11 - Chapter 2

Chapter 2 Literature Survey
Chapter 2
LITERATURE SURVEY
2.1 Introduction
A detailed survey of literature was carried out on various aspects of copper

corrosion in transformers. These included (a) factors responsible for copper corrosion (b)
Evaluation methods for understanding the effect of corrosive sulphur (c) mitigation
technics including passivator usage, their advantages and adverse effects on transformer
operation and their limitations (d) extraction of sulphur compounds from transformer oil
(e) moisture assessment in insulation, (f) dielectric measurements under copper corrosion.
Results of published research carried out by scientists and engineers from different parts
of the world are discussed in this chapter.
2.2 Literature on sulphur compounds
Jongen and coworkers [1] have observed that the presence of mercaptan sulphur
is the main cause for the formation of copper sulphide rather than other forms of sulphur.
Mercaptans sulphur is one form of the sulphur which is very reactive. It is very low in
concentration in case of fresh oils and it is consumed at high temperatures and its value
goes down from 1 ppm to almost zero levels when thermal ageing is carried out. The
corrosive oils have shown random variation in mercaptans sulphur content with thermal
ageing.
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Toyama and coworkers [2] have used gas chromatography mass spectrometry
using alumina base solid phase extraction technique for the detection of bibenzyl (BiBZ),
dibenzyl sulphide (DBDS) and DBDS of lower concentrations. A good relationship
between the weight change of copper strip and BiBZ/ DBS generation is obtained under
heating with insulating oil including DBDS and copper strip. Hence they observed that
BiBZ and DBS are the byproducts of the reaction of formation of copper sulphide.
Work includes the elucidation of chemical reaction formula between DBDS and
copper and generation of DBDS-Cu rate are also estimated. The reaction mechanism for
the formation of copper sulphide has been explained.
Lewand and others [3] have discussed that there are different types of sulphur
compounds in refined transformer oil but not all types are considered to be corrosive or
reactive. They have reported that the reactive and corrosive sulphur components are of
very low order in fresh transformer oils but during service, some sulphur components are
converted to reactive and corrosive forms which react with copper forming copper
sulphide. It is also reported that elemental sulphur present may result in some corrosive
acids. Further mercaptan can directly react with copper forming copper sulphide and the
effect of sulphide on copper is negligible. It is reported that disulphides and thiophenes
are also quiet stable.
B.P Singh and coworkers [4] have carried out a set of experiments in which
detailed studies are carried out with a view to understand the dielectric degradation
phenomena of the transformer insulation. Direct ageing of samples of cellulose, several
specific conditions like pre-determined quantum of mercaptan sulphur in different
environment like nitrogen and air, nitrogen blanketing at elevated temperatures for long
durations as well as different thickness of paper and conductor are considered and the
results are discussed.
Specific instruments like ESCA, SEM, EDAX, IC and AAS have been used to evaluate
cellulose paper and conductor samples from failed transformer for their metallurgical and
chemical properties. The experimental evidences suggest the likely presence of CuO,
Cu2S and individual elements like C, O and sulphur.
21
V. Tumiatti and coworkers [5] have compared different standard test methods
for the detection of corrosive sulphur in oils and they observed that method DIN
31353, which has been recommended by the IEC, is incapable of detecting corrosive
sulphur in mineral oils at a sensitivity level which is necessary for preventing
breakdown faults in oil immersed power apparatus. However, it has been demonstrably
shown that the ASTM Test Method D1275 can readily accomplish this task, provided the
silver strip specimen is substituted with a copper strip specimen and the test
temperature is increased to 140C and the testing duration is extended to either to 48
hours or preferably to 72 hours. Since it is of paramount importance to intercept new
oils containing corrosive sulphur before they are deployed in transformers (either as
refill oils or as oils in newly manufactured transformers) and in order to avert
the massive types of winding failures described in this paper, it is strongly recommended
that IEC TC 10 committee should adopt the modified ASTM method. Whilst it is
desirable to reclaim the rejected new oils that are determined to contain corrosive
sulphur, it has been found that traditional reconditioning or reclaiming processes are
ineffective. However, there is a possibility that this task may be accomplished by
removing the mercaptans from the mineral oils by means of special techniques of
selective oil depolarization. These techniques were found to be very effective in
removing the mercaptans and organic sulphides from the oil.
Ryder [6] has stated that sulphur corrosion is not merely an oil problem, but a
problem of complete transformers. It appears that certain conditions which favor sulphur
corrosion can be created by errors in construction or design. The author has
s t a t e d t h e purpose of this paper is to present three case studies where copper
corrosion has occurred and to draw conclusions of general interest to them. Case Study 1
1000 MVA Autotransformer; Case Study 2 600 MVA Generator Transformer; Case
Study 3 192 MVA Generator Transformer
The author observed clear links between transformer design and sulphur
corrosion in these three case studies. It is stated that in every case, the designer has
inadvertently created conditions which favor sulphur corrosion higher temperatures
and low levels of dissolved oxygen. The high temperatures also promote solid
insulation aging, even in the absence of potentially corrosive sulphur in the oil.
22
Manufacturers and operators are therefore advised carefully to review designs to

ensure that all parts of windings receive sufficient oil flow. Operators are also advised
that sulphur corrosion can and does affect transformers built before oil containing
excessive amounts of potentially corrosive sulphur came into widespread use. Refilling
or topping-up with such oil can have significant consequences later.
The conditions which promote sulphur corrosion also promote solid insulation
aging. In two of the case studies discussed in this paper, furan analysis gave an
indication of developing problems. Unfortunately this indication will not always be
present, and will not always be clear when it is present. Good transformer design should
be combined with careful selection of oil using improved tests available for potentially
corrosive sulphur.
A paper by Jain Li [7] has discussed the details of the influences of copper
sulphur corrosion and copper sulphide deposition on copper wires and oil-paper
insulation in power transformers. Thermal aging tests of paper-wrapped copper wires and
bare copper wires in insulating oil were carried out at 130 C and 150 C in laboratory.
The corrosive characteristics of paper-wrapped copper wires and bare copper wires were
analyzed. Dielectric properties of insulation paper and insulating oil were also analyzed
at different stages of the thermal aging tests using a broadband dielectric spectrometer.
Experiments and analysis of results show that copper sulfide deposition on surfaces of
copper wires and insulation paper changes the surface structures of copper wires and
insulation paper. It is stated that copper sulphur corrosion changes the dielectric
properties of oil-paper insulation and the copper sulfide deposition greatly reduces the
electrical breakdown strength of oil-paper insulation. Further the authors have concluded
that metal passivators are capable of preventing copper wires from sulphur corrosion. The
experimental results may be helpful for investigations on fault diagnosis of internal
insulation in power transformers.
Mats [8] in their report have mentioned about the problems associated with the
effects of corrosive or potentially corrosive sulphur compounds in insulation oil which
has gained considerable attention in recent years. Large efforts have been made in the last
few years to find more sensitive tests than previously used ASTM D 1275 and DIN
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51353. Especially extended versions of the ASTM copper strip test (e.g. D 1275B), and
various tests involving paper wrapped copper (e.g. that proposed by CIGRE WG A2-32),
have found wide-spread use. Some progress has also been reported in identification of
active sulphur compounds. There is consensus that mercaptans are very aggressive to
metals in general and copper in particular. However, many oils that are corrosive sulphur
contain very little free mercaptan sulphur. Disulphides is another group of sulphur
compounds suspected of being potentially corrosive, and one such compound, dibenzyl
disulphide (DBDS) has been identified, and found in substantial amounts in many oils
showing corrosive behavior. Even though it seems that much of the problems
experienced lately are due to the presence of DBDS, also some oils without this
substance have caused failures due to copper sulphide formation, and give extensive
sulphide formation in the new test methods involving paper. It seems a natural next step
to look for other disulphides than DBDS. However, it is said that to look for other
individual compounds of this type may prove very difficult.
CIGRE Working Group Report WG A2.32 [9] gives a brief introduction to the
formation of copper sulphide and its consequences. It is reported that temperature is a
strong influencing factor in the formation of copper sulphide. In this report, test methods
for detection of corrosive and potentially corrosive sulphur in mineral oil are suggested.
Tests for corrosion are carried out with different insulating oils like unused transformer
oils of types which have caused failures, unused oils with unknown behaviour, highly
aged used transformer oils etc, and the test results are evaluated. The possible mitigation
techniques like oil passivation, oil change, oil treatment etc, are also discussed. This
report highlights briefly the mechanism of copper sulphide formation.
Plaza and others [10] studied the homogeneous and heterogeneous

decomposition of DBDS over a temperature range of 170-150 C. Authors have
determined the sulphur containing decomposition products. Products formed during
homogeneous conditions are elemental sulphur, dibenzyl monosulphide, thiol, hydrogen
sulphide and mono sulphide. Products formed due to heterogeneous conditions are
elemental sulphur, monosulphide and oxidized species formed by oxidation of DBDS.
24
According to Lance Lewand [11] dibenzyl disulphide (DBDS) is one of the

