COPPER SULPHIDE LONG

TERM MITIGATION AND RISK

ASSESSMENT
Working Group A2.40

TUTORIAL
WG members
Members
J.Lukic, convenor&TF 01 leader (RS), G.Wilson, TF 02 Leader (UK), F.Scatiggio, TF03
Leader (IT), M.Dahlund, (SE), R.Maina (IT), J.Rasco (USA), L.E.F. de Lemos (BR),
A.Peixoto (PT), T.Buchacz (PL), C. Perrier (FR), I.A. Hhlein (DE), A.Skholnik (IL),
P.Wiklund (SE), B.Nemeth (HU), H.Ding (UK), A.Lombard, (ZA), Y.Bertrand (FR), J.Van
Peteghem (BE), P.Smith (DE), S.Dorieux (FR), M.Facciotti (UK).

Corresponding members
G.Krikke (NL), M.Grisaru (IL), L.Lewand (USA).

Former members
L. Eiselstein (USA), S.Laboncz, (HU), J.Tanimura (JP), A.Yamada (JP), J.Yare (UK), T.
Amimoto (JP), T.C.S.M Gupta, former TF 01 leader (IN), W.Mc Dermid, (CA).

Contributors
H.F.A. Verhaart (NL), A.Petersen (AUS), C.N.Fares (UY), M.A.Martins (PT).

Publication 2015
 Outline
Introduction
Risk Assessment

Copper Sulphide Long Term Mitigation

Monitoring and Maintenance Procedures

Conclusions
 Copper Sulphide Long-term
Mitigation and Risk Assessment
Introduction
WG A2.40 was set up in May 2009 as continuation of the work of A2.32.: "Copper
Sulphide in Transformer Insulation" (TB 378) based on the main topics highlighted in
the conclusions and proposed activities for the future work.

The scope of A2.40 was to improve understanding of the mechanism of copper

sulphide formation and mapping of influential factors in order to provide more precise
risk assessment. It was also required that long-term effects of mitigation techniques,
like addition of metal passivators and oil treatment processes, should be examined
and an evaluation of their efficiency and any side effects be investigated.

This report reviews the current best understanding of the mechanism of copper
sulphide formation, details of service experiences, reported failures and problems due
to copper sulphide and the results of mitigation techniques.
Outline
Introduction

Copper Sulphide Formation Mechanism

Risk Assessment
Copper Sulphide Long Term Mitigation
Monitoring and Maintenance Procedures
Conclusions
 Copper Sulphide Formation Mechanism

Deposition of copper sulphide on copper

or in the paper is dependant on:
Temperature
Base oil composition / degree of oil
refining Paper from conductor of failed converter transformer
- copper clean, paper contaminated with Copper sulphide
Oxygen content
Inhibitors in the oil

Conductors from failed converter transformer: left - inner paper

layers, right outer paper layers
Copper and paper contaminated with copper sulphide
 Copper Sulphide Formation Mechanism
Mechanism:
copper in oil dissolution - absorption in the paper reaction of copper and
sulphur and deposition of copper sulphide in the paper

Copper sulphide deposition on the copper and transfer to adjacent paper layer

Scheme of copper sulphide formation in the paper

Legend:
R-S-S-R: disulphide (for example dibenzyl disylphide-DBDS)
Cu: Copper
T: Temperature
AC/DC: Electrical fields
Cudiss.: Dissolved copper compounds (Cu+(O2R)- )
ROOH: hydroperoxides
ROH: alcohols, phenols and derivates (DBPC, DBPh)
CuxS: Copper sulphide
Copper Sulphide Formation Mechanism
Influence of Temperature

Formation of copper sulphide at temperatures from 80C to above 300C, from

different reactive sulphur compounds.

