The Evolving Problem of

Corrosive Sulfur in
Transformer Oil
IEEE/PES Transformers
Committee
Memphis, Tennessee
 Knowledge Is Power SM
Apparatus Maintenance and Power Management
for Energy Delivery

Corrosive Sulfur in Oils, and

Transformers; Why it is Such a
Problem
Lance R. Lewand
Doble Engineering Company
What is Corrosive Sulfur?

US Definition found in ASTM D 2864 -

“elemental sulfur and thermally unstable sulfur
compounds in electrical insulating oil that can
cause corrosion of certain transformer metals
such as copper and silver”
Why is Corrosive Sulfur such a Problem?

• Reacts on contact with copper

• Does not require heat to promote the reaction
• Heat makes the effect more pronounced
• More pronounced in sealed systems
• May lead to deposition of copper-sulfur compounds
in the paper insulation
• Copper-sulfur compound deposition in the paper
insulation will lead to a weakened dielectric strength
The Problem

Ø Large power transformer and reactor failures

starting in 2000. Doble has recorded about 25+
units that have failed worldwide
Ø Many of these are units only 5 to 7 years olds,
(represents high asset cost)
Ø Very little advance warning:
§ No observable PD in tear downs
§ No generation of combustible gas even on the day
before
Effects on Copper
Adverse Effects: Copper Conductor
Initiation of Attack
Copper Conductor

Copper, ≈ 95.5%
Sulfur, ≈ 0.5%
Bulbous Structures on Cu Surface

Copper Conductor

Copper, ≈ 85% (80%)

Sulfur, ≈ 15% (20%)

Copper(I) Sulfide -
aka “Cuprous Sulfide”
Cu2S Layer Buildup

Area of continual
buildup

Compacted Copper
Sulfide Layer
Adverse Effects: NLTC Contacts
Cu2S Deposition on Conductor
Regular Paper

Kraft Paper Crepe Paper

Adverse Effects: Contaminated Paper
Adverse Effects: Plating on Paper
Effects on dielectric strength

Layer 3: 1370 V/mil Layer 2: 1050 V/mil Layer 1: 80 V/mil

Mechanism
Ø Process
§ Corrosive Sulfur presence or formation
§ Attack of metal surfaces, copper sulfide deposition on
conductor
§ Deposition of copper sulfide in paper insulation
Ø Copper ions migrate to the insulating paper adjacent to
the conductor, react with corrosive sulfur compounds (or
transfers over to the paper as a copper/sulfur compound).
Ø Mechanism: Reduction of dielectric strength - voltage of
the conductor exceeds the insulating capacity of the
paper insulation and BIL rating. Result: arcing between
two or more turns/discs and a subsequent failure.
Failure
 HV Winding Dissection
29th Turn
14th Turn
1st Turn

130TH Disk – near very top of transformer

Top

97TH Disk – area of failure

Middle

10 TH Disk – near very bottom of transformer

Bottom
 Disk 10
1200
1st Turn,Copper Result, mg/kg
14th Turn, Copper Result, mg/kg
1000
29th Turn, Copper Result, mg/kg
Cu Concentration, mg/kg

Turn 29

800

600

400

Turn 14
200
Turn 1

0
Layer 1 Layer 2 Layer 3
Layer 4 Layer 5 Layer 6 Layer 7
Layer 8 Layer 9
 Disk 97
1200

1000
Cu Concentration, mg/kg

800

600 29th Turn

400
1st Turn

7th Turn
200

0
Layer 1 Layer 2 Layer 3 Layer 4 Layer 5 Layer 6 Layer 7 Layer 8 Layer 9
(Crepe)
 Disk 130
1200

29th Turn
1000
Cu Content in Paper, mg/kg

800

600
14th Turn

400
1st Turn

200

0 S3
S1
Layer 1 Layer 2 Layer 3 Layer 4 Layer 5 Layer 6 Layer 7 Layer 8
Example Conductor

1136 ppm
233 ppm
122 ppm
92 ppm
91 ppm
71 ppm
86 ppm
136 ppm
Copper Migration/Deposition
The oil flow lines in the HV
Disk 130 winding take place in every
disk just not those shown.

