Copper Sulphide in

Transformer Insulation

Tutorial of Cigre WG A2-32

Convener: Mats Dahlund, Sweden
 Different examples of
copper sulphide growth
 What is the problem?
•Cu2S is a conductor

•Extensive growth may form a conducting bridge through

the conductor insulation

•Lowered PD inception voltage may occur already with

moderate amounts of sulphide formation

•Local heat evolution may lead to degradation of paper

•Other possibilities?

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 3

 Extent of problem

During the last 15 years: 100 failures of large units?

All major transformer manufacturers affected

Several different oil suppliers

Many observations of copper sulphide

- but not always a cause of failures

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 4

 WG A2-32 tasks
•Understanding the mechanisms of sulphide
formation and failures

•Find relevant methods to test oil

•How to identify units at risk

•Identity mitigation techniques

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 5

 Not tasks of A2-32:
•Copper corrosion or effects of corrosive
sulphur in general

•Tap changers/ Selectors

•Bushings

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 6

 WG Members
• Mats Dahlund, convenor, Sweden
• Ivanka Höhlein, (TF 01), Germany
• Riccardo Maina (TF 02), Italy
• Nick Dominelli (TF 03), Canada
• Trond Ohnstad TF 04), Norway
• Tsuyoshi Amimoto, Japan
• Yves Bertrand, France
• Xue Chendong, China
• Clair Claiborne, USA
• Paul Griffin, USA
• Jelena Lukic, Serbia
• Lars Lundgaard, Norway
• Julie Van Peheghem, Belgium
Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32
• Volker Null, Germany
• Jayme Leite Nunes Jr, Brazil
• Marit-Helen Ese, Norway
• Alfonso de Pablo, Spain
• Christophe Perrier, France
• Fabio Scatiggio, Italy
• Viktor Sokolov†, Ukraine
• Kjell Sundkvist, Sweden
• Yongyuth Vachiratatarapadron, Thailand
• Junji Tanimura, Japan
• Peter Smith, Germany
• Vladyslav Mezhvynskiy, Germany
7
 Task Forces of WG A2.32
• Task Force 1
New test for detection of corrosive sulphur
(new standard IEC 62535)

• Task Force 2
Metal passivator – analysis methods and stability

• Task Force 3
Sulphur speciation

• Task Force 4
Recommendations for users

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 8

 WG A2-32 now closed
• All original tasks adressed, Broschure No. 378 published

• Other related CIGRE and IEC working bodies active

now:

Oil testing and specification IEC TC10 MT21

Oil maintenance IEC TC10 MT22
Sulphur speciation IEC TC10 WG37

Copper sulphide - long term mitigation and risk

asessement (starts in 2009) CIGRE WG A2-40

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 9

 Cu2S formation mechanism
•Details of mechanism are not understood
- but some progress made

•Some active sulphur compounds identified

- disulphides in general, DBDS in particular

•Influence of oxygen clearly demonstrated

- some explanations proposed

•Influence of non-corrosive oil components

is still not well understood

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 10

 Proposed Cu2S formation
mechanism
DBDS-Cu complex By-products

CH 2 CH 2
CH BiBZ
CH
2
2
Insulating oil

S-S
CH 2 S CH 2
CH 2 S-S
S- CH 2 Cu Cu ＤＢS
ＤＢＤS Diffusion

Absorption Reaction
Dissolution
Step 1
Make particles
Coordination
CH
2 CH
2
Step 2 Cu2S
S-S S
CH
CH
2
2 Decomposition
S-S Cu Cu Cu Cu
Copper

Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu
Insulating paper
Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 11

 Main influential factors

• Corrosive sulphur in oil

• High temperature

• Oxygen content

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 12

 Corrosive oil
The presence of corrosive (or potentially corrosive)
sulphur is a prerequisite for copper sulphide
formation

Oil failing IEC 62535 or ASTM D1275-B should be

considered as corrosive

Metal passivators may block the effects of corrosive

components, even under the severe conditions of
these tests

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 13

 Problems only with uninhibited oil?

• Most problems were with uninhibited oil

(these need more sulphur content for oxidation stability)

• Some oils with inhibitor also caused failures

• Inhibitor may influence deposition

– but problem not restricted to one type or another!

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 14

 Temperature
•The rate of all chemical reactions is governed by
temperature

•The rate of sulphide formation reactions seems to

approximately double for every 10ºC increase of
temperature

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 15

 Oxygen content
•Oxygen promotes copper transport to
paper, but there seems to be an optimal
range

•Some sulphur compounds become more

active when oxidized, or is there an effect
of other oxidation products in oil helping
solubilize copper?