Arrhenius Law for temperature ranges from 80-100C up to 200C

the rate of copper sulphide formation approximately doubles with every 10C
increase

A first order reaction was suggested for temperatures up to 150C with estimated
activation energy of 123 KJ/mol ; kinetics of DBDS depletion is more complex -
rate falls off less rapidly than expected from true first order
 Copper Sulphide Formation Mechanism
Influence of Oxygen and Oxydation proces

At temperatures up to 120C
rate of copper sulphide formation higher in
sealed conditions comparing to the rate of
formation in breathing conditions

At temperatures above 150C

Rate of copper sulphide formation in the
paper higher in breathing conditions

Oxidation process can promote oil corrosiveness, some sulphur species may become
more reactive when oxidized (less refined uninhibited oils)
Copper Sulphide Formation Mechanism
Influence of Base oil Composition and inhibitors
120C/150C breathing 120C/150C non-breathing naphtenic oil A, uninhbited
naphtenic oil A,
uninhbited 16000 naphtenic oil A, uninhibited
40000 with added DBPC
naphtenic oil A, naphtenic oil B, inhibited
uninhibited with 14000
added DBPC paraffinic oil , inhibited

Copper content in the paper, ppm

35000
Copper content in the paper, ppm

naphtenic oil B,
inhibited
30000 12000
paraffinic oil ,
inhibited
25000 10000

20000 8000

15000 6000

10000 4000

5000
2000

0
120C - 3 days 120C - 7 days 150C - 3 days 150C - 7 days 0
120C - 3 days 120C - 7 days 150C - 3 days 150C - 7 days

Naphthenic oils have a slightly higher propensity for copper sulphide deposition on the paper
Uninhibited corrosive oils with 0.3% added DBPC, DBPh and
variable oxygen content
40000
initial Oil
35000 DBF

Copper content in the

30000 DBPC

paper, mg/kg
25000
20000
15000
10000
5000
0
D D + O2 MO MO + O2
Oils

Addition of inhibitors DBPC and DBPh to uninhibited oils comprised to significant copper
sulphide deposition on the paper, which was pronounced in oxygen environment
Copper Sulphide Formation Mechanism
Reactivity of sulphur compounds

Reactivity of different classes of sulphur compounds in the temperature range from 80C to 180C

IEC 62535 test in white oil 80C 100C 120C 150C 180C

Mercaptans (thiols) - - - + +
Monosulphides - - - + +
Disulphides + + + + +
Oxidized sulphur compounds: - - - + +
sulphoxides/sulphones
Oxidized hydrocarbons - carbonyl +
compounds containing sulphur

Thiophenes +/-

Reactivity of corrosive sulphur compounds for copper sulphide deposition on the paper
according to IEC 62535 is as follows:

ELEMENTAL SULPHUR > DISULPHIDES > MERCAPTANS AND OXIDIZED SULPHUR

COMPOUNDS > MONOSULPHIDES AND TIOPHENES
 Copper Sulphide Formation Mechanism
Copper in Oil Dissolution

Copper content (mg/kg) in oil

Copper content (mg/kg) in paper

4,5 700,00

Copper content (mg/kg) in paper

Copper content (mg/kg) in oil

1,4 Oil # 1 Oil # 2 1400 Oil # 1 Oil # 2 Inert Inert

Oil # 3 Oil # 4 Oil # 3 Oil # 4 4 atmosphere atmosphere
600,00
1,2 Oil # 5 Oil # 6 Oil # 5 Oil # 6 (Argon) (Argon)
1200 3,5
Oil # 7 Oil # 8 Oil # 7 Oil # 8
Oxidative 500,00 Oxidative
1
1000 3 atmosphere atmosphere
0,8 (Oxygen) (Oxygen)
2,5 400,00
800
0,6 2 300,00
600
0,4 1,5
400 200,00
0,2 1

0 200 0,5 100,00

-0,2 0 0 0,00
90 100 110 120 130 140 150 90 100 110 120 130 140 150 Oil # 1 Oil # 5 Oil # 1 Oil # 5
Temperature, C Temperature, C (inhibited) (uninhibited) (inhibited) (uninhibited)
Oil type Oil type
Figure 9 Copper contents in the oil and paper at different
temperatures (oils from Table 2). Figure 10 Effect of atmosphere on copper content in the oil
left and copper content in the paper right at 100C.

