SC A2: Transformers

PS 2: Reliability and Risk Assessment of Transformers in Service

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Mineral Oil with Corrosive Sulfur Method Evaluation to Identify False

Negatives and Its Performance with blends of Natural Ester
GAUGER, G., LEMM, A., MARTINS, M., RAPP, K.
Cooper Power Systems
U.S.A.
ggauger@cooperpower.com

SUMMARY: Over the past ten years failures of large power transformers and reactors have
occurred which are attributed to the presence of corrosive sulfur in mineral oil. Intensive
investigations of the failure phenomena, associated detection, and remedies have been
pursued by many experts on an international scale. Improvements in screening procedures,
such as ASTM D 1275 Method B [1] and the Covered Conductor Deposition (CCD) method
[2][3], have been introduced that allow more effective detection of corrosive sulfur
compounds in mineral oil. Long-established methods assumed that all corrosive sulfur
compounds present in transformer oils existed in their ordinary as received - unused state,
or were extracted from solid materials, such as rubber gaskets or other construction materials.
This study shows that, as testing proceeded, the corrosive sulfur can also be generated from
reactions or rearrangement of non-corrosive sulfur species in the oil, some of which may have
had beneficial antioxidant properties.
Given the high cost of equipment failure resulting from corrosive sulfur, detection methods
susceptible to false negatives are of particular concern when evaluating oils for corrosive
sulfur. This study uses a more aggressive copper strip screening test for sulfur compounds
having corrosive potential. To accomplish this, higher test temperatures and longer aging
times are used to promote the reactions and rearrangements needed for these species to react
with copper. A severity index is created to compare this method to ASTM D 1275 Methods A
and B. We evaluate mineral oils from different suppliers and origins, along with synthetic
and natural ester fluids. The judgement of whether an oil sample is corrosive or not is, in
part, determined by the intensity of discoloration observed on a copper strip. However,
discoloration of a strip, especially at higher temperatures and longer aging times, can be due
to non-sulfur sources. Semi-quantitative elemental surface analysis, using x-rays to confirm
the presence of sulfur, provides the needed correlation of strip discoloration with sulfur
corrosion. Some of the oil samples that are found to be non-corrosive using ASTM D 1275
Method B are corrosive when evaluated using the more aggressive aging procedure.
The corrosive residue that forms is the result of chemical reactions between metallic copper
and some sulfur compounds. We find high concentrations of dibenzyl disulfide (DBDS) in
several mineral oil samples that give positive corrosive sulfur results. In addition, precursor
reactions may occur with time and temperature that cause rearrangement of non-corrosive

sulfur to corrosive species. The reaction products have been shown to migrate into or on the
cellulose insulation.
Gas chromatography is used to determine sulfur species by the ASTM D 5623 method [4].
The chromatograms of various mineral oils show that the highest concentrations of sulfur
compounds are unidentified volatile sulfur species. Our analysis shows that natural and
synthetic ester fluids have essentially no sulfur compound profile, correlating with no
observed corrosivity on the copper strips.
Recently, other researchers have found that simply adding passivator chemicals to mineral oil
transformers and reactors that contained the corrosive sulfur agent DBDS in the oil delayed
the corrosive effects, but did not stop them. Some of the passivated units eventually failed.
Retrofilling corrosive sulfur contaminated equipment with non-corrosive oil has been an
effective mitigation tool. We show that typical retrofill blends of natural ester fluid with
sulfur-contaminated mineral oil passes the ASTM D 1275B method as non-corrosive.
However, these retrofill blends are still corrosive to copper using the more severe screening
method. Retrofilling with natural ester fluid did decrease the reaction products of sulfur on a
copper strip by nearly 76% and extended the time to corrosive discoloration by 5 times
compared to the corrosive mineral oil prior to blending.

KEYWORDS: Corrosive Sulfur, Natural Ester, Dibenzyl Disulfide, Severity Index, Sulfur
Speciation, metal passivator, retrofill