The 3 black dots represent the

Disk 97
turn with the highest copper
found in the testing. The size
of the dot indicates the relative
HV concentration.
LV
Core
Winding Winding

Varnished
wire, no
paper
insulation

Disk 10

Designed
Oil Flow
 Specification & Testing
of Transformer Oils
with Respect to
Corrosion
Insert image
here

Clair Claiborne
ABB Inc, Power Technologies Div., Raleigh, NC
© Copyright 2005 ABB
All rights reserved
 Background/History

F.M. Clark – 1962 – “Sulfur compounds are inevitably present in all commercial
insulating oils” – Insulating Materials for Design and Engineering Practice

Transformer oils contain varying levels and kinds of sulfur compounds

Procedures were standardized to test for corrosive sulfur in the early 1950’s

Relatively few incidents since these standardized tests

-
 Recent History

HVDC Converter Transformers and GSU’s

Reported:
§ CIGRE working group, Paris, 2004
§ ABB Review, 2004
§ IEEE Transformers HVDC section, Las Vegas, 2004
§ Doble Conference, Boston, 2005
§ ASTM D27, Reno, 2005
§ ABINEE, Sao Paulo, 2005
-
 Conditions and Evaluations

Design and operation within industry standard practice

§ No unusual temperature or other environmental factors
§ Sealed units with relatively low oxygen content in oil
§ Relatively high and constant load
Investigation: Cuprous Sulphide, Cu2S
§ On insulation paper
§ On copper conductor
§ Other transformer components
-
 SEM/EDX - Cu2S Deposition from HVDC
Unit

cps
6
O

4 C

Cu
S
Cu Cu
0
0 2 4 6 8 10
Energy (keV)

SEM EDX
-
 Current Situation

Mineral oil/Transformer oil requirements

§ Oxidation stability more important to long life
Sulfur compounds desirable for enhanced stability
Some organic sulfur compounds act as peroxide scavengers in an oxygen-
rich oil
§ Life extension of insulation overriding concern
§ Relatively few cases result from corrosive sulfur
Standards were believed to be strong enough to prevent problems
Only recently (last 5-10 years): Standard tests not always conclusive
-
 ASTM Test D 1275
Corrosive Sulfur in Electrical Insulating Oils
.
§ ASTM D 1275 used since 1953 – Superseded ASTM D 117
§ D 117: 5 hours at 100oC. D 1275: 19 hours at 140oC.

§ F.M. Clark and E. L. Raab, Proc. ASTM, Vol. 48, 1948, pp. 1201- 1210:
§ Demonstrated inadequacy of D 117 at this low temperature and duration.
Could not identify corrosive oils
§ For same level of tarnish, D 117 took 432 hours, but only 5 hours at 140 oC
(temperature chosen for D 1275).
§ D 117 sensed only free sulfur.
-
 Examples of Copper Corrosion Tests

ASTM D 1275: Copper Based Test

Oils at 140oC, 19 hrs

New oil
(Plant oil)

Field Unit 1: Very Field Unit 2:

slightly corrosive Slightly corrosive
-
 Definition of Corrosive Oil - ASTM D 1275

Appearance of Copper Strip

Noncorrosive:

Orange, red lavender, multicolored with lavender, blue or silver, or

both, overlaid on claret red, silvery, brassy or gold, magenta overcast
on brassy strip, multicolored with red and green showing (peacock)
but no gray

Corrosive:

Transparent black, dark gray or dark brown, graphite or lusterless

black, glossy or jet black, any degree of flaking
-
 DIN 51353 – Detection of Corrosive Sulfur –
Silver Strip Method
§ Prüfung auf korrosiven Schwefel - Silberstreifenprüfung
§ Deutsches Institut für Normung e. V.