several sulphur compounds known to cause copper corrosion in transformers under
certain circumstances. Remedial processes such as adsorbents, absorbents, and oil
change-out have been known to reduce the concentration of DBDS in the oil. However, if
not destroyed or removed below several mg/kg (ppm), breakdown of the DBDS to benzyl
mercaptan or a DBDS-Copper complex can still cause corrosion of copper and the
formation of copper sulfide. Passivators are also being used to protect the copper against
corrosive sulphur attack but it does not remove or destroy any corrosive sulphur species
or those sulphur compounds that can become corrosive. This paper discusses a process in
which the destruction of DBDS is complete to below 1mg/kg and it can be performed at
the transformer and the oil may be reused in the same unit and it was concluded that both
the laboratory process and the PSS process (as used in the field) were completely
successful in destroying DBDS (dibenzyl disulphide) from the oil. This process does not
work on all types of sulphur compounds that are corrosive as experiments have been
conducted in this respect. However, it may be just as successful on other sulphur
containing compounds such as certain types of mercaptans, sulfides and disulphides (but
possibly not all) and has not been tested out in this regard. It is most likely that sulphur in
the form of sodium sulfide or related compound is formed by the process and removed. It
is further stated that research needs to be conducted in this respect.
Like other mitigation techniques, the removal of DBDS does not affect corrosion
that has already taken place. However, this process will destroy DBDS and benzyl
mercaptan that is remaining in the oil. For now, it is recommended that besides the
process to remove the DBDS, clay treatment followed by the addition of synthetic
oxidation inhibitor to a concentration between 0.22 and 0.30% (by weight) be
incorporated into the process. In removing the DBDS, the oil might be less stable towards
oxidation and thus the reason for the addition of an oxidation inhibitor. The reason for
this is that most oils with DBDS are not inhibited and therefore require some sort of
stabilization for oxidation after the process of DBDS destruction and thus the
recommendation to add DBPC (BHT) or DBP. For sealed transformers this is less of a
concern.
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Authors have further put forth a theory that DBDS is cleaved into corresponding
mercaptides and other six ring products. Four possibilities are suggested as follows:
Benzyl mercaptide was the most likely result. The mechanism taking place is as in
equation 2.1.
(2) Cu2S, Cuprous Sulfide

SH (Copper Sulfide)
+
HEAT HEAT
+
CH3
+
S (2) H (4) Cu
S SH
CH3
benzyl mercaptan
dibenzyl disulfide ethylbenzene
(2.1)
Benzyl mercaptide is volatile and would not ordinarily be present in the newly
refined transformer oil, as it would be easily removed. However, once produced there is
no escape in a well-sealed transformer. It is very oil soluble and it is very reactive to
copper and silver surfaces.
The same is not true in free breathing transformers where oxygen is present in
higher concentrations. It is concluded that degradation of organic sulphur compounds
involves an oxidative attack which is localized at the sulphur atoms. As a result benzyl
mercaptide molecules are oxidized and some DBDS is actually reformed as in equation
2.2. Some of the benzyl mercaptides is likely to be lost through free breathing nature of
the conservator. Copper sulphide is formed but atleast half or less than what would be
formed in a sealed transformer. It is most likely that some water is also formed, but the
amount would be so minute in comparison to the water content already existing in the
transformer, it would be indistinguishable.
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Cu2S, Cuprous Sulfide

SH (Copper Sulfide)
HEAT HEAT
+ +
S (2) H (2) Cu
S SH Oxidation
+ H2 O
benzyl mercaptan S
S
dibenzyl disulfide
(2.2)
Experiments were carried out by Lance Lewand and Scott Reed to make sure that
DBDS aided the corrosive sulfur compounds in the oil that attacked copper and caused
the production of a copper sulfide deposit on the copper surface. DBDS was added to
white mineral oil in varying concentrations of 5, 50,125 and 250 ppm. It is observed that
fresh mineral oil has a very low total sulfur content, measured at maximum of 2-3 ppm.
White oil that was used in the experiments was tested without the addition of DBDS and
did not exhibit any signs of copper corrosion (ASTM D 1275B) or copper sulfide
formation on the paper insulation by the Covered Conductor Deposition (CCD) test
method. The authors claim that as the concentration of DBDS increases, the time taken to
failure reduces. The white oil with 250 ppm of DBDS was tested using ASTM Test
Method D 1275B. It was seen that the oil failed this test within 40 hours. In addition, the
concentration of DBDS was determined before and after the test and it was observed to
be reduced by more than 50% with a final concentration of 116 ppm.
Lance Lewand [12] has reported some of the details of the teardown and
laboratory investigation of a failed GSU transformer. The failure involved sulfide
contamination of the paper conductor and copper sulfide in the associated paper
insulation in the upper third portion of the field winding. The theory is put forth that a
combination of time and temperature and corrosive sulphur in the oil created conditions
to exist in the transformer that caused this problem despite the oil having passed the
standard test criteria for corrosive sulphur. Although the mechanism is still unclear,
copper ions migrate to the insulating paper adjacent to the conductor, react with corrosive
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sulphur compounds, and cause a reduction in dielectric strength. At some point, the
voltage being carried by the conductor exceeds the insulating capacity of paper insulation
and BIL rating of the transformer. The result is arcing between two or more disks and a
subsequent burn through.
Vander Tumiatti [13] describes some corrosion phenomena involving copper,

insulating oil and solid insulation of oil-immersed transformers and reactors. The paper
reports evidences of presence, occurrence and effects of dibenzy disulfide (DBDS),
other Corrosive Sulfur compounds and No-Sulfur Corrosion in insulating mineral oil.
Both copper sulfide deposition and dissolved copper formation are investigated; giving
evidences derived both from field experience and laboratory tests. A new diagnostic
method, called Total Corrosive Sulfur, to quantitatively detect the presence of
corrosive sulfur compounds in the oil and Finger Print are described.
The available techniques for diagnostics of corrosion phenomena and evaluation

of the tendency of the oil to form conductive deposits are described. A review of the
available mitigation techniques to reduce the effects of corrosion phenomena is reported
with regards to their effectiveness. The removal of corrosive compounds or dissolved
copper by means of on-load and off-load Selective Depolarization is compared with
other mitigation techniques.
These methods are capable of drastically reducing the reaction times for the
corrosivity test, typically from 72 to 12 hours, on passivated oils and from 500 to less
than 24 hours for the aging test on inhibited oils and reducing the volume of oil used
(typically from 250 ml to 15 30 ml for the test with copper strip) with a fast quantitative
evaluation of the properties of the oil tested and the equipment with which the oil is in
contact, such as for example, insulating paper in transformers. The methods include tests
capable of determining and implementing optimized formulations for the
decontamination, depolarization and detoxification treatments of the oils.
R. Maina and others [14] have studied the behavior of corrosive sulfur in
mineral oils in terms of the failures observed in transformers, the surfaces of the copper
sulfide covered conductors and degraded paper insulating tapes. Authors have described
the role of Dissolved Gas Analysis (DGA) in the evaluation of the risk of copper sulfide
28
formation. 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. Paper describes a number
of mitigation techniques for corrosive sulfur.
Authors conclude that 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 fiber 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.
Exact process of how elemental copper is transformed into miscible ions that
augment the tan values of oils is not well understood. The presence of copper in the
paper tapes was detected even in absence of copper sulfide deposits, 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 semi
conductive copper sulfide, which, because of its ionic character, will enhance the overall
dielectric losses of the paper tapes.
Jill R and coworkers [15] have discussed the problems caused by corrosive
sulfur and have reasoned out why the problem has resurfaced. New test methods
developed to detect corrosive sulfur and remedies suggested to prevent further
destruction are presented.
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Authors have a view that while corrosive sulfur problems were originally
discovered decades ago, it wasnt until the past several years that serious problems have
once again surfaced. The electrical Power industry has responded strongly with the
development of new and more stringent test requirements as well as various effective
remedial action options. The industry is now moving toward requirement of all new
transformer oil to meet both the 1275B and CCD tests. It is recommended that all critical
transformers in-service with oil purchased from the late 1990s to the early 2000s be
tested for corrosive sulfur using both the 1275B and CCD tests before more possible
damage occurs to the integrity of the insulation system, hence the life of the transformer.
If the oil fails either test, the 1275A and DBDS concentration tests may also be
performed. If the transformer also fails the 1275A test, it is highly recommended to
replace the oil and also consider passivating the oil if it has been in-service for several
years. It is not possible to remove all the oil as some will remain on the core and coils. If
it passes the 1275A test, passivate the oil and monitor DBDS concentration.
Hermi Visser [16] has reported in 2005 in his paper that sealed transformers
running at high temperature are considered to be at risk of copper corrosion. Author also
explains the factors responsible for corrosive sulphur activities. Following are the key
factors responsible for copper corrosion.
Direct contact between bare copper and oil