INTRODUCTION: The issue of corrosive sulfur and then the subsequent impact it has on
transformer life has become a rising issue to utilities today. The level of corrosiveness can
continue to increase until it ultimately leads to failure of the equipment. Sulfur, in its many
forms, is present in many of the components that are used within the equipment. Aside from
the mineral oil, it exists in gasket materials, the kraft paper and even the copper.
Elemental sulfur is the most reactive form. In most cases, the sulfur exists as part of an
organic complex. The deeper within the molecule the sulfur is the less reactive it is. Many
sulfur compounds are stable and do not contribute to the available reactive sulfur, however,
with temperature and the right conditions, these stable compounds can be converted into some
reactive species.
Copper is a very reactive metal and can readily react with many of the sulfur compounds
forming a variety of products which over time can bridge gaps and spaces and result in a
potential for dielectric failure. These deposits can also lead to overheating of the conductor
which can aggravate the issue. Other reactive components can react with the copper and
leave surface discontinuities or even holes in the conductor. Additional deposits can also be
built up on or within the insulating paper and reduce the insulating capabilities of the paper.
Thirty dielectric coolants were evaluated in this study. The oils represented domestic (North
American) and foreign mineral oils, natural esters, synthetic ester and samples of oils
representative of compositions that could result from the retrofill of mineral oils with natural
ester oils.

BACKGROUND: The issue with corrosive sulfur has been around for a long time and was
responsible for the development of the initial test methods to evaluate for corrosive sulfur.
Over the past ten years, there has been reported a growing number of field equipment failures
that have been associated with the issue of corrosive sulfur.[,5,6,7,8,9,10,11,12] Current
testing methods and recent changes to those methods are still inadequate to screen out
potential corrosive sulfur issues.

SCOPE: The scope of this investigation was multifaceted.

1)
The goal was to provide a comparison of fluid performance using various
testing methodologies and demonstrate how some of these methods may be
inadequate to sufficiently screen fluids which can cause issues with corrosive
sulfur.
2)
Demonstrate the problems that can arise with the use of a subjective evaluation
of the discoloration to determine a pass or failure.
3)
Demonstrate if sulfur speciation analysis can be an effective means of
screening insulating fluids for the presence or source compounds for corrosive
sulfur formation.
4)
Demonstrate that retrofilling a transformer with a sulfur free dielectric fluid
can inhibit the progression of the corrosive sulfur.

EXPERIMENTAL: Testing for the determination of corrosive sulfur was performed using
approved standard testing methodologies. The current ASTM D 1275 and ASTM D 1275 B
represent the most common methods used in North America. The ASTM D 1275 method is
also equivalent to ISO 5662.
The current DIN 51353 method [13] was used as it utilizes a silver strip which has been
claimed to be more sensitive than the copper.
An alternative method, performed by Doble Engineering, was used to significantly accelerate
the reactivity of the sulfur compounds and also to accelerate the potential conversion of nonreactive species into reactive species. The Doble/Cooper Research method consists of
preparing samples in accordance with the requirements of ASTM D 1275B. The samples are
placed into a forced air oven that has been heated to 150C and maintained for 48 hours. At
the end of that time the copper strip is observed in comparison to the standard color detailed
by ASTM D 130 [14]. If they are classified as non-corrosive, the samples are returned to the
forced air oven and the temperature is increased to 160C and maintained for 24 hours. At the
completion of the 24 hours, the samples are removed and the copper strip is observed in
comparison to the standard color detailed by ASTM D 130. The testing is continued, as long
as the sample remains classified as non-corrosive, by increasing the temperature by 10C and
observing at the end of each 24 hours. When the temperature reaches 180C, the temperature
increments are stopped and the sample is observed every 24 hours for 7 days. The testing is
terminated at this time. The testing is also terminated whenever the specimen is classified as
corrosive. The results are reported as corrosive or non-corrosive based on length of time at
temperature.
The proposed severity index, as listed in Table 1, is calculated by doubling the severity for
each 100C increment of temperature and successively multiplying the time at each
3

temperature divided by the 19 hours of strip aging in the ASTM D1275 method. Thus,
ASTM D 1275 method is described as severity index 1 and ASTM D 1275 method B has a
severity index of 5. Extrapolating this to the end of the Doble modified method would result
in a severity index of 331 over the ASTM D 1275 method.
.
Sulfur speciation testing was performed in accordance with ASTM D 5623 using gas
chromatography and a sulfur selective detector.
Simulated retrofill blends were prepared by blending natural ester fluid with mineral oils
containing high levels of corrosive sulfur compounds. Additional simulated retrofill blends
were prepared with a passivator to investigate their potential impact.
EXPERIMENTAL DATA:
Table1:
Insulating Fluid