•Paper surface more efficient sorbent for

intermediates when oxidized?

•At very high O2 content precipitation of

oxidation products becomes significant

•Conclusion so far: low to intermediate

oxygen content seems worse than high (or
absent O2)

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 16

 Closed vs. open breathers
Initial failure statistics seemed to be dominated by closed units, but we
also see cases with open breathers.
Closed:
•Major population works under high load

Open breathers:
•Oxygen in moderate amounts is promoting Cu2S formation
•But process could also be slower due to competitive oxidation reactions

A constant (high) load means the transformer is not breathing, even if it

is nominally a ”free breather”
The problem is thus not restricted to one type or another, high load is the
dominant risk factor
Actual oxygen content is more important than ”closed” or ”open” type

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 17

 Applications
•Failure statistics were initally dominated by
- Shunt Reactors
- Generator step-up transformers
- HVDC transformers

•Growing number of failures in other groups,

e.g.
- Industrial (rectifiers)
- Transmission and distribution (varying sizes)

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 18

 Test methods for detecting
corrosive sulphur in oil
• Metal strip tests

• Tests involving copper and paper

• Chemical analysis (“speciation”)

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 19

 Metal strip tests
• Silver strip tests

DIN 51353 100˚C, 18 hours

• Copper strip tests

ASTM D1275-A 140˚C, 19 hours

(ISO 5662)

ASTM D1275-B 150˚C 48 hours

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 20

 Test involving paper

Objectives of Task Force A2-32.01:

• The test should reflect the environment in a real

transformer

• To provide relevant results in an accelerated mode

• To cover the existing failure modes

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 21

 Proposed method from TF A2-32.01

• Carried out in a 20 ml head-space vial

• 15 ml air saturated oil + 5 ml air

• 3 cm copper conductor
8 mm x 2 mm, 1 paper layer
wound „gap to gap“

• 72 hours at 150°C

• Now IEC 62535

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 22

Evaluation of copper and paper after the test
The result is “corrosive” if one or both of the following is found:
-dark grey, dark brown or black discoloration of copper

or

-shiny deposits on paper

corrosive

noncorrosive
 Specific sulphur compounds

Some researchers have pointed out the presence of a

dominant sulphur containing compound in many corrosive
oils.

This dominant compound was identified as dibenzyl-

disulfide (DBDS)

DBDS has been shown to be a strong copper sulphide

forming agent, present in most (but not all) oils involved

Most oils introduced recently do not contain detectable

amounts of this substance

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 24

Gas Chromatography with sulphur-
specific detector (e.g. AED) used to
reveal the presence of DBDS

Oil with DBDS

Dominant peak found in sulphur
chromatogram, identified as DBDS

Oil without DBDS

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 25

 Sulphur speciation TF A2-32.03
recommended methods

• Dibenzyl disulphide (DBDS)

- GC-ECD
- GC-MS
- GC-AED

• Sum of disulphide and mercaptan sulphur

- potentiometric titration with Ag/Ag2S electrode

• More details in separate report

• Work is carried on by IEC TC10 WG37

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 26

 DGA
•Not useful for direct detection of Cu2S formation

•However, DGA may be a valuable component in

overall risk assessment, by detecting conditions
that lead to higher risks of Cu2S formation:

- oxygen depletion
- overheating

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 27

 Oil tests – conclusions

• Qualitative tests have highest priority:

- IEC 62535 covered conductor test
- ASTM D1275-B copper strip test

• Determination of content of corrosive components

can be useful additional information

• Limited possibilitites to detect Cu2S formation

- though depletion of DBDS and build-up of
known by-products may give some indication

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 28

Other ways to detect copper
sulphide formation?
• Dielectric response methods (e.g. FDS, Power Factor
Tip-Up, PDC, FRA?) may give some guidance

• Very limited experience so far

• Interpretation difficult

• May indicate the presence of conducting contaminants,

but location and amounts of contaminants is difficult to
assess

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 29

 FDS (or DFR)
Dielectric Response Method
Frequency Domain Spectroscopy or Dielectric Frequency Response

–Measurement of dielectric properties: (capacitance, loss, tangent

delta/power factor) over a range of frequencies
(typical frequency range: 1mHz – 1000Hz)

–Typical applied voltage: 140V rms

–Interpretation with modeling of contamination in insulation system

requires knowledge of geometric design parameters of insulation
system, dielectric characteristics of the oil and oil-impregnated
cellulose under different moisture and temperature conditions

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 30

 FDS Analysis of Winding to
Core Shield Insulation
•Measurement
deviates from
normal unit model
•Estimated extent of
contamination:
–1-2% volume of
solid insulation

•Estimated
conductivity of
contaminant:
–2E-10 – 5E-11 S/m
(clean paper:
approx 10-16S/cm)
Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 31
 Power Factor tip-up

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 32

 Inspection of windings

• Copper sulphide deposits are normally

not seen unless oil is removed

• Deposits may be very localized, both axially and

radially in windings (and in paper layers!)