Aromatic compounds and oxygen promote copper in oil dissolution and absorption of copper in the
paper
 Copper Sulphide Formation Mechanism
Copper in Oil Dissolution

Change of paper surface resistivity after ageing of paper/oil with 1 l/h oxygen flow; left inner paper layer,
right-outer paper layer

Copper compounds absorbed in the paper after ageing with non-corrosive oils
were found not to have conducting potential
Outline
Introduction

Copper Sulphide Formation Mechanism

Risk Assessment
Copper Sulphide Long Term Mitigation
Monitoring and Maintenance Procedures
Conclusions
Risk Assessment
Service experiences: Transmission transformers
Free-breathing, 1000MVA, 400/275 kV transmission auto-transformer, in service for 11 years

HV winding turn-to-turn failure

hotspot was most likely above 100C for long periods,

transformer design was found to have contributed to the failure as the placement of an oil
guiding washing reduced oil flow to the top disc especially under ON conditions.

copper sulphide deposition precipitated the failure

Risk Assessment
Service experiences: GSUs

inter-turn fault was found in the HV winding

Normal working temperatures
The transformer failed suddenly in 2010
after 15 years with corrosive oil
(containing DBDS)

During inspection paper was found in good

condition, DP > 600.

2) A 192 MVA, 400/15 kV ONAF transformer

failure after 8 years in service
Suffered from overheating due to problems in design (cooling oil
ducts)
inter-turn fault in HV winding with copper sulphide deposition
Risk Assessment
Service experiences: Industrial applications

1) 63MVA, 230 kV industrial transformer

evidence of flashovers on the LV winding
and extensive evidence of copper sulphide
deposition
frequent load changes but the average oil
temperature was not believed to have
exceeded 60C.

2) 44 kV, 33 MVA industrial rectifier

a turn-to-turn failure in the HV winding
only nine months after an oil
change which was carried out to
revitalize insulation system.
The transformer was already aged
and suffering from overheating
problems but the copper sulphide
deposition precipitated failure
Risk Assessment
Service experiences: Industrial applications

3) 93.4 MVA, 66/0.4 kV, cooling ODAF,

windings CTC
Oil uninhibited, containing DBDS = 159ppm
Failure in 2010 without prior warning from
DGA
Copper sulphide deposits were found on
enameled conductors, on the copper and
on the paper
Flakes on enameled conductors, formation
of bubbles
Risk Assessment: Failure Cases Statistics
TransformerApplication
ShuntReactor Industrial Distribution
11% 3%
7%

Transmission
GSU
25%
36%

Rectifier
18% TransformerFailureType
Mechanical
Gassing
4%
11%

Dielectric
25%

Interturn
failure
39%

Tapchanger
fault
21%
Risk Assessment: Failure Cases Statistics
Sulphur TransformerFailureCause
corrosion+ Silver
Sulphur Throughfault sulphideon
corrosion+ 4% OLTC
Overheating contacts
fault 14%
11%
Sulphur
corrosion+ Sulphur
Normalsolid corrosion+
insulation Abnormal
ageing Sulphur solid
14% corrosion+ insulation
Operation+
ageing TransformerFailureandDBDS
Maintenance
46%
11% Content DBDS<20
ppmor
none
DBDSnot 21%
measured DBDS20
51% 50ppm
7%

DBDS>100
ppm
21%
Risk Assessment:Failure Cases Statistics
TransformerFailureandOilType

Inhibitedoi l Uninhibi tedoi l Unknownoil

Unknownoil
7%
Inhibitedoil
36%
Uninhibited
oil
57% Transformerfailureandpreservationsystem
Unknown
7%

Sealed
21%

Free
breathing
72%
Risk Assessment:Failure Cases Statistics
Transfromerfailureandloadprofile
Unknown
14%
Variable
32%

Constant
high
54%
TransformerFailureDiscovery
Unknown
3%

Removedfrom
serviceby
gassingorasset
healthreview
36%
Failedin
serviceby
several
protections
61%
Risk Assessment
Risk Factors
Experiences and failure case statistics showed that copper sulphide deposition
and consequential failures were spread over the range of transformer applications.