ASTM D
1275
Method
B

NE-1

Pass

NE-2

Pass

DMO-1

Pass

EMO-1

Pass

EMO-2

Pass

SAMO-1

Pass

SE

Pass

NE-3

Pass

NE-4

Pass

EMO-3
EMO-4
(Passivated)**

Fail
Pass

NE-5

Pass

DMO-2

Pass

DMO-3

Pass

SE

Pass

DMO-4

Fail

Corrosive Sulfur of Dielectric Fluids

Doble/Cooper
Research Method

Corrosive @
180C; 144 hrs.
Corrosive @
180C; 144 hrs.
Non-Corrosive @
180C; 168 hrs.
Corrosive @
180C; 24 hrs.
Corrosive @
180C; 24 hrs.
Corrosive @
180C; 24 hrs.
Non-Corrosive @
180C; 168 hrs.
Non-Corrosive @
180C; 168 hrs.
Non-Corrosive @
180C; 168 hrs.
Corrosive @
150C; 48 hrs.
Corrosive @
180C; 24 hrs.
Non-Corrosive @
180C; 168 hrs.
Non-Corrosive @
180C; 168 hrs.
Non-Corrosive @
180C; 168 hrs.
Non-Corrosive @
180C; 168 hrs.
Corrosive @
150C; 48 hrs.

Severity
Index

Sulfur
Speciation
Total
(ppm)

Dibenzyl
Disulfide
Total
(ppm)

SEM
Verified
Relative
%S

262

<1 ppm

<1 ppm

nd

262

nd

331

nd

81

386

70

23.2

81

18.8

81

22.6

331

nd

331

nd

331

nd

893

321

7.9

81

16.6

331

nd

331

<1 ppm

<1 ppm

nd

331

<1 ppm

<1 ppm

nd

331

<1 ppm

<1 ppm

nd

<1 ppm

11.1
4

DMO-5

Pass

Non-Corrosive @
180C; 168 hrs.
Non-Corrosive @
180C; 168 hrs.

331

80

<1 ppm

nd

nd
DMO-6
Pass
331
33
<1 ppm
*NE Natural Ester, SE Synthetic Ester, DMO Domestic Mineral Oil, EMO European
Mineral Oil, SAMO South American Mineral Oil
**Dielectric fluid received containing a passivator
Table 2:

Corrosive Sulfur of Simulated Retrofilled Blends

Severity
SEM
Doble/Cooper
ASTM
Index
Verified
D 1275 Research Method
Insulating Fluid
Method
B
5% EMO
95% NE-1
10% EMO
90% NE-1
5% SAMO
95% NE-1
10% SAMO
90% NE-1
10% SAMO
90% NE-1
5% EMO
95% NE-1

5% EMO/95% NE1
(500 ppm passivator)
10% SAMO
90% NE-1

Pass
Pass
Pass
Pass
Pass
Fail

Relative
%S
Corrosive @
180C; 72 hrs.
Corrosive @
170C; 24 hrs.
Corrosive @
170C; 24 hrs.
Corrosive @
170C; 24 hrs.
Corrosive @
160C; 24 hrs.
Corrosive @
160C; 24 hrs.

130

4.5

32

6.8

32

18.0

32

21.9

13

14.9

13

12.7

331

nd

7.7
5.0

Fail

Non-Corrosive @
180C; 168 hrs.
Corrosive @
150C; 48 hrs.

10%SAMO/90%NE1
(500 ppm passivator)

Pass

Corrosive @
180C; 144 hrs.

262

5%SAMO/95%NE1
(50 ppm passivator)

Pass

Non-Corrosive @
180C; 168 hrs.

331

10%SAMO/90%NE1
(50 ppm passivator)

Pass

Corrosive @
180C; 168 hrs.

331

10%SAMO/90%NE1
(500 ppm passivator)

Pass

Non-Corrosive @
180C; 168 hrs.

331

Pass

4.6
22.7
nd

DATA ANALYSIS AND REVIEW: All of the oils evaluated passed the standard ASTM D
1275 (Method A) test; at 140C for 19 hours. Four of the oils evaluated failed the ASTM D
1275 (Method B) test conditions; 150C, 48 hours. All of the oils which failed the ASTM D
1275 (Method B) test had moderate, but not high, levels of sulfur on the copper strips.
In the case of the more severe Doble/Cooper Research method, as described in this paper,
there were 17 out of the 30 samples that qualified as corrosive based on the subjective
appearance of the strip color.
5

