
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 16, No. 6; December 2009 1661

Figure 13 delineates schematically the depolarization

Corrosivity according to Cigre's CCD

ASTM D 130 scale
ASTM D 1275 B

Corrosive

Corrosive
system employed for the removal of DBDS from Cigre's CCD
4c
transformer specimens under on-load conditions. It can be 4b
also employed to remove the metal passivator added to the 4a
3b
oil to protect the copper conductors surface against 3a
2e
corrosive sulfur. 2d
2c
Max 800 lt/h 2b

Non Corrosive

Non Corrosive
2a
1b
1a

Max 800 lt/h 0 1 2 3 4 5 6 7 8 9 10

Number of treatment cycles
Transformer oil
PUMP
Mechanical
Figure 14. Corrosivity of the treated transformer oil as a function of the
F filter number of treatment cycles, with the corrosivity test method as a
parameter.

Figure 15 portrays an interesting behavior of tan and

TAN (total acidity number). It can be perceived that tan
evinces a dispersed peak over first six cycles of the
Mechanical
Max 5000 lt/h
depolarization treatment. This is a consequence of an
F Chemical solid
filter
reagents increased concentration of polar molecules that are created
Heating Cooling
at the beginning of the treatment procedure. However, as
Main the number of the polar molecules diminishes, the tan
circuit
PUMP
Max 1500 lt/h
DBDS chemical values are decreased, because an increased number of the
Modification
(80-90C) ionic charge carriers are eliminated from the oil. It is thus
most noteworthy that the variation of tan with number of
Absorption solid
treatment cycles in Figure 15 is strikingly similar to that of
reagents
VACUUM PUMP corrosivity using ASTM D1275B in Figure 14, i.e., the
charge carrier concentration, which determines the
tan value, is proportional to the corrosivity of the oil. The
Vacuum
Modified DBDS
Retention dehydrator fall in the acidity number is attributed directly to a
Auxiliary Max 3500 lt/h
(55-60C)
reduction in the concentration of oxidized molecular
circuit
constituents of the oil. The depolarization treatment has two
Figure 13. System for removal of DBDS from transformer oil: scheme for other advantages in that both the interfacial tension (IFT)
On-Load Depolarisation Process. and water content are improved. Whilst initially the IFT
values are low according to IEC 60422, with subsequent
Figure 14 delineates the variation of the corrosivity with treatment cycles they rise to acceptably good values
the number of treatment cycles, with the corrosivity being (3210-3 N/m). The water content after exhibiting an
determined using both the ASTM D 1275B and IEC 62535 increase is subsequently reduced to approximately 5 mg/kg
methods. At the onset of the depolarization process, both after 10 depolarization cycles (cf Figure 16).
the test methods for the corrosiveness of the oil are seen to
yield a negative result because of the presence of the metal 0,16
passivator; as the passivator content decreases to a level
TAN (mg/g) - tan

0,14 tan
tan delta
that becomes insufficient to protect the copper, the TAN
0,12
corrosiveness is augmented.
0,1
The data in Figure 14 would suggest that the ASTM
0,08
method is more sensitive to corrosive sulfur than the IEC
method, which is directly attributed to the two different 0,06