High volumes of reactive sulphur mainly elemental and mercaptan sulphur
Reduced oxygen levels in oil
High temperature spots inside the transformers.
P.M. Mitchinson and coworkers [17] have explained the possibility of gassing
of hydrocarbon compounds containing sulphur and or hydrogen sulphide gas from
sulphurous mineral oil when the local temperature is sustained at a high value for a
minimum time resulting in copper sulphide formation. The mechanism involves thermal
action on sulphurous oils leading to the evolution of a range of sulphurous gaseous
compounds. One or more of these compounds immediately react with the copper to
produce copper sulphide deposits. The gaseous compounds are quickly consumed or
dissipated making forensic analysis difficult.
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Author also explains that the mechanism of copper sulphide formation is fostered
by high temperatures such as the hotspots. This explains observed deposition of copper
sulphide at the tops of transformers. In general, the paper highlights the omission of the
detection of sulphorous compounds either as a gas or dissolved in oil.
Rajan and coworkers [18] have demonstrated that monitoring of mercaptan and
total sulphur are important from the stand point of the heath of insulation of the
transformer. Authors have concluded that oils that have total sulphur of less than 15 ppm
and mercaptan sulphur of less than 0.2 ppm are less susceptible to copper corrosion. But
these are not always sufficient conditions for the oil to be corrosion free. Their study has
also showed that total sulphur content of the thermally aged oil increases with inclusion
of gasket material. Even paper, pressboard, glue are potential sources of sulphur. Authors
also found that mercaptan sulphur is consumed rapidly during thermal/electrical ageing
of paper-oil insulation but its level can increase due to interaction of oil with other
components. Further, their investigation shows that mercaptan sulphur formation is more
predominant under dc than ac voltages, but with irgamet 39 and pressboard, it is
significant under ac, indicating the complexity of the electro-chemical reactions in the
insulating system.
V. Tumiatti and coworkers [19] have described a state of the art method
developed by IEC TC-10 WG-37 for quantitative determination of a highly corrosive
sulphur compounds like dibenzyl disulphide (DBDS) and other corrosive sulphur
compounds in unused and used insulating liquids. The method reported in this article
permits a non-subjective quantitative determination of DBDS and total corrosive sulphur
(TCS) in insulating liquids. The state of the art chemical instruments described permit
sensitive and selective determination of DBDS. The highest specificity for DBDS is
obtained with a gas chromatograph interfaced to tandem mass spectrometer (GC-
MS/MS). The method not only permits an objective quantification of corrosive species in
insulating liquids, but also permits ranking of sulphur compounds according to their
corrosivity towards copper.
F. Kato and others [20] have investigated the effect of DBDS concentration on
copper sulphide formation on kraft paper by heating tests stipulated by IEC 62535. The
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heating duration and the amount of additive DBDS are used as parameters of the tests
with three mineral insulating oils. Regardless of oil, they have observed enhancement of
corrosion of copper strips used in IEC 62535 upon addition of DBDS. Since copper
sulphide formation occurs after some duration of heating, the incubation period can be
defined by the time of the inflection point of formation rate. The incubation period
decreases with an increase in the DBDS concentration. The experimental formula
consists of two terms. The first term reflects the oil property that gives the concentration
dependence of DBDS while the second term is determined by the temperature. This paper
also explains that high concentration of DBDS accelerate the onset of copper sulphide
formation on the kraft paper, which increases the risk of failure due to copper sulphide
formation in transformers.
H. Kawarai and co-authors [21] have developed a heating test to investigate the
influence of dissolved copper and oxygen on copper sulfide generation by adding DBDS
in alkyl benzene insulating oil. The dissolved and deposited copper mass has been
measured to systematically study the effects. The oxidation of both alkyl benzene and
insulating paper were observed to accelerate Cu2S generation. The authors have tried to
clarify the role of oxygen in copper sulfide generation as it would help in deciding
whether the transformer should be free breathing or sealed.
A paper by M. Dahlund and others [22] has discussed the effect of copper
corrosion and the online reclamation technique for removal of sulphur compounds from
transformer oil with reactivating sorbent. Authors conclude that it is possible to attain
complete removal of sulphur compounds from transformer oil by online reclamation.
This was achieved both in pilot scale as well as in service equipment. Hence online
reclamation is an attractive alternative for oil exchange when passivation is not sufficient.
According to L. Arvidsson [23] the conditions required for the formation of

copper sulfide originating from the DBDS oil additive which was identified by Scattigio
(Terna, Italy) in 2005 is: sufficiently high copper and higher temperature leads to
copper corrosion will appear. This paper describes the findings when a transformer has
allegedly failed by corrosive sulphur was inspected with regards to the presence of
32
copper corrosion. Strong corrosive attacks were found and their relation to temperature
was very evident.
A paper titled Failures due to copper sulphide in transformer insulation by

Dahlund [24] has reported that the failures of equipment occured mostly when operating
at elevated average temperature, although (with some exceptions) within accepted
temperature limits, and were normally without warning from commonly used oil tests,
including DGA. Several different oils were involved. All oils fulfilled present IEC and
ASTM specifications when new but, at least in some cases, the oils changed during
operation, turning corrosive and causing growth of Cu2S. Authors have felt that there are
no reliable and universally known and accepted methods to identify units at risk or oils
that may cause problems, nor diagnostic techniques to identify already affected
equipment. There is so far quite a low level of general understanding of the phenomena
which include the influence of transformer materials, temporal development, temperature
dependence, service conditions, impact of design, etc. Some mitigation techniques,
namely the addition of metal passivator, have been tried with apparent success, but more
knowledge of possible side effects and long term stability of these is needed and the was
conclusion was given that It is necessary to work intensively in several directions.
Several urgent aspects have been identified, each with more or less priority. These
aspects are: a) Oil testing and specification issues; b) Methods to identify units in danger;
c) Recommendations for counter-measures to stop or retard the processes; d) Improved
understanding of this complex problem.
G.A Oweimreen and coworkers [25] have examined the kinetics of the net
depletion of DBDS from its solution in mineral insulating oil due to copper corrosion at
elevated temperatures in power transformers. Authors have carried out measurement of
DBDS with initial concentrations of 3, 6, 9, 12, 15 ppm in insulating oils at an interval of
24 hours till 168 hours at 150 C and observed that depletion of DBDS significant in
insulating oils containing copper strips than the one without copper strips. The analysis
of kinetic data reflects the complexity of corrosion process and the possibility of
corrosion even at DBDS concentration of 1 ppm. The study also indicate that the
corrosion does not occur to a measurable extent even when DBDS concentration is 150
ppm if the temperature of ageing is below 100 C. The study has clearly indicate that the
33
kinetics for the depletion of DBDS in mineral insulating oil in contact with copper are
quiet complex and the order varies with both the initial concentration of DBDS as well as
the duration of the reaction.
M. Lukic [26] and co-workers have investigated the influence of mineral

insulating oil oxidation and the presence of metal passivators on copper sulphide
deposition by covered conductor deposition (CCD) test on the naphthenic insulating oil
containing DBDS. Deposition of copper sulphide on insulating oil after CCD test was
observed only when oils were pretreated using accelerated oxidative treatment. Oil
oxidation resulted in the increased dilution of copper in mineral oil. Study reveals that
prolonged oil oxidation followed by the CCD test enhanced growth of Cu2S deposits and
it reduces the surface resistivity of insulating paper.
Observations from the study have shown that aminomethyl substituted

toluylbenzotriazole (TTA) was found to inhibit copper dissolution in oil during oxidative
heat treatment. The results show that TTA is absorbed in the paper insulation, as the
consequence of TTA migration from oil to paper which is observed to increase with
duration of the treatment. Observations from experiments showed that the presence of
TTA in the paper wrapped conductors was found to inhibit copper sulphide deposition for
120 h of heat treatment at 140 C. Under conditions with low oxygen concentration in oil,
Cu2S formation on copper plate started after 120 hours whereas under conditions of high
oxygen content, Cu2S formation is observed on paper after 120 hours. Hence authors
conclude that increased dissolution of copper in oil is the necessary step for the formation
of Cu2S precursors in insulating paper.
Paper describes that presence of oxygen or oxygen donating compounds like

peroxides, acids and ketones could propagate the formation of CuO through
decomposition of copper hydroperoxide. Formed oxide reacts with thiols, thiolate
radicals and thiolate anions to form Cu2S as follows.
(2.3)
(2.4)
(2.5)
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CIGRE working group report [27] has investigated into specific sulfur
compounds which are present in insulating oils and are responsible for copper corrosion.
Report discusses the source and nature of different sulphur compounds present in oil. The
report furnishes the results of round robin test performed on different oil samples,
analysis of DBDS by GC-AED, analysis of DBDS, DBS and other sulphur compounds
by GC-MS, analysis of sulphur compounds by GC-AED and their results, analysis of
total mercaptan sulphur and disulphide by titration. Report concludes that analysis for
DBDS by GC/ECD is simple, sensitive and fairly reliable. The method can be applied to
new and aged oils with little interference and minimal sample preparation to levels below
1 ppm. Analysis for DBDS can also be accomplished by GC/MS and GC/AED. Analysis
by GC/MS is more definitive and can identify other target compounds (DMS etc.)
concurrently, but is less sensitive and not as readily available. Analysis by GC/AED has
the advantage of detecting all sulfur compounds but is prone to more interference and is a
more expensive and less common laboratory instrument. Analysis for total mercaptans
and disulfides was successfully achieved by authors using Ag/Ag2S electrode titration.
The method is more tedious and requires frequent electrode cleaning and adjustments
need to be made for higher concentrations. Determination of total sulfur by ICP gave
poor reproducibility among labs. Other methods are available as substitutes but since
total sulfur has little or no correlation to corrosive sulfur, it is suggested that it is not
worthwhile pursuing further.
Plaza and others [28] have carried out Flash thermolysis of dibenzyl and
diphenyl disulphides at 500C and 1000C. Experiments were carried out under reduced
pressure 1.510-3 Torr in a heated horizontal quartz tube. The decomposition products
were identified by gas chromatography fitted with a mass spectrophotometer. Dibenzyl
disulphide decomposes mainly to elemental sulphur, dibenzyl and stilbene. The results of
the study indicate that dibenzyl disulphide pyrolysis mainly to elemental sulphur. It is
stated that during flash thermolysis, the extent of decomposition of DBDS is higher than
that of DPDS.
J. Griffin and R. Lewand [29] have developed two test methods for oils that are
useful for detecting potential problem based on different failure modes. The authors have
stated that in-service oils can be tested and evaluated based on the application and
35
mitigation methods such as passivation need rigorous evaluation. Accordingly, two tests
for corrosive sulfur are recommended for new transformer oils. The test methods are
ASTMD 1275B and the Doble CCD test. These two tests have similarities with bare
copper and copper sulfide deposits in paper failure modes respectively. The authors
suggest that these tests can be applied to in-service oils and some guidelines for
determining units at risk have been provided. It is also said that passivators in oil can be
used to reduce risk but there remains some evidence that the long-term effectiveness of
passivators would require further study.
L. Lewand [30] in their publication on dibenzyl disulphide in transformer oil