RISK factors for copper sulphide formation related to equipment design and
manufacture are:

cooling design and design defects

sealed or free-breathing system

RISK factors related to the state of the paper/oil insulation are:

type and amount of corrosive sulphur species,

type and amount of additives other than DBDS
oil oxidation process and insulation ageing

RISK factors related to service conditions are:

working temperatures and loading conditions

electrical stresses (especially transients in HVDC apparatus and industrial
applications).
Risk Assessment - Diagnostic methods
Standardized tests:
IEC 62535 (corrosion of paper wrapped conductors)
DIN 51353 (silver plate corrosion)
ASTM D 1275 B (copper corrosion)
IEC 62697 (DBDS quantification)

Non-standardized tests:
Determination of elemental sulphur using gas chromatography with Electron capture detector
under development in IEC TC 10 WG 37
Determination of DBDS ad other sulphur species reactive to silver using gas chromatography
with Photometric Flame detector
A method for Total Corrosive Sulphur content in mineral insulating oil under development in
IEC TC 10 WG 37
Detection of total amount of disulphides, mercaptans and elemental sulphur using
potentiometric titration
Detection of benzyl mercaptan, benzyl-group (Benzyl alcohol, Benzaldehydes, Benzoic acid),
toluene and elemental sulphur using Gas Chromatography with Mass Spectrometry Detector
Change in sulphur and copper concentrations in corrosive oils as detected by XRF
Risk Assessment
Service experiences: Silver Corrosion
Silver corrosion of OLTC silver plated contacts reported in number of transformers

In majority of the cases copper was intact

Oils with DBDS, but also oils without DBDS were involved

Dominantly failures caused by silver corrosion were reported after (improper) oil
reclamation

In most of the cases silver corrosion did not lead to a failure, indications were
obtained from DRM and DGA; corroded contacts replaced/cleaned and re-silvered

Scant reports of failures of transformers during service due to silver corrosion; no

warning or weak indications from DGA, failures due to detachment of conductive silver
sulphide particles, electric arcs/flashover.
Risk Assessment
Source of Silver Corrosion

Formation of S8 from different sulphur containing species (at high temperatures, above
200C) during oil reclamation /reactivation of adsorbent, heat dissipated from electric arcs
Once formed S8 easily reacts with silver at lower temperatures (from 80C onwards)
S8

Ag + S = Ag2S 1% reclaimed oil in non-corrosive oil

5% reclaimed oil in non-corrosive oil

Traces of S8 are enough to cause corrosion to silver

10% reclaimed oil in non-corrosive oil

0% reclaimed oil in non-corrosive oil

Figure 40b Tap selector contact heated in mixture of reclaimed corrosive oil and non-corrosive
oil.
Risk Assessment
Silver Corrosion: Failure in Service

A 150MVA, 230/130 kV transmission transformer

Irgamet 39 added in 2007 after 2 years of

service, oil corrosive , DBDS = 150ppm.

No depletion of metal passivator was detected.

Failure in 2010, silver corrosion - Ag2S particles

had flaked off and contaminated the windings.

Irgamet 39 was found not to be effect in

protection of silver surfaces.
Risk Assessment
Service experiences: Silver Corrosion

Example of silver corrosion following reclamation (l) prior to reclamation (c) contacts
one year after reclamation, (r) three years after original switch out.