ways that the copper test specimen is exposed to the 0,04

corrosive containing oil. In the ASTM method the copper 0,02
conductor is exposed directly to the oil, whilst in the IEC 0
method a single paper tape is interposed between the 0 1 2 3 4 5 6 7 8 9 10
copper and the remainder of the oil external to it. For the Number of treatment cycles
corrosivity scale ASTM D 130 is employed, which is based Figure 15. Dissipation factor (tan) at 90C and acidity of the treated
on a graded color code of the copper conductor. transformer oil as a function of the number of treatment cycles.
1662 R. Maina et al.: Corrosive Sulfur Effects in Transformer Oilsand Remedial Procedures
- Water (mg/kg)
35
30
25
IFT
20
Water
-3N/m)
15
10
IFT (10
5
0 transformers and shunt reactors containing corrosive oils,
0 1 2 3 4 5 6 7 8 9 10
Number of treatment cycles
Figure 16. Interfacial tension (IFT) and water content of the treated
transformer oil as a function of the number of treatment cycles.
6 CONCLUSION
Copper conductors and paper tape specimens
retrieved from corrosive sulfur induced failures in
transformers and shunt reactors indicate that the
highest concentration of copper sulfide occurs on the
surface of the Kraft paper layer adjacent to the copper
conductors and thereafter its concentration decreases
with each successive outer tape paper layer, i.e., the
diffusion gradient is an inverse function of the distance
from the highest to the lowest concentration. However,
the outward migration of copper sulfide through the
relatively open fibre structure of the paper is not the
only mechanism active; there are other factors that play
a contributing role to the appearance of copper sulfide
on the Kraft paper tapes. The formation of a copper-
DBDS complex has been suggested by some
researchers to be responsible for the copper migration
onto the solid insulation, but the transfer of the copper
itself on the paper surface was observed either in
presence of corrosive sulfur and in non corrosive oils;
thus, this migration mechanism is still far from being
fully elucidated and will need further studies.
The occurrence of elemental copper in the insulating
oils of power apparatus and cables and its attending
effect to increase the dissipation factor in mineral oils
has been well recognized now for many decades.
Though the exact process of how elemental copper is
transformed into miscible ions that augment the
tan v alues of oils is not well understood [9, 10, 13],
the presence of copper in the paper tapes was detected
even in absence of copper sulfide deposits [9], after
reaction of the paper wrapped copper conductor with
oils free from corrosive sulfur. The elemental copper in
the paper will thus eventually react with the corrosive
oils to form the semiconductive copper sulfide, which,
because of its ionic character, will enhance the overall
dielectric losses of the paper tapes.
While most corrosive sulfur oils contain DBDS, there
is a significant percentage that do not [14]. In most cases
where a corrosive oil is found to be free from DBDS, a
relevant amount of disulfides and mercaptans can be
detected; laboratory simulations of the depletion of total
mercaptans and disulfides during the contact with bare or
paper wrapped copper may be useful to assess the
effective corrosiveness of the oil. In order to take
preventive measures against the corrosive sulfur in the
oils, the copper conductors should be effectively
passivated to prevent copper sulfide formation. Likewise
should have the corrosive sulfur constituents removed.
There are several techniques available for this purpose,
but at this time it would be appear that the technique
employing the on-load depolarization process is the most
versatile. Copper contaminated oils, in which tan rises
to undesirable values, can be decontaminated with the
same technique, reducing copper content and,
consequently, the losses [9].
Note from the Editor-in-Chief: Since two of the authors (M. Pompili and R.
Bartnikas) are Guest Editors of this special issue on Liquid Dielectrics, the
reviews of this paper were handled by the another Associate Editor in order
to preserve the anonymity of the reviewers.
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sulfide generation in insulating oil, 75th Annual Intern. Doble
Client Conference, Boston, USA, 2008.
[8] T. Amimoto, E. Nagao, J. Tanimura, S. Toyama, Y. Fujita, H.
Kawarai and N. Yamada, Identification of Affecting Factors
of Copper Sulfide Deposition on Insulating Paper in Oil, IEEE
Trans. on Dielectrics and Electrical Insulation, Vol. 16, pp.