has carried out experiments to elucidate the formation of corrosive sulfur compounds in
oil from degradation of DBDS. In these experiments DBDS was added to white mineral
oil in varying concentrations of 250, 125, 50 and 5 ppm (mg/kg). It was determined that
DBDS was found in certain oils which were removed from transformers that had failed
due to corrosive sulfur attacks. Experiments have shown that DBDS easily degrades into
sulfur species that are highly reactive to copper and which attacked the copper forming
copper sulfide films. Theories are put forward indicating that at least one of the DBDS
breakdown products is benzyl mercaptan and testing of this compound directly showed
that it is highly corrosive. Chemical reactions showing the interaction of DBDS, benzyl
mercaptan and components in the oil such as copper, hydrogen, and oxygen are provided
and a distinction is observed between sealed transformers and free breathing conservator
transformers. This distinction is important as the failures of transformers due to corrosive
sulfur attack with oils containing DBDS has been more prevalent in sealed transformers
then those with free breathing conservator systems.
T. Amimoto and co-workers [31] have investigated copper-sulfide deposition on

coil insulating paper used for power transformer insulation with the aim of obtaining the
concentration dependence of corrosive sulfur. Several mineral insulating oils containing
dibenzyl disulfide (DBDS) are used as sample oils. Thermal aging tests are performed at
140 C in air up to 1296 hours 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. The copper sulfide deposition is fairly low in oils that
36
contain less than 1 ppm of DBDS even after 1296 h of heating. 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. The effect of sulfur compounds other
than DBDS was not significant on the copper-sulfide deposition from a long-term
perspective in these experiments. The paper also concludes that reducing the DBDS
concentration in oil is very effective for suppressing the copper-sulfide deposition.
Reducing the DBDS concentration by half is considered to double the lifetime of
transformers and reactors.
S. Eeckhoudt and others [32] have explained that since 2005 Electrabel, the
largest power utility company in Belgium, in close collaboration with Laborelec, the
technical competence centre of the Belgian electricity industry, has taken several actions
to minimize the risk of corrosive sulphur related incidents within their fleet of power
transformers and the transformers of their industrial customers. This paper focuses on the
research that has been performed recently and also on the preventive and corrective
actions that have been taken by asset management team and the electrical maintenance
department.
Ren and others [33] have discussed a comparatively detailed summary of

research status about sources of sulphur, their detection, and prevention and mitigation
phenomenon. Mechanism of copper sulphide as given by authors is as shown in equations
2.6 and 2.7.
(2.6)
(2.7)
Where RSH is mercaptan R is alkyl or other hydrocarbon group. Paper explains the role
of metal passivation, sulphur removal techniques such as treatment with sorbents,
selective depolarization, treatment with KOH/PEG, liquid-liquid extraction and the role
of oil change.
Tsuyoshi Amimoto and others [34] have carried out corrosive sulfur tests such as
ASTM D1275 (now termed ASTM D 1275A), Modified ASTM D1275 (ASTM D
37
1275B) and IEC 62535 on three transformer oils used in Japan and the possibility of
deposition of copper-sulfide on insulating paper was observed to be significantly lower
by the authors. These three transformer oils have been mainly used in power transformers
in Japan. The authors have concluded that dibenzyl disulfide (DBDS) in transformer oil is
known as one of the main compounds causing the deposition of copper-sulfide, which
decreases the dielectric strength of oil insulation and leads to fatal failures in majority of
the cases. A highly sensitive analytical method of detecting DBDS has been developed by
Mitsubishi Electric Corporation and discussed in this paper.
F. Scatiggio and co-workers [35] have evaluated 14 different oil specimens in

their study. In the 14 oil specimens evaluated, all of which were either paraffinic or
naphthenic, the oils were observed to be corrosive irrespective of whether they
contained Dibenzyl disulfide (DBDS) or otherwise. This suggests that Dibenzyl disulfide
was specifically added to the oils as an additive antioxidant. However, it has been
emphasized that exclusion of DBDS from the oils does not ensure non-corrosivity of oil,
because some oils without DBDS were also corrosive so that DBDS is not the only
culprit of the sulphur corrosion problem. Again of the 14 unused oils examined, oils
which contained DBDS, the concentration of DBDS found vary between 100 and 350
ppm. When oil, in which DBDS is present, is exposed to copper the rate of decrease in
the DBDS concentration will be a function of the copper surface area, the contact time
and the temperature. The different causes for failures of transformers and shunt reactors
induced by corrosive sulfur are examined by the authors. Dielectric losses of the
contaminated paper-oil insulation have increased significantly. Dissipation factor is found
to be more than 1.0 even at room temperature in affected insulation system. Thermal
instabilities occur leading to increased loss currents and thus ultimately lead to short
circuits between the turns. This is supported and substantiated by on-field observation
that shows charred breakdown regions along insulation system. The authors have
tabulated total sulphur content in mineral insulating oil over the years from 1964-2008
and they have demonstrated that the total sulphur contents have fallen from 6000 ppm in
1964 to less than 1000 ppm in 2008 due to the introduction of improved refining
techniques, over a period of 44 years. Gas chromatography and atomic emission
spectroscopy have been used by the authors for specific elemental detection.
38
The press board samples were thermally aged at different intervals of 0, 120, 250
& 400 hours. Differently aged samples are put into petroleum ether to remove residual oil
and then dried in a vacuum oven. Polarization and depolarization currents (PDC) and
frequency domain spectroscopy (FDS) measurements are performed on water and oil
removed specimens. Different aged specimens have shown different electric response
after ageing characteristics. The authors have concluded that besides water, the
deterioration of cellulose itself causes increased press board conductivity and thus have
an influence on PDC and FDS results. To evaluate the condition of paper-oil insulation
system, along with conventional diagnostic techniques such as dissolved gas in oil
(DGA), partial discharge (PD), furan analysis, several noninvasive diagnostic methods
such as PDC and FDS, return voltage measurements have been carried out by the authors.
Shota Kamishima and others [36] have discussed how changes in the molecular
structure of sulfur compounds in mineral insulating oils affect their corrosivity. A method
for the quantitative evaluation of corrosivity of insulating oil was developed and used in
this study. Several types of sulfur compounds were observed to cause sulfur corrosion.
However, hydro treated oil was non-corrosive because the sulfur compounds which cause
sulfur corrosion were easily removed through hydro treatment. The results of thermal
aging tests using model sulphide compounds showed that the corrosivity of sulphide-
added oils increase with longer heating times due to generation of sulfoxide. The
corrosivity of aged oils would depend on the concentration of sulfoxide in the oils.
However, the corrosivity of commercial insulating oil did not change drastically in the
thermal aging test, despite the fact that this oil contained a certain amount of sulphide. In
this study, the authors have investigated the structural changes of sulfur compounds in
insulating oils caused by oxidative deterioration of the oils, and the relation between
these structural changes and corrosivity of the oils. They have performed quantitative
analysis of the four types of sulfur compounds in the oils; thiol (Mercaptan), disulphide,
sulphide and thiophene. For this analysis, potentiometric titration was used in
combination with zinc-catalysed reduction method and 13C-NMR. Thiol content was
determined by potentiometric analysis. The thiol sulfur was precipitated as silver
mercaptides and the end point of the titration was indicated by a large change in cell
potential. The zinc-catalysed reduction method was used to quantify the disulphide
39
content. One molecule of disulphide was reduced to two molecules of thiol in the
presence of a zinc catalyst, after which the thiol was quantified by potentiometric
titration. 13C-NMR was used to quantify the thiophene and the sulphide. The sulfur
compounds in the oils were methylated using methylating reagents (CH31 and Ag BF4).
The methylated sulfur compounds were analyzed using 13C-NMR. The peaks of the
methyl carbon added to thiophene can be separated from the peaks of the methyl carbon
added to the other sulfur compounds. The amount of thiophene was calculated from the
NMR peak area ratio and the total sulfur content of the oils. The amount of sulphide was
the value calculated by subtracting the amounts of thiol, disulphide and thiophene from
the total amount of sulfur in the oils.
2.3 Literature on passivators and stray gassing
Maria Augusta G. Martins and Ana R. Gomes [37] have worked on the
concentration of passivator Irgamet 39 that can prevent oil corrosiveness from the
presence of a certain DBDS concentration, from about 7 to 400 ppm in oil and also
minimum concentration of DBDS that makes the oil potentially corrosive. The tests were
carried out in accordance with IEC 62535 and the oil used was from Shell Diala D, which
was noncorrosive oil.
This paper also discusses the influence of Irgamet 39 on the oxidation stability of
both inhibited and uninhibited mineral oil. The results of the work showed that DBDS
concentration of 10 ppm in mineral oil makes oil potentially corrosive when tested
according to IEC 62535. It is also concluded that for DBDS concentration of less than 15
ppm, concentration of Irgamet 39 required to prevent corrosiveness due to DBDS is 20
ppm and for higher DBDS concentrations of 20 to 200 ppm, passivator concentration
required is 50 ppm. The paper explains that presence of Irgamet 39 improved oxidation
stability of mineral oil since passivated oils produce less sludge and acidity than the non
passivated oils. It is also explained that thermal degradation of DBDS increases with
temperature and in the presence of copper indicating the catalytic role of copper.
T. Wan and coworkers [38] have added Irgamet 39 to a 500 kV transformer to