Energy Dispersive X-ray (EDX) analysis was used to verify the presence of elemental sulfur
on the surface of the copper strips. The EDX analysis readily passes through the coating on
the copper strip reflecting back X-rays predominantly characteristic of elemental copper. The
remaining X-rays, characteristic of the discoloration/coating material represent the sulfur in
the coating as well as background elements from the base metal. The nature of the
background radiation is such that, for practical purposes, it is difficult to positively confirm
the presence of sulfur in the test strip below a concentration of about 3%. In the event of very
thin film discolorations, EDX analysis is unable to detect the species contributing to the
discoloration.
On the basis of the 17 copper samples which were judged positive by the Doble/Cooper
Research method, only 14 could be confirmed to have levels of sulfur in the low to
intermediate range.
None of the natural or synthetic esters were found to contain any detectable sulfur levels
despite the corrosive designation assigned after the Doble/Cooper Research method. This
demonstrates the need for some type of supplemental verification of sulfur presence on the
copper strip so that false positives can be avoided..
The majority of oils that failed the Doble/Cooper Research method were from European or
South American sourced oils. The one North American sourced oil was a light paraffinic oil.
To simulate retrofill conditions, mixtures of natural ester with 5% and 10% respectively, of
corrosive mineral oil, demonstrated to be corrosive by the Doble/Cooper Research method
conditions, were prepared and tested. The results, shown in Table 2, indicate that even under
best case retrofill conditions, (5% mineral oil), the residual corrosive oil in the blend is
enough to cause the retrofilled oil to be ranked as corrosive. The results do indicate that the
blends do require significantly more severe conditions before being ranked as corrosive.
In another experiment, the retrofill conditions were repeated (5% and 10%) with corrosive
oils that were supplemented with 500 ppm of a metal passivator. In this case, the passivator
containing corrosive blend was non-corrosive in the Doble/Cooper Research method at a 5%
loading but ranked as corrosive at the 10% level.
To evaluate the effect of metal passivator concentration, the retrofill experiment was applied
to passivator levels of 50 ppm and 500 ppm. In this case, the 5%SA-mineral oil blend with 50
ppm passivator remained non-corrosive under the Doble/Cooper Research method, but ranked
corrosive at the 10% SA-mineral oil level. Unlike previous tests with 500 ppm passivator, in
this test at the 10% spike level, the simulated retrofill was non-corrosive in the Doble/Cooper
Research method.
Sulfur speciation was performed by ASTM D5623 to attempt to correlate specific sulfur
compounds with the results from the Doble/Cooper Research method. The number of specific
sulfur compounds analyzed by the D5623 method was 48. Even so, the largest number of
compounds detected by chromatography were of unknown composition. The presence of
larger amounts of sulfur compounds, from known and unknown sources, did correlate with a
tendency for greater corrosivity via the copper strip tests.

The sulfur specific chromatographic analysis was also able to show that, in certain cases
involving highly refined mineral oils, natural esters and synthetic esters, no detectable
amounts of sulfur species were present in the respective dielectric fluids even though the more
severe copper strip appears to have significant discoloration.

CONCLUSION:
Neither the current ASTM D 1275 methods nor the added sensitivity of
the silver in DIN 51353 are sufficient enough to indicate the presence of corrosive sulfur in
the dielectric fluids evaluated. Thus, false negatives are probable and consideration for a
more effective method is indicated.
As the test conditions become more severe, as in the Doble/Cooper Research method, there
are other reactions that may cause discoloration of the copper strip. During a subjective
visual evaluation of the copper strip for the determination of corrosive sulfur, the potential
exists for an evaluation to inaccurately rank the results of the test. The use of SEM/EDS, or
other comparable methodology, to evaluate for the presence of the sulfur on the copper test
strip is crucial to eliminate false positives. Further work needs to be completed to help
identify alternative reaction products causing strip discoloration.
The determination of the sulfur species present in a dielectric fluid provides valuable
information into the types of sulfur compounds present, however it also may be insufficient to
reflect the potential for a corrosive sulfur issue, as most analyses show the majority of sulfur
compounds present as unidentifiable. Research to determine the composition of unknown
sulfur species will prove valuable in better understanding the corrosive sulfur problem and its
remediation.
Retrofilling units, which previously contained corrosive sulfur contaminated oil, with a sulfur
free dielectric fluid is an effective means of improving the effects of corrosive sulfur. The
addition of an effective passivator to the retrofilling dielectric fluid will further reduce the
impact of the corrosive sulfur.

BIBLIOGRAPHY
[1]

[2]
[3]
[4]

[5]

[6}

[7]

[8]
[9]

[10]
[11]

[12]

[13]

[14]

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