Examples of coatings on silver plated selector contacts

Risk Assessment
Silver Corrosion: Detection of target
DIN 51353 compounds

GC ECD - IEC 62697 (DBDS content)

GC ECD - Detection and quantification of S8 under development in IEC TC 10 WG 37

GC FPD method for detection of sulphur species reactive to silver

Risk Assessment
Silver Corrosion Diagnostics
In Service Diagnostics:
DGA - detection of fault gases mainly ethylene (indicator of overheating of contact
contaminated with Ag2S), good indicator of problem to prevent failure
Dynamic Resistance Measurements sensitive to detect changes in resistances, due
to overheating of contacts contaminated with Ag2S, good indication of silver sulphide
problem

Resistance diagrams from oscillograms following resistance measurements of healthy (left) and
likely contaminated contacts (right)
Outline
Introduction

Copper Sulphide Formation Mechanism

Risk Assessment

Copper Sulphide Long Term Mitigation

Monitoring and Maintenance Procedures
Conclusions
Copper Sulphide Long Term Mitigation
Mitigation Techniques Survey

Distribution of mitigation survey responses among countries

It is estimated that more than 10.000 units around the world had been subjected to
mitigation against copper sulphide

Replies came from 16 countries, more than 1200 cases were reported
Copper Sulphide Long Term Mitigation
Mitigation Techniques Survey
More than 20 electrical utilities mainly operating in:

generation (24%)
transmission (70%)
distribution (1%)
industrial applications (3 %)

All kinds of power apparatus

(transformers, auto-transformers, shunt-reactors, rectifiers, etc.)

free-breathing (64%)
sealed units (36%)

naphthenic oils (98%)

paraffinic oils (2%)

uninhibited oils (85%)

inhibited oils (15%)
Copper Sulphide Long Term Mitigation
Mitigation Techniques

Spread of mitigation actions, according to TF 03 survey

 Copper Sulphide Long Term Mitigation
Metal Passivators
Metal Deactivator - Ciba IRGAMET 39 (liquid pure reagent)
Cobratec TT100 Tolutriazole (solid pure reagent)
Nynas AB - Nypass (pre-blend of 10% passivator and a transformer oil base stock)
Shell Diala Concentrate P (10% concentrate)
DSI Sulphur Inhibitor liquid concentrate mixture of sulphur stabilizer, metal
passivator and phenolic antioxidant.
Metal Deactivator - Ciba IRGAMET 30

Concentration of metal passivator typically suggested is 100 mg/kg,

but amounts around 200 mg/kg are also recommended to achieve higher buffering effect
and decrease costs of on-site re-passivation.

Concentrations < 50 mg/kg of metal passivator are considered ineffective (IEC 60422) -
stringent rec. with higher safety margin.
Copper Sulphide Long Term Mitigation
Metal Passivator Efficiency

TF03 survey: Around 1100 units were subjected to metal passivator addition

Around 20 units were reported to have failed after addition of metal passivator, including units
reported in early period of copper sulphide problem (2004-2007) before WG A2.40 was established

These unsuccessful experiences were attributed to late addition of metal passivator, but service
conditions and design weaknesses had an additional contributory effect towards failure; several
cases from this group were attributed to silver corrosion which was unsuccessfully mitigated with
Irgamet 39

Irgamet 39 was found to be inefficient to counteract silver corrosion, while Irgamet 30 was
found to be inefficient to counteract copper corrosion

DSI mixture was found to be efficient to counteract silver corrosion tried on lab scale, but can not
be recommended for real applications, since the chemical composition of the mixture is unknown
Copper Sulphide Long Term Mitigation
Metal Passivator Efficiency and Oil Condition

Oil condition strongly affects performance of metal passivator

Different oils have consumed metal passivator in different time spans, nevertheless
thickness of metal passivator layer on the copper was the same in all investigated oils
Copper Sulphide Long Term Mitigation
Metal Passivator Thermal Stability

Metal passivator Ion profiles in vacuum for BTA and TTA ions in different oils, copper surface treated with 100
ppm of Irgamet 39

Temperature profile of metal passivator was very similar for all investigated oils
In real service conditions, in air, with conductors immersed in oil,
the boundary temperature would above 100C
Copper Sulphide Long Term Mitigation
Metal Passivator Thermal Stability

Figure 58 SSIMS images (tolyltriazole green, copper red, sulphur blue) of a reference
copper sample treated with Irgamet 39 in mint conditions (left), outmost conductor of the top
(middle) and bottom (right) disc of a 400/275 kV scrapped autotransformer.