solve the problem of corrosive sulphur. The organic film of Irgamet 39 formed over the
40
copper surface was analyzed by scanning electron microscopy, X-ray photoelectron

spectroscopy, attenuated total reflection Fourier Transform Infrared spectroscopy and
time of flight secondary ion mass spectrometry. The properties of transformer oil with
Irgamet 39 were also analyzed.
According to the analysis, deactivation mechanism of Irgamet 39 proceeds via

alkyl carbon fractures which form coordination complex films on the copper surface. It is
also observed that Irgamet 39 film formed on the copper surface remains stable at high
temperature and oxygen conditions. Addition of Irgamet 39 to oil improves the oxidation
stability and dielectric loss of transformer oil. No influence was observed on the surface
tension, electrostatic charging tendency and volume resistivity.
F. Kato and others [39] have studied 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 sulphide deposition are investigated by changing the time
when passivators are added to oil. All corrosive sulphur tests performed in the study was
according to IEC 62535. A simulation was made where addition of passivators to
preheated oil simulates the condition where passivator is added into the transformer after
a period of operation and adding passivators into non-preheated oil simulates the
condition where passivators is added before operation. However, suppressive effect of
passivators was confirmed in both the cases. Copper sulphide deposition continued in
preheated oil passivated after 24 or 48 hours of heating even though a passivator was
detected in the oil. This indicates the existence of copper sulphide precursors before
adding passivators. The duration of the suppressive effect for preheated oils passivated
after 24 or 48 hours of heating is short compared to that for non-preheated oils passivated
before heating. It is also explained that the deposition rate of copper sulphide in
preheated oil is lower than in passivator-free oil after passivator depletion, which reflects
gradual deterioration of the complex layers created on the surface of the copper.
Per Wiklund [40] explains the chemical stability of benzotriazole (BTA) copper
surface passivators in insulating oils. The study has shown that benzotriazole derivatives
decay under the action of hydroperoxides. These hydroperoxides which are the direct
products of hydrocarbon peroxidation result in hydroxyl radicals, which in turn attck the
41
benzotriazoles, leading to decay. This explains the depletion of BTA and

tolylbenzotriazole (TTA) in transformer oil upon oxidation. The rate of depletion of BTA
and TTA in real insulating transformer oil is very slow because of the presence of sulphur
compounds and phenolic antioxidants. It was also found that UV radiation from sunlight
can induce the decay of benzotriazoles.
R. A. Venkata Laxmi and T. S. R Murthy [41] have discussed the corrosion

phenomena involving copper, corrosive sulphur and solid insulation of oil immersed
transformers. The paper insulated copper conductors with transformer oil are aged for
1400 hours at 140 C with and without passivator namely Irgamet 39 and both copper and
paper insulation are analyzed by XRD, SEM and EDX. The results of SEM, XRD and
EDX scans after ageing for 1400 hours at 140 C indicate the formation of thin film of
passivator over copper surface. The results also indicate scattered deposit of copper
sulphide showing the formation of copper sulphide on the copper surface as well as on
the paper insulation.
R. A. Venkata Laxmi and T. S. R Murthy [42] in another study have carried

out ageing of transformer oil with and without passivators for 2000 hours at various
temperatures of 105, 120 and 140 C. The passivators used in the study were Irgamet 39,
BTA, 2-(2H-Benzotriazole-2-yl)-4,6Bis-(1-mrthyl-1-phenyl-ethyl)phenol (BMPEP) with
concentration of 100 ppm. The study reveals that Irgamet 39 is better passivator than
other passivators. Tan , capacitance and insulation resistance values of the insulated
copper conductors aged with oil containing Irgamet 39 passivators have shown only
marginal variation. It is also observed that Irgamet 39 is a liquid and has better miscibility
with oils. BTA is a solid and is difficult to dissolve in the oil. BMPEP is not
recommended due to its deleterious decomposition products.
R. Maina and coworkers [43] have studied the behavior of corrosive sulphur in
mineral oils in terms of the failures observed in transformers; the surfaces of the copper
sulphide covered conductors and degraded paper insulating tapes. The degree of
corrosiveness of some oils containing different sulphur compounds is determined and
compared using kraft paper wrapped- copper test (standard IEC 62535). Shiny surface
deposits of copper and paper were identified by means of SEM/EDX techniques. Copper
42
conductors and paper specimens from failed transformer and shunt reactors indicate that
higher copper sulphide deposits occurs on the surface of the kraft paper layer adjacent to
the copper conductors and there after its concentration decreases with each successive
outer tape paper layer. However, the outward migration of copper sulphide through the
relatively open fiber structure of the paper is not the only mechanism active. Paper also
discusses the possible evolution of gases after passivation of the oil with Irgamet 39.
Introduction of passivator was observed to increase hydrogen evolution.
Fabio Scatiggio and others [44] have discussed stray gassing in transformers
after it has been passivated. Paper examines the observations recorded in field as well as
reproduced in laboratories. Paper explains that though there was release of significant
amounts of hydrogen and carbon oxides, hydrocarbon gas generation was not observed.
The generation of hydrogen gas may lead to interpretational difficulties, since it is not the
unique indication of the effects of passivators. It can also be due to other mechanisms
such as partial discharge, electrosis and core lamination heating.
Paper reveals the fact that the generation of H2 and CO occurs primarily at the
beginning of the oil ageing processes and this constitutes an indirect means for
identifying passivator induced oil effects. It is also strongly suggested that the presence of
oxygen can play an important role in the observed mechanism.
Per Wiklund and others [45] have carried out experiments on copper dissolution
in acidified oil and the role of passivator is discussed. The authors opinion is that copper
dissolution occurs by corrosion which subsequently leads to copper deposition in the
form of oxides, sulphides or other compounds on insulating cellulose. Hence they suggest
that dissolution itself should be prevented. A copper helix specimen is immersed in 200
mL of acidified (0.1mg KOH/g) white oil and placed in an open beaker at 80C, to
observe copper dissolution. The copper dissolution reaches maximum before acid number
in oil increases. When the oil begins to oxidize, the acid number goes up and sludge
formation begins. In many transformer oils (inhibited grade), to prevent copper
dissolution, manufactures add phenolic antioxidants. A metal passivator (Irgamet 39-
manufactured by M/s Ciba in this case) is used to prevent contact between oil and copper.
43
In the process, a passivating layer is formed, to protect copper dissolution even in

presence of severe oil oxidation.
M.M. Antonijevic and M.B. Petrovic [46] have presented a review article on
copper corrosion inhibitors. Authors have investigated factors dealing with
electrochemical corrosion of copper and possibility of its prevention using inhibitors.
They have studied both organic and inorganic compounds. It is reported that action
mechanisms are different for different inhibitors. Inorganic compounds act through oxide
film formation whereas organic compounds mostly act via adsorption on metal surface
and complex formation. That is the basis of the adverse effect of high temperature on the
efficiency of organic compounds.
Paper has also confirmed that molecular structure of inhibitor is the main factor
determining its characteristics. Presence of hetero atoms (S, N and O) with free electron
pairs, aromatic rings with delocalized electrons, high molecular weight alkyl chains,
and substituent groups in general improves inhibition efficiency. It is also reported that
group position is also important, 2- and 5- positions are shown to be more convenient.
It is also mentioned that thiazoles, triazoles, benzotriazoles give good protection

except in strongly acidic media. However, there is no universal solution for efficient
copper corrosion inhibition; corrosion inhibition efficiency using specific inhibitor is a
complex function of numerous parameters.
A. Schaut and coworkers [47] have studied the performance of undeclared