• Carry out all inspection in an unbiased manner

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 33

 Mitigation techniques
• Oil additives (metal passivators)

• Oil treatment

• Oil exchange

• Modified operating conditions

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 34

 Metal passivators
• Experiences

• Consumption/ Monitoring

• Side effects

• Effects of oil treatment

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 35

 Metal passivators
• Efficiency demonstrated in many different corrosivity test
set-ups

• Extensive experience - have been used for a long time

(e.g. in Japan)

• Procedures developed to add on site

• Limited life in some cases, especially for aged oils –

recommended to monitor the passivator content

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 36

 Metal passivators
• Monitoring , analysis
• HPLC method developed by TF02

BTA Final results from RRT:

50 ppm

Irgamet39
50 ppm

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 37

 Metal passivator - depletion
2 different cases

120 140

Irgamet 39 conc. (mg/kg)

Irgamet 39 conc. (mg/kg)

100 120

100
80
80
60
60
40
40
20 20

0 0

24/03/2006

13/05/2006

02/07/2006

21/08/2006

10/10/2006

29/11/2006

18/01/2007
24/03/2006

02/07/2006

10/10/2006

18/01/2007

28/04/2007

06/08/2007

14/11/2007

22/02/2008

01/06/2008

09/09/2008

Sampling date
Sampling date

Only some initial decrease Steady rate of depletion

(absorption by paper?)

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 38

 Passivator - side effects and
caution
1000

• Stray gassing! 800

H2 (ppm)
600

400

200

07-06-17

07-08-06

07-09-25

07-11-14

08-01-03

08-02-22

08-04-12

08-06-01
• Treatments on passivated oil:

- reclaiming will remove passivator

- reconditioning OK (with care)

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 39

Oil treatments for sulphur removal
continuous on-line treatment with sorbent

“selective depolarization”
(a combination of reagents and sorbents)

mobile on-line reclaiming, with reactivating sorbent

treatment with KOH/PEG, similar to established PCB removal

technology

liquid-liquid extraction

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 40

Treatment of oil – general concerns

•Do not expect every combination of oil and treatment

to work

•Not only corrosive sulphur is affected

•Always verify the result by established oil tests and

the new severe tests for corrosive sulphur

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 41

 Oil exchange
• A complete change to non-corrosive oil is
obviously desirable

• Exchange is never truly complete in real life

• Due to contamination from old oil, exchange may

sometimes not totally eliminate further corrosive
reactions – test before, with a pessimistic ratio of
old oil:new oil

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 42

 Operating conditions
•Keep temperature down
- load restrictions
- improved/forced cooling

Winding Hot Spot Temperature

108
106 Forced Air Cooling
104 Natural Cooling
102
100
°C
98
96
94
92
90
12.00 15.00 18.00 21.00 0.00 3.00 6.00 9.00 12.00
t ime

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 43

 Recommendations
•Guidelines for data
collection and ranking

•Decision making
scheme, that uses
- oil tests (trends)
- maintenance history
- operating conditions
Selection made in present
range of available mitigation
techniques

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 44

 What if I already have Cu2S deposits?
•Minimize risk of further Cu2S formation

•Avoid overvoltages

•Use experience from “brothers and sisters” to assess

seriousness

•Plan for repairs/ replacements

•Remember:
Presence of Cu2S does not necessarily lead to failure

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 45

 Conclusions
•Copper sulphide is still a real problem, due to large
numbers of transformers having corrosive oil
•A growing range of mitigation techniques is at hand
•Relevant test methods for corrosive sulphur in oil are
now available
•Precise diagnostics and risk assessment methods are
still not well developed
– WG A2-40 will carry on the work

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 46

 Thank you for
your attention!

Brochure 378 available

at www.e-cigre.org

Copper Sulphide in Transformer Insulation - Tutorial from Cigre WG A2.32 47