Transformer had suffered prolonged overheating of the top discs (design and cooling issues)

Copper Surface was found not to be efficiently protected with metal passivator
Copper Sulphide Long Term Mitigation
Metal Passivator Interactions with Solid
Insulation
c o p p e r d iss o lv e d in th e o il 800
a m in o m e th yl su s b st.T T A co n e n tra tio n in th e o il
amino methyl subst. TTA concentration in the oil, mg/kg

c o n ce n tra tio n o f a m in o su b s t.T T A in th e p a p e r*, m g /k g

25 700

600

subst. TTA in the paper*, mg/kg

Copper dissolved in the oil, mg/kg

Concentration of amino methyl

20

500
Simultaneous decrease of metal passivator
15
in the oil and increase of metal passivator in
400

10
the paper at 150C over 350 h, without
300
formation of copper dissolved in the oil
5
200

0 100

Hi gh Ox ygen Low O xygen

50 100 150 200 250 300 350 400

te s t d u ra tio n , h

450
Lowoxygen aged oil CI a) C I a ged oi l 120h b) C I a ged oi l 120h
400 Lowoxygen aged oil CII
Lowoxygen new oil CI
Metal passivator absorbed in 350 Lowoxygen new oil CII
High oxygen newoil CI
the paper suppress copper in 300 High oxygen newoil CII
Copper dissolved in the oil, ppb

High oxygen aged oil CI c) C I ne w oil 120h d) C I ne w oil 120h

oil dissolution for some time - 250 High oxygen aged oil CII

prolonged protection of 200

conductors 150
e) C II a ge d oi l 120h f) C II a ge d oi l 120h
100

50

0
g) C II ne w oi l 120h
h) C II ne w oil 120h
20 40 60 80 100 120
test duration, h

Copper in the oil and images of paper wrapped conductors heated in corrosive oils for 120 h at 140C
Copper Sulphide Long Term Mitigation
Metal Passivators - Side effects

stray gassing
13%
fast depletion
w ithout stray 15%
gassing and
depletion
norm al
55%
depletion
17%

Stray gassing production of hydrogen, carbon oxides

Depletion of metal passivator up to 40%/year from initial concentration is considered as normal
absorption in cellulose materials
Fast depletion of metal passivator from the oil more then 40%/year from initial concentration
Copper Sulphide Long Term Mitigation
Metal Passivators Stray Gassing
Decomposition of metal passivator yield H2, CO and CO2.

Generation of hydrogen by elimination of hydrogen from benzo triazole molecule

H2 (Metal passivator 500 ppm)

H2 (Metal passivator 100 ppm)

Stray gassing due to metal passivator addition is not a fault condition, but may interfere with
diagnostics using DGA.
Improved DGA interpretation affords the correct identification of this phenomenon.
Copper Sulphide Long Term Mitigation
Metal Passivators Service experiences
EXAMPLE OF TRANSFORMER WITH METAL PASSIVATOR ADDED
1,00
Corrosiveness
test (ASTM
0,75
D1275-B)
p.u.