additive Irgamet30 in transformer oils. Study was carried out to determine the stability
of Irgamet39 and it was clear that Irgamet39 protected the copper surface. As the
structure of Irgamet30 is comparable to that of Irgamet39, its stability, impact on
oxidation stability of the oil and corrosive sulphur compounds were tested on lab a scale.
Stability of the compound was determined according to IEC61125C and it was
determined that Irgamet30 becomes undetectable within 24 hours. The impact on the
oxidation stability was tested according to IEC61125C. The results of this study shows
that Irgamet30can inhibit the oxidation of the oil. However, it is not able to form
protective layers on the surface as it does not act as metal passivator in oil.
44
S. Krawiec [48] has focused on the technologies currently available for the
production of severely refined, corrosive sulphur free base fluids used in the formulation
of high quality transformer fluids. This paper discusses the formulation, evaluation and
performance characteristics of transformer fluids manufactured from corrosive sulphur
free, iso-paraffin base fluids. It has been shown that these fluids can pass the latest
corrosive sulphur tests without the use of passivators. In addition, it is stated that, it will
cover increased oxidative stability, heat transfer and biodegradability characteristics as
compared to common naphthenic mineral oils.
Paper explains that copper passivators try to slow down the effects of corrosive sulphur in
oil. From industry investigations, it is becoming more apparent that copper passivators
may not be the long term answer. Better refining technology is required to lower or
eliminate the corrosive sulphur content of transformer oils.
Ivanka Atanasova-Hohlein [49] has explained the mechanism of stray gassing,

the typical stray gas formation of mineral oil, as well as of further insulating liquids like
synthetic or natural esters under various temperature conditions, examples of possible
interference of the straygassing pattern with diagnostics and also the method to
distinguish stray gassing from fault cases in DGA evaluation.
The paper explains the methods to prevent stray gassing. The reduction of oxygen
concentration in oil, reduction in operating temperature of transformers, oil purification
by fuller earth with subsequent inhibition reduces the risk of stray gassing.
The study of J. Weesmaa and others [50] have studied stray gassing generation
due to interaction between oil and other equipment material and also on tests performed
at more realistic temperatures than existing standard method like ASTM D 7150 which
runs at 120 C. In this paper, the authors compare variations of the method ASTM D
7150 to test stray gassing and look at the influence of oil preparation and test conditions
such as temperature, time of heating and oxygen concentration. Paper discusses the
difference in stray gassing behavior of inhibited and uninhibited mineral insulating oils.
Paper also explains the effect of different transformer materials on the results of
Dissolved Gas Analysis (DGA).
45
Daniel Martin and others [51] have investigated the effect of stray gassing of
oils in the fault diagnosis of transformers. This paper presents the analysis of the gases
generated by mineral oil and cellulose transformer insulation, at temperatures lower than
those expected in actual thermal fault. Gassing at relatively low temperatures of 100C to
200 C, often presents a problem to the asset manager since it can be difficult to
distinguish this event from that caused by an actual fault. In the present work, mineral oil
under 20 different conditions of oxygen and water content were tested for up to nearly
100 days and it is observed that at low temperature levels and high oxygen levels, the
generation of ethylene was more significant when compared to other hydrocarbon gases.
During accelerated ageing investigations, the generation of hydrocarbon gas was
observed to be related to the water content of oil and ethylene was found to be a major
stray gas under certain conditions of ageing.
The work of Alexandros E. Papadopoulos and Constantinos S. Psomopoulos

[52] presents a study on DGA findings in mineral insulating oil samples with corrosive or
suspicious corrosive action according to the test ASTM D1275B method. Samples were
collected from power transformers operating in Greece. Some serious indications were
obtained from DGA results in case of copper corrosion. Hence, paper reveals that the
DGA results can be used to monitor the evolution of the copper corrosion phenomenon
and to detect the critical time for passivation. Authors explain the need for combining
DGA tests with laboratory tests of passivators and DBDS and other corrosive sulphur
compounds.
CIGRE [53] report has discussed transformer oil sample analysis as a useful,
predictive, maintenance tool for determining transformer health. Along with the oil
sample quality tests, performing a dissolved gas analysis (DGA) of the insulating oil is
useful in evaluating transformer health. The breakdown of electrical insulating materials
and related components inside a transformer generates gases within the transformer. The
identity of the gases being generated can be very useful information in any preventive
maintenance program. This method involves sampling the oil and testing the sample to
quantify the concentration of the dissolved gases. It is recommended that DGA of the
transformer oil be performed at least on an annual basis with results compared from year
46
to year. In this article, it is discussed that DGA is a useful, predictive, maintenance tool
and the need to review some methodologies for evaluating test results are discussed.
S. Annelore and Eeckhoudt Steve [54] have performed laboratory studies such
as stability/degradability, impact on oxidation stability and corrosive sulphur for the
undeclared triazole additive (TTA). The stability of the compound was determined by
performing a heating test based on IEC61125C. After 24h, TAA could no longer be
detected. In the presence of a Cu coil, the decrease in TAA was accelerated. The
IEC61125C oxidation stability test was performed to verify the impact of this additive on
oxidation stability, once without any pre-treatment, secondly after IX-resin treatment and
finally after IX-resin treatment and readdition of the compound. It was clear that the resin
treatment removed additive from the oil but also some other (natural) inhibitors.
Readdition did not fully recover the oxidation stability of the oil. This could indicate that
not only the triazole compound was removed from the oil by the IX-resin treatment but
also that some other (natural) inhibitors were present in the oil. The impact on corrosive
sulfur was examined by applying the IEC62535 before and after IX-resin treatment but it
seemed that the oil was not protected against DBDS. From these laboratory studies, the
authors have concluded that only the oxidation stability of the oil is improved by the
addition of TTA.
D. Sundin [55] from DSI has explained a multi-step method that is been proven
to change oils from corrosive sulfur into non-corrosive status, as well as significantly
slowing down oxidation and ageing of insulating oil and paper. This paper outlines the
history of the problem as well as the research that has led to a successful commercial
launch of a product known as DSI sulfur inhibitor. DSI Sulfur Inhibitor uses a blend of
several different metal passivators. The authors have stated that the new sulfur protection
and reduction scheme protects transformers in three different ways, which work in
synergistic manner as explained below.
1. DSI Sulfur Inhibitor uses a blend of several different metal passivators. The
research has observed that a mixture of metal passivators is much more effective in
preventing dissolution of copper into oil than a single compound.
47
2. The developed product contains a powerful blend of different antioxidant

chemistry that protects oil and paper from accelerated ageing and inhibits their ability to
enter into chemical reactions.
3. Developed product is a mixture of sulfur scavenging and passivating compounds.
These chemicals seek out corrosive sulfur in oil and bind with it to prevent its interaction
with metals, paper, or oil. The bound sulfur is effectively rendered harmless.
J. S. Rajan and co-workers [56] have carried out experiments to understand the
role of metal passivators in preventing corrosion of copper conductors in transformers.
Transformer oil from three different sources, one of which was naphthenic and the other
two were paraffinic were taken up in this study. Fresh, vacuum dried and degassed oil
samples were aged in specially designed glass bottles which had provision for bubbling
of nitrogen gas to simulate the condition of a sealed transformer. Ultra-pure and dry
nitrogen gas was continuously bubbled into oil during thermal and electrical ageing. The
thermal ageing temperatures ranged from 80 to 140C and the applied voltage was 0.8,
1.3 and 1.8 kV. Three different voltage stresses corresponding to normal, lowest and
highest stresses that occur in a power transformer at normal working conditions and those
due to voltage dip and over voltages were used. The authors have carried out a series of
thermal/electrical ageing tests using oil samples and their total sulphur and mercaptan
sulphur content have been monitored during the ageing process in presence of paper,
pressboard, glue, gasket etc. The experiments showed that with metal passivator, the
deterioration of paper, pressboard and gasket were insignificant. This clearly indicates
that the interaction of oil with copper is primarily responsible for the reactions that
follow. Important findings of their study are:
(l) Metal passivators are stable even at higher temperatures and during the laboratory
ageing of paper-oil insulation. Hence passivators should perform satisfactorily in service.
(2)Use of metal passivator results in higher concentration of mercaptans which in turn
affects components like paper, pressboard, when depletion of passivator occurs in these
components.
(3)Total sulfur and mercaptan sulfur concentrations and their variation in transformer oil
are dependent on the oil temperature. Hence effect of temperature and dependence of MS
and TS on temperature are important for understanding the chemical processes involved.
48
L. Arvidson VP and others [57] have studied the stereo chemical aspects of
BTA and Irgamet 39. Authors explain that Irgamet 39 can not cure copper sulphidation
related problems at any time. i.e, either when transformer is new or when the transformer
has been in use. Authors suggest that the experiment reported with Irgamet 39 were
carried out either with limited oxygen supply or with no oxygen access. Since BTA and
its derivatives are extremely oxidation sensitive, experiments without oxygen present
give results which can be misinterpreted.
Paper reports data of screening of 14000 transformers containing 0.1 ppm to 200
ppm DBDS and nine of these 14000 units had failed. This shows that DBDS itself is not
the problem. Instead, the problem is what triggers DBDS to form radicals to abnormal
extent.
Ingvild Tronstad and co-workers [58] have investigated the effect of Irgamet 39
in transformer using a quartz crystal microbalance with dissipation monitoring. Effect of
Irgamet 39 is significant provided that the passivator is added to the oil before use in
concentration above 25 ppm. Further, it is stated that temperature affects the amount of
adsorbed Irgamet 39. Effectiveness of the passivator decreases if it is added after the
formation of copper sulphide.
2.4. Literature on liquid extraction
J. M. Lukic and others [59] have investigated selective liquid-liquid extraction