§ Used in IEC (mostly outside USA)

§Previous Editions: Jan. 1965, Sept. 1977
§Current Edition: Dec. 1985
§ Adopted in response to many color shades on copper
§ Same sample configuration but silver strip
-
 Examples of Silver Corrosion Tests

DIN 51353: Silver Based Test

Oils at 100o C, 18 hrs

New oil
(Plant oil)

Field Unit 1: Very Field Unit 2:

slightly corrosive Slightly corrosive
-
 Definition of Corrosive Oil - DIN 51353

Appearance of Silver Strip

Non-corrosive:

No noticeable affect, or a weak golden yellow discoloration

Corrosive:

Light grey or brown shade to a distinct grey up to black

-
 ASTM D 1275 vs. DIN 51353

Two tests with very nearly the same result

ASTM D 1275 DIN 51353

Copper strip in oil Silver strip in oil
Nitrogen bubbled Loose fitting cap
1 minute (oxygen)
19 hours @ 140oC 18 hours @100oC
-
 Alternative Corrosion Tests
n Doble Engineering Extended/Modified ASTM D1275
Same parameters as D1275 except:
n 48 hours @ 150oC (replacing 19 hours @ 140 oC)

n ASTM D 5623 – Sulfur Compounds in Light Petroleum by Gas

Chromatography and Sulfur Selective Detection

n Potentiometric titration method to determine mercaptan level

n ABB Covered Conductor Corrosion & Deposition (CCCD) test

-
 Why different tests?

n Not all sulfur compounds react in same way

n Environmental dependences:
Presence/Absence of oxygen
Different temperatures
Presence of passivators

n Not all transformers operate with same conditions

-
 Experimental Set-up - CCCD

Gas

Tube with
sample

Thermostatted
block
-
 Experimental Arrangements - CCCD

Cu + pressboard Cu + paper + excess Cu Cu + layered paper

-
 Summary: Methods to Study Problem

n Cu2S deposition reproduced in laboratory

Test materials & environment similar to real transformer
service, e.g. temperature, oxygen content etc
n Result: Cu2S deposition can be reproduced
On conductor
On paper facing the conductor
On free cellulose surfaces
Deposition can occur at low temperatures, 80oC and 100oC
Time required for test 12 weeks at 100oC, 3 weeks 120oC
-
 Promising Tests

§ Metal strip test method such as D 1275 --higher temperature and longer
time
Produces quick screening test
Somewhat sensitive to oxygen
Proposed to ASTM but not accepted – Too few actual cases

§ New ABB CCCD test method preferred

Produces results we want to avoid in transformers
Relatively time consuming
Reliable, produces results close to real case
-
 Conclusions

n Sulfur and potentially corrosive sulfur have always been present

in transformer oil

n Currently available tests not always completely capable of

finding potential problems

n Further development and verification of new standard methods

should be (and is) being pursued

-
The Basics of Crude Oil
Selection and Refining

IEEE/PES Transformers Committee

Fall 2005 Meeting
 Crude Oil Selection
Considerations
1) Availability/Logistics: How much is there and where is it.
How does it get to the plant?

2) What does it look like: Can we run it? Sweet/Sour vs.

Plant Design

3) Will it work?: Target Markets and Specifications

Sulfur evaluations are typically for overall sulfur content only

– no speciation of specific sulfur compounds is necessary
 Major Refining Steps for Naphthenic Oils
Step Objective
Distillation Split into desired Fractions for:
Viscosity
Boiling Range
Volatility
Flash Point
Hydrotreating Convert Aromatics to Naphthenics for:
Better Heat Stability
Better Color Stability
Control of Compatibility
Removal of Impurities
Solvent Extraction Removes Aromatics which:
Improves Stability
Reduces Compatibility
 REFINED LUBE PROCESSING
NAPHTHENIC
CRUDE
UNIT
VACUUM HYDRO-
DISTILLATION GENATION