265-272, 2009.
[9] R. Maina, V. Tumiatti, M. Pompili and R. Bartnikas,
Dielectric loss characteristics of copper contaminated
transformer oils, paper submitted to IEEE Trans. Power
Delivery (TPWRD-00943-2008).
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 16, No. 6; December 2009
[10] R. Bartnikas, Editor, Engineering Dielectrics, Vol. III,
Electrical Insulating Liquids, Monograph 2, ASTM
Philadelphia/West Conshohocken, 1994 (available from
www.astm.org/digitallibrary).
[11] R. Maina, F. Scatiggio, S. Kapila, V. Tumiatti, M. Tumiatti and M.
Pompili, Dibenzyl disulfide (DBDS) as corrosive sulfur contaminant
in used and unused mineral insulating oils, CIGRE Sub Committee
A2, Paris (www.cigre-a2.org/Site/Publications).
[12] M. Dahlund, L. Pettersson, H. nnerud, K. Gustafsson, R.
Leandersson, S.Karlsson, Detection of total mercaptans and
disulfides in corrosive insulating mineral oils, CIGRE Joint A2/D1
Colloquium, Brgge, 2007.
[13] R. Bartnikas and K.D. Srivastava, Power and Communication
Cables, Wiley/IEEE Press, New York, 2003.
[14] CIGRE WG A2-32, Copper sulphide in transformer insulation,
Final Report, Brochure 378, 2009.
Riccardo Maina was born in Torino, Italy in 1971.
He received the Master degree in pure Chemistry
from the University of Turin in 1996. After a brief
experience in R&D in the field of surface coatings,
he is with Sea Marconi Technologies since 2001 as
Laboratory Manager. His work deals with oil
analyses and diagnoses of the degradation of
transformers and insulating fluids. He is a member
of Cigre and IEC, he is active in numerous working
and research groups.
Vander Tumiatti was born in Ariano nel Polesine-
(RO - Italy) in 1946. He is the founder and owner of
SEA MARCONI TECHNOLOGIES (Torino
Italy), an international Company working in
research, technologies, products and services for
decontamination and diagnosis for energy and
environment management. Mr. Tumiatti has more
than 40 international patents. He also is author of
about 85 international technical and scientific
publications. Since 1990 he is the Assistant
Secretary of IEC TC10, being also a member of several international
groups, with intense participation in technical activities (CEN, IEC,
CIGRE).
1663
Massimo Pompili was born in Roma, Italy on 16
September 1956. He received the Dr.-Ing. degree in
1981 and the Ph.D. Degree in 1985 in electrical
engineering from the University of Roma La
Sapienza. He joined the same University in 1989
as a Researcher and since 1993 is an Associate
Professor in Components and Electrical
Technologies. Since 1987 he is the Chairman of
TC10 Fluids for Electrotechnical Application of the
Italian CEI, and since 1988 he is the Secretary of the same IEC Technical
Committee. His main interests concern electrical technology with
particular reference to dielectric fluids and the characterization of new
materials to be employed in electrical power components. He is the author
of more than 100 papers, presented at international conferences or
published in the permanent Italian and international scientific literature. In
2007 he was honoured with the IEEE Hans Tropper Memorial Lecture,
given at the IEEE International Conference on Dielectric Liquids (ICDL)
held in Poitiers, France. Since 2009 he is an Associate Editor of the IEEE
Transaction on Dielectric and Electrical Insulation.
Ray Bartnikas (S56-M58-SM69-F77-LF97)
received the B.A.Sc. degree from the University of
Toronto in 1958 and the M.Eng. and Ph.D. degrees
from McGill University in 1962 and 1964,
respectively, all in electrical engineering, and the
D.Eng. degree (honoris causa) from the University
of Waterloo 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 film dielectrics and integrated circuits. In 1968 he joined
the Institut de Recherche dHydro Quebec, Varennes, Quebec, where he
was engaged in dielectrics and discharge research on high power apparatus
and cables. He is currently an Adjunct Professor at the Ecole
Polytechnique of Montreal, University of Waterloo and McGill University
and a Visiting Professor at the University of Roma La Sapienza (since
1995 to present). Dr. Bartnikas is the Editor of the ASTM monograph
series on Engineering Dielectrics and several other books including Power
and Communication Cables. He is a Fellow of ASTM, the Insitute of
Physics (UK), the Royal Society of Canada (Academy of Science) and the
Canadian Academy of Engineering. He has been active in various ASTM,
IEEE, IEC and CIGRE Committees. Presently he is also the Chairman of
the IEC TC10.