using N-methyl-2-pyrrolidone solvent for the purification of mineral insulating oils by
removal of compounds and precursors responsible for copper sulphide formation. The
efficiency of extraction process was evaluated using corrosive sulphur test IEC 62535,
SEM/EDX measurements of paper before and after the IEC 62535 test, and
measurements of DBDS concentration in oil using GC-ECD method. The oxidation
stability of refined oils was evaluated using the IEC 61125 method. Precursors of copper
sulphide deposits were completely removed from different mineral oils as a result of
purification by extraction with N-methyl-2-pyrrolidone and 1.0 wt %water as a co-
solvent. The total aromatic and sulphur contents were significantly reduced, thus
indicating a high degree of refining. The oxidation stabilities of the refined oils were
49
within limits typically found for unused oils, thus indicating the possible reuse of these
oils in power transformers or other electrical equipment.
R. Qi and co-workers [60] have studied solvent extraction process for sulphur
removal from gasoline. The study involves the investigation of efficiency of three
preferred polar solvents, PEEG 400, TTEG and NMP for extractive desulphurization.
Experimental results indicated that NMP possesses the highest desulphurization ability
but has the lowest selectivity towards thiophenes, whereas TTEG holds highest
selectivity for thiophene but lower desulphurization rate than NMP. Experiment involves
the study of the effect of ratio of TTEG and NMP in the combined-solvent, the ratio of
solvent to oil, composition of the organ sulphurs present in the feed and the operation
temperature on desulphurization efficiency and also oil recovery ratio. It is observed that
increasing the ratio of solvent and oil will reduce the sulphur concentration in the
extracted stream, but it is at the expense of feed and energy consumption. Lower
temperature is favourable for sulphur removal and enhances the raffinate recovery.
A. Muttaleb Yousef Jaber and others [61] have described a unique single
liquid-liquid extraction pre-treatment step for the determination of dibenzyl disulphide
(DBDS), 2, 6-di-tert-butyl-p-cresol (DBPC) and 1, 2 , 3 benzotriazole (BTA) prior to
their determination by gas chromatography and HPLC techniques. The optimum volume
ratio used in the pre-treatment step was determined as 5:2:5 for mineral oil/n-
hexane/acetonitrile, respectively. The method is simple and quick with minimum use of
solvents. Analytical results indicate that the method is relatively sensitive, accurate and
precise for each of the three components in fresh and used mineral oil. The detection limit
for DBPC, DBDS and BTA are 100, 0.80 and 2.04 ppm respectively. Authors explain
that determining low concentrations of these three components would help to study their
interaction effects in insulating oil and its corrosion and passivation actions under the
transformer operational conditions.
2.5 Literature on UV-Visible spectroscopy to for detecting copper
Norazhar Abu Bakar and others [62] have discussed the effect of conducting
materials on UV-Visible spectral response characteristics. Spectroscopic analysis is
employed to measure furan concentration in transformer oil. Light absorbance and
50
spectral bandwidth are used as indicators to estimate furan concentration level in

transformer oil. Series of tests were carried out to study the impact of dust on the spectral
response characteristics. Oil samples with various furan concentrations along with certain
amount of copper powder are examined. Experimental results show that conducting
material present in transformer oil affect the spectral response when it is measured
straight away after collecting the sample from in-service transformer. However, if the
spectral characteristic is measured in about 5 minutes after collecting oil sample, the
impact of the conducting materials on the spectral response is less than 0.01%, and is
negligible after 10 minutes.
Navneet Thakur and O.P. Rahi [63] have discussed the basic information about
UV spectrometer, sampling and testing of transformer oil. The paper presents the results
of UV spectrometer of nine oil samples drawn from transformers of 6.3 to 100 MVA
ratings. The results reveal that UV-spectrometry is most effective technique for oil
dehydration or oil replacement. The technique is an alternative for oil conductivity
assessment. It also indicates the dielectric response and ageing assessment of transformer
oil. Since the equipment cost is very less, UV spectral response can be measured instantly
to determine the contamination present in oil, both qualitatively and quantitatively.
T. K. Saha [64] has evaluated a number of transformers using FDS and PDC
techniques for better understanding of dielectric properties. A circuit model was
simulated using Matlab to describe the dielectric behaviour of the transformers main
insulation system from the data of frequency domain measurements, return voltage and
PDC. Authors have also discussed frequency and time domain techniques to understand
the condition of transformer insulation in terms of moisture and ageing estimation.
Simulation results were supported by actual time domain field test results for one
transformer using the Tettex 5461 recovery voltage meter to illustrate possible
relationship between time and frequency domain diagnostic techniques.
Radha Karthik and others [65] have performed condition assessment of

transformer oil under various working conditions using UV-visible spectrophotometer.
Test samples include both laboratorial prepared ones and those obtained from in service
transformers. An index table of spectral responses for various faults which
51
predominantly occur in the transformer has been developed. The index table will act as a
reference for spectral response of fault transformer oil. In this paper, an attempt has been
made to determine the quality of transformer oil using their spectral response
characteristics.
Jian Hao and others [66] have carried out thermal ageing experiments of four
combinations of oil-paper insulation samples which consisted of Karamay 25#
naphthenic oil, Karamay 25# paraffinic oil, Kraft paper wrapped with and without copper
strip at 110C and 130C. The oil acidity, viscosity, breakdown voltage and ultraviolet-
visible (UV) spectroscopy of the insulation oils with different ageing condition were
analyzed. Results show that the oil acidity increases with oil ageing. The viscosity and
breakdown voltage of different oils shows fluctuation in the ageing process. The oil aged
with copper has higher oil acidity than that without copper, especially in the later period
of ageing. The oils aged with copper have higher UV absorption peak values. The
relationship between oil acidity and the UV absorption peak for oils aged with copper is
different from that aged without copper.
Copper has influence on the UV spectroscopy of the oil. The oil aged with
copper has higher absorption peak values than the oil aged without copper. It is stated
that when one uses the UV spectroscopy method to measure oil acidity, the effect of
copper must be considered.
2.6 Literature on dielectric measurements for study of copper corrosion effects
Pankaj Shukla and co-workers [67] have presented experimental results of the
work on temperature dependency of water content in mineral transformer oils. Moisture
sensor measurements (online measurement) and absolute water content determination by
Karl Fisher titration method (off-line method) were performed in the laboratory to
investigate solubility of different types of mineral transformer oils. Results of
experiments explain that present moisture solubility model of moisture sensor
affects the accuracy of water content determination. Test setup and procedure for
verification and calibration of moisture sensor with specific-oil solubility parameters is
described and then evaluated. This method allows greater accuracy of online water
52
content monitoring in the operating transformers under the changing temperature

conditions.
The results obtained in the paper show that temperature variation and the sharing of
moisture between the oil and paper affect the condition of transformers. The results
obtained also show that temperature variations have great influence on the moisture
migration between oil-paper insulation systems of the transformer. The experimental
results have emphasized the online monitoring off-line monitoring for water content in
insulating oil measurements.
Tapan K.Saha [68] and co-workers have discussed a circuit model, which
describes the dielectric behaviour of the transformers main insulation system. The values
of the parameters of the model have been identied from the dielectric tests. This paper
reports a detailed study on the effects of temperature on dielectric measurements of a
transformer under controlled laboratory conditions. Some results of practical on-site
testing are also presented to demonstrate the possibility of errors that may be introduced
in analysis of dielectric test results unless temperature effects are taken into
consideration. Polarization and depolarization current magnitudes and oil and paper
conductivities are estimated from these results and the current tends to be higher at higher
temperatures. The oil and paper conductivity, and insulation resistance have been
observed to increase with increase in temperature. On-site test results presented in the
paper indicate the need for careful understanding of the effect of temperature on the
dielectric response measurement for correct analysis and interpretation.
J. H. Yew and co-workers [69] have investigated Frequency Domain Dielectric