EXTRACTION
OR FINAL

SOLVENT
DISTILLATION
HYDRO-
CRUDES GENATION
OR

AROMATIC OR
FINISHED
EXTRACTS PRODUCTS
OR
EXTRACTION
SOLVENT

REDUCED
CRUDE
AROMATIC
2005 Calumet EXTRACTS
Lubricants Co.
Corrosive Sulfur in Oil

Joao Baldauf

IEEE TC – Fall 2005

Two new Transmission lines in
the Brazilian Grid :
North/South II
Southeast/Northeast
North/South Line:
o 30 single phase reactors 550/v 3 kV,
55 MVAr plus 6 spare units.In
service 1.5 years.

12 units with oil “A” and

24 units with oil “B”

IEEE TC – Fall 2005

Southeast/Northeast Line:

o 03+1spare reactors 500/v 3 kV 45.3 MVAr

o 06+2spare reactors 500/v 3 kV 33.3 MVAr
o 12+2spare reactors 500/v 3 kV 66.6 MVAr
o 09+2spare reactors 500/v 3 kV 50.0 MVAr

In service 2.5 years. All units with oil “A”

IEEE TC – Fall 2005

o All reactors were filled with oil
tested according to ASTM D 1275
and the result was “non corrosive”.
o After appoximately 6 month in
service some units of North/South
line filled with oil “A” presented
corrosive sulfur when tested with
the same method.
o Units filled with oil “B” did not test
positive for corrosive sulfur

IEEE TC – Fall 2005

o In march 2005, after approx. one year in
service, one of the units of the
North/South line with oil “A” returned to
factory, without having failed, to be
examinated.
o A new heat run test with sensors in the
winding indicated a maximum hot spot of
59.8°C ( copper/ambient).
o DP of paper varying from 900 to 1000
o The copper of 1/3 of the winding was
contaminated with copper sulfide that
migrated to the first two layers of
insulating paper.
IEEE TC – Fall 2005
Copper from the middle of upper disc

IEEE TC – Fall 2005

First two layers of paper

IEEE TC – Fall 2005

Test made with reactor conductor samples

IEEE TC – Fall 2005

o August 2005 one of the 33.3 MVAr
reactors of the Southeast/Northeast line
that failed after 2.5 years in service was
opened in the factory.
o All the copper was contaminated with
copper sulfide.
o Until the end of september 2005 eight
reactors from different manufacturers of
this line failed, all with oil “A”

IEEE TC – Fall 2005

Failure in the second disc from the top

IEEE TC – Fall 2005

Contaminated copper and first seven paper layers

IEEE TC – Fall 2005

o There is also a transmission line of
another utility with:
6+1 spare reactors 550/v 3 55 MVAr
6+1 spare reactors 550/v 3 35 MVAr
o All filled with oil “A” with corrosive sulfur
and energized since the end 2002
(approx. the same age of the
Northeast/Southeast line ).
o No one failed.

IEEE TC – Fall 2005

o To finish three conclusions and one
question:
1- The copper sulfide migrates from the
conductor to the insulation paper reducing
it´s dielectric strenght.
2- The corrosion of the copper conductor
begins with temperatures below those
allowed by the standards and is more
significant the higher the temperature.
3- The contamination (copper and paper)
increases with the time.
o 1- Why some TL are more subjected to
failures than others? (Transients ?)
IEEE TC – Fall 2005
Tamyres Luiz Machado Junior

Corrosive Sulphur
 Corrosive Sulfur
Since December 2004 , 12 Single Phase Shunt Reactors 525 kV
of the North – Southeast Brazilian Interconnection failed due
to the problems with corrosive sulfur (7 units delivered by
Siemens and 5 units by another Brazilian manufacturers)

Recently, a second single phase GSU units of Nuclear Power

Station – Angra 2 failed.
The ASTM special tests was performed in the oil of all four
units and it was detected the presence of corrosive sulfur in
the oil of the two failed units.
The failure investigation showed a high degree of copper
sulphide contamination on the paper insulation of the tap
leads and HV winding conductors .
The most likely cause of the failure is still in discussion.