Spectroscopy (FDS) for a model transformer at different operating temperatures. FDS
data is then used to simulate polarization and depolarization currents. A correlation has
been investigated between the operating temperature and measured data of FDS, which is
then extended to simulate the PDC data. Finally the problems of a clear and transparent
interpretation of the dielectric test results have been explained. The results obtained from
the FDS have shown that the transformer operating temperature has a significant effect
on the dissipation factor and complex capacitance.
53
Anuradha Kumar and Satish M. Mahajan [70] have subjected a medium

voltage (69 kV, 1200 A/5 A) current transformer (CT) was to thermally accelerated tests.
The elapsed insulation life was calculated as per IEEE C57.91-1995. Insulation
diagnostic tests including PDC were performed at various aging stages of the CT. Results
have indicated that PDC tests can be applied to instrument transformers as well. A
correlation between time and frequency domain spectroscopic measurements was also
established. Measurement of furanic compounds in the oil was consistent with the paper
conductivity trends observed in the PDC measurements. A good correlation was found
between the measured FDS readings of the dissipation factor and the complex
capacitance, with those derived from the PDC measurements. If values of complex
capacitance and dissipation factor in the higher frequency are required, a combined FDS
and PDC test should be performed. The authors have suggested that such a combined test
can reduce the testing time considerably. PDC is a single sweep measurement technique
and can alone precisely assess the oil and paper insulation separately.
R. Maina and others [71] have explained that mineral oil reacts with the copper
conductors in oil impregnated transformers, leading to the formation of dissolved and
suspended copper in the oil finally leading 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. The authors have commented that inherent properties
of oil in 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 are described.
This paper also discusses two different methods to estimate the copper dissolution and
deposition tendency. Preliminary results obtained from a set of unused oils selected from
the market indicate that:
54
(1) copper in oil dissolution is limited at high temperatures, especially for uninhibited
oils, which are prone to oxidation;
(2) copper in paper transfer and deposition is favoured by the increase of oxygen and
inhibitor (DBPC); it is advisable that a Cu-DBPC complex participate to this mechanism;
(3) 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;
(4) 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, transfer of copper onto the paper is hampered;
(5) Passivators reduce both copper dissolution in oil and copper deposition onto the paper
(6) Increasing amounts of copper absorbed in the paper do not affect paper surface
resistivity, implicating that good insulating properties of the paper are preserved.
IEEE transformers committee [72] has reviewed the published literature on

dielectric response methods. The task force reports that there is a good agreement
between the dielectric response measurement and Karl Fischer moisture titration on paper
samples, but inconsistent agreement with moisture from oil samples have been reported.
This is mainly due to moisture dynamics from paper to oil or vice versa. Further,
dielectric response measurements are reported to furnish valuable information on the
state of paper-oil insulation in particular the moisture content, temperature and ageing.
The presence of ageing byproducts influence the dielectric response but it is very difficult
to distinguish ageing byproducts from water content. Hence, chemical oil analysis is
required to understand effects of ageing.
2.7 Literature on oxidation of copper
Shuangzan Ren and coworkers [73] have studied the influence of atmosphere
on the reaction of DBDS with copper in insulating oil. A mineral insulating oil containing
500 ppm of DBDS was aged under different temperatures of 105 and 165 C and under
nitrogen and oxygen. DBDS in insulating oil was determined using HPLC technique. It
was observed that Cu2S is formed both the cases of oxygen and nitrogen. Under nitrogen
condition, Cu2S is on present copper surface since there is more sulphur deposited on
55
surface whereas under air, the copper complex tends to dissolve in oil resulting in higher
copper concentration in oil as compared to nitrogen condition. Under nitrogen condition,
DBDS in oil only reacts with copper at certain temperatures. However in air condition,
DBDS would react both with DBDS and oxygen. Work also involves the calculation of
activation energy for the reaction of DBDS with copper in oil which was approximately
98.61 kJ/mol.
H. Kawarai and others [74] have investigated copper sulphide deposition on

cellulosic insulating materials in oil immersed transformers by heating tests according to
IEC 62535 with controlled atmosphere. Their observations showed that the weight of
copper sulphide deposition on insulating paper was found to increase when the oxygen
concentration was increased up to 20 volume %. Analysis using X-ray absorption near
edge structures (XANES) shows the copper deposits on the insulating paper which is
mainly Cu2S and small deposits of CuO.
R. Crisostomo Rabelo Neto and others [75] have presented a kinetic

experimental study of the oxidation reactions of a naphthenic mineral oil (with and
without additives) as a function of temperature. Oil samples were doped with phenolic
antioxidants (AOX), a metal passivator (MPA), and combinations of these (AOX and
MPA) in order to verify the efficiency of such additives in increasing thermo-oxidative
stability. All doped and nondoped oil samples were submitted to an accelerated oxidation
test according to modified ASTM D-2440 method. The level of degradation was assessed
by monitoring the area under the carbonyl band (around 1713 cm-1) in the FTIR
spectrum and comparing it to that obtained for the new nonoxidized oil. The results
obtained for the oxidation of nondoped oil samples showed that the kinetic behaviour
may be well represented by a first-order homogeneous reaction rate law, with energy of
activation of around10 kcal/mol. The results also show that hindered phenolic
antioxidants significantly reduce the formation of oxidation products. The addition of a
metal passivator, even at very low levels (8 ppm), causes a synergetic effect with all
antioxidants tested leading to a significant improvement in the resistance of the oil
against oxidation.
56
2.8 Conclusions of literature survey
Corrosion of copper conductors is one of the major problems affecting the

performance of power transformer. Reaction of sulphur compounds from oil on copper
conductors in transformers leads to the formation of copper sulphide which degrade both
the oil and paper insulation. Dibenzyl disulphide (DBDS) is observed to be a major
sulphur source in oil which undergoes thermal degradation finally leading to copper
corrosion. Literature survey reveals that:
Temperature is the main factor leading to the formation of copper sulphide

Among chemical methods, determination of total sulphur, mercaptan sulphur,
DBDS, oil acidity are promising methods for understanding the chemistry of the
processes involved.
Copper corrosion phenomenon is predominantly observed at temperatures of 90 to

150 C
Use of metal passivator is observed to be effective in arresting copper corrosion.
Use of other additives like Irgamet 30 and TTA as metal passivator is observed to
be ineffective as compared to the use of Irgamet 39 metal passivator.
Metal passivators are useful when added initially and can only prevent further
damage to transformers due to copper corrosion. But the passivators cannot undo the
damage which is already present.
Liquid-liquid extraction is observed to be promising method for the removal of

sulphur compounds from mineral insulating oil.
With this background of literature, the details of experimental apparatus and method of
measurements and plan of experiments are discussed in next chapter.
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65

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Chapter 2 Literature Survey

A detailed survey of literature was carried out on various aspects of copper

2.2 Literature on sulphur compounds

Manufacturers and operators are therefore advised carefully to review designs to

Plaza and others [10] studied the homogeneous and heterogeneous

According to Lance Lewand [11] dibenzyl disulphide (DBDS) is one of the

(2) Cu2S, Cuprous Sulfide

dibenzyl disulfide ethylbenzene

Cu2S, Cuprous Sulfide

Vander Tumiatti [13] describes some corrosion phenomena involving copper,

The available techniques for diagnostics of corrosion phenomena and evaluation

formation. The degree of corrosiveness of some sulfur compounds is examined and

Direct contact between bare copper and oil

According to L. Arvidsson [23] the conditions required for the formation of

A paper titled Failures due to copper sulphide in transformer insulation by

M. Lukic [26] and co-workers have investigated the influence of mineral

Observations from the study have shown that aminomethyl substituted

Paper describes that presence of oxygen or oxygen donating compounds like

L. Lewand [30] in their publication on dibenzyl disulphide in transformer oil

T. Amimoto and co-workers [31] have investigated copper-sulfide deposition on

Ren and others [33] have discussed a comparatively detailed summary of

F. Scatiggio and co-workers [35] have evaluated 14 different oil specimens in

2.3 Literature on passivators and stray gassing

T. Wan and coworkers [38] have added Irgamet 39 to a 500 kV transformer to

copper surface was analyzed by scanning electron microscopy, X-ray photoelectron

According to the analysis, deactivation mechanism of Irgamet 39 proceeds via

benzotriazoles, leading to decay. This explains the depletion of BTA and

R. A. Venkata Laxmi and T. S. R Murthy [41] have discussed the corrosion

R. A. Venkata Laxmi and T. S. R Murthy [42] in another study have carried

In the process, a passivating layer is formed, to protect copper dissolution even in

It is also mentioned that thiazoles, triazoles, benzotriazoles give good protection

A. Schaut and coworkers [47] have studied the performance of undeclared

Ivanka Atanasova-Hohlein [49] has explained the mechanism of stray gassing,

The work of Alexandros E. Papadopoulos and Constantinos S. Psomopoulos

2. The developed product contains a powerful blend of different antioxidant

2.4. Literature on liquid extraction

J. M. Lukic and others [59] have investigated selective liquid-liquid extraction

2.5 Literature on UV-Visible spectroscopy to for detecting copper

spectral bandwidth are used as indicators to estimate furan concentration level in

Radha Karthik and others [65] have performed condition assessment of

2.6 Literature on dielectric measurements for study of copper corrosion effects

content monitoring in the operating transformers under the changing temperature

J. H. Yew and co-workers [69] have investigated Frequency Domain Dielectric

Anuradha Kumar and Satish M. Mahajan [70] have subjected a medium

IEEE transformers committee [72] has reviewed the published literature on

2.7 Literature on oxidation of copper

H. Kawarai and others [74] have investigated copper sulphide deposition on

R. Crisostomo Rabelo Neto and others [75] have presented a kinetic

2.8 Conclusions of literature survey

Corrosion of copper conductors is one of the major problems affecting the

Temperature is the main factor leading to the formation of copper sulphide

Copper corrosion phenomenon is predominantly observed at temperatures of 90 to

Use of metal passivator is observed to be effective in arresting copper corrosion.

Liquid-liquid extraction is observed to be promising method for the removal of

[2] S. Toyama, J. Tanimura, N. Yamada, E. Nagao, T. Amimoto, Highly sensitive

[52] Alexandros E. Papadopoulos, Constantinos S. Psomopoulos, Dissolved gas analysis

Related to Dielectric Properties of Liquid and Solid Insulation, IEEE International

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