23.10.2005
 Single Phase Shunt Reactors
50 MVAr and 66 MVAr
525 kV

23.10.2005
 Reactor core&coil assembly

23.10.2005
 Reactor Failure

23.10.2005
 Reactor Failure

23.10.2005
 Disc conductors from the upper part

Reactor Failure

outer strand of twin Inner strand of twin

Turn at the outer diameter Turn at the inner diameter

23.10.2005 Inner strand of twin Outer strand of twin

 Reactor Failure
Copper Sulphide deposits at different
disc locations

23.10.2005
 GSU Transformer Failure

23.10.2005 Source : EPRI Report 09/2005 to Eletronuclear – Mr. Nichols C. Abi-Samra

 GSU Transformer Failure

23.10.2005 Source : EPRI Report 09/2005 to Eletronuclear – Mr. Nichols C. Abi-Samra

 GSU Transformer Failure

23.10.2005 Source : EPRI Report 09/2005 to Eletronuclear – Mr. Nichols C. Abi-Samra

 GSU Transformer Failure

23.10.2005 Source : EPRI Report 09/2005 to Eletronuclear – Mr. Nichols C. Abi-Samra

 GSU Transformer Failure

23.10.2005 Source : EPRI Report 09/2005 to Eletronuclear – Mr. Nichols C. Abi-Samra

 GSU Transformer Failure

23.10.2005 Source : EPRI Report 09/2005 to Eletronuclear – Mr. Nichols C. Abi-Samra

 Copper Sulphide deposit mechanism

2. Catalytic
deposition of
Cu2S

1. Superficial
corrosion of
copper

23.10.2005
 Failure Mechanism

COPPER

PAPER

PAPER

COPPER

23.10.2005
 Failure Mechanism

COPPER

PAPER

PAPER

COPPER

23.10.2005
 Sulfur Source

Fonte: Nynas

Source: Nynas

SourceS: EPRI Report 09/2005 to Eletronuclear – Mr. Nichols C. Abi-Samra

Nynas report

23.10.2005
 Corrosive Sulfur Test

23.10.2005
23.10.2005 Source : EPRI Report 09/2005 to Eletronuclear – Mr. Nichols C. Abi-Samra
 Oil Passivator (Nypass)

Conductor
surface

The passivator protects the copper surface against to

the new attack of the corrosive sulfur.
The passivator can stop the cooper sulphide
generation but it is not able to remove the existing
23.10.2005
deposits on the paper insulation.
 Recommended Actions
•Oil Corrosive Sulfur test performs using the
ASTM modified test (150 ºC and 48h with O2
removed).
•Addition of Passivator where the corrosive
sulfur attack are still not critical, according to
oil supplier recommendations.

23.10.2005
 Open questions
• Critical operating temperature level and
surround conditions.
• Breakdown mechanism
•Diagnostic method to evaluate the
contamination degree and the insulation
strength reduction.
• Long term performance of the Passivator.
23.10.2005
Corrosive Sulfur Tests
Results
Salt River Project
By Tom Lundquist
Transformer Oil Test Results
Modified ASTM D-1275

• 198 transformer tested

• 19% (38) failed the Modified test
• 2.0% (4) failed the standard D-1275 test
• All were built between 1998 & 2004
• 4 manufacturers transformers involved
Transformer Oil Test Results
Modified ASTM D-1275

• No Significant Indicators from oil screen

tests
• 218,000 gallons of oil
• $22 million transformers at risk
• At least 2 oil refiners involved one
unknown
Transformer Oil Test Results
Modified ASTM D-1275

• Both inhibited and uninhibited oils

• To stop the corrosive sulfur issue
– adding metal deactivators to the transformer
oil at 100 PPM.
– Require any new oil shall pass the Modified
D1275 test before receipt.