0,50 DBDS

0,25
Irgamet 39
0,00
Passivation

Passivation

service
Start-up

Still in
2nd
H2

0 12 15 18 19 20 23 26 32 33 36 40 44 46
operation time (months)

Stray Gassing was observed to level off after one to two years after addition of metal passivator
Fast depletion of metal passivator from the oil absorption and degradation of metal passivator

No abnormal change of oil properties were observed after addition of metal passivators
No correlation of oil properties (acidity, dielectric dissipation factor) to stray gassing was found.
Copper Sulphide Long Term Mitigation
Metal Passivators Partition of Furans

Service Experiences - no significant change

of furans

1200
30.00
Oil 1
1100 Oil 1
Oil 1+IR39
Oil 2 Oil 1+ IR39
Experiments in the lab 1000 Oil 2+ IR39
Oil 3
25.00
Oil 2
Oil 2 +IR39
Oil 3+ IR39 Oil 3
accelerated high temperature 900
Oil 4
Oil 4+ IR39 20.00 Oil 3 +IR39
800 Oil 4
test

2-F AL, pp m
Oil 4 +IR39
DP

700 15.00

Rise of furans changed 600

10.00
500

partition of 2-FAL after 400

5.00
Irgamet 39 addition and 300

absorption in the paper 200

initi al 3 days 6 days 9 days 12 days
0.00
initial 3 day s 6 days 9 days 12 days

Figure 68 Change of 2-FAL concentrations in different corrosive oils before and after addition
metal passivator during IEC 62535 ageing test set up for 12 days, wet paper at 140C
Copper Sulphide Long Term Mitigation
Oil Change

1,00

0,75
Corrosiveness
Test (ASTM
p.u.

0,50 D1275-B code)

DBDS
0,25

0,00
Start-up Oil change Still in
service

0 12 14 15 24 32
operation time (months)

Residual oil volume can be kept within the range of 5-10%.

Single rinse of the bottom of the tank with a small extra-amount of unused oil as well as the use
of the hot-spray technique to rinse both the tank and the windings is adequate.
Copper Sulphide Long Term Mitigation
Oil treatment
Oil reclamation using specific adsorbents

Chemical treatment combined with reclamation, processes based on PCB Technologies

Solvent extraction process

Oil reclamation and chemical treatment applied on site with success

1,0
Corrosiveness
test (ASTM
0,8 D1275-B)
DBDS
p.u.

0,5
Acidity
0,3
BDV
0,0 depolarization

still in servic e
DDF

0 6 18 30 42 60

months
Copper Sulphide Long Term Mitigation
Oil treatment- Side effects
Formation of free sulphur after oil reclamation with reactivation of adsorbent

Rise of ethylene in the oil after

reclamation process
Copper Sulphide Long Term Mitigation
Oil treatment- Side effects

During oil reclamation, reactivation of adsorbent , at high T > 300 C thermal and catalytic crakying
(adsorbent alumosilicate is catalyst) reactions can occur from various sulphur based compounds,
not only DBDS :

T>300C, air, catalyst

Hydrocarbons & Sulphur containing compounds Olefins (C2H4, C3H8,..),
H2S, Elemental S

Created elemental sulphur attack bare copper and silver surfaces and produce silver sulphide and/or
copper sulphide:

Cu + S = Cu2S Ag + S = Ag2S

Elemental sulphur is more prone to react with silver and at lower temperatures
Copper Sulphide Long Term Mitigation
Cost Effective Risk Mitigation Strategies

Mitigation Techniques ranking

METAL
OIL
CATEGORY PASSIVATOR OIL CHANGE
TREATMENT
ADDITION

SIMPLICITY /
TIME CONSUMING /
ON LOAD APPLICATION Not applicable
EFFICIENCY / /
OIL PROPERTIES RESTORATION
LONG TERM PERFORMANCE
ENVIRONMENTAL Unknown
COST /
Recommendations

Addition of metal passivators (Irgamet 39) would be an efficient solution, especially if

performed in the early days of service with corrosive oil.

In order to make a decision whether to perform a second addition of metal passivator, monitoring oil
corrosiveness and concentration of reactive sulphur compounds is important:

If the total disulphide content is depleted to a value below 5 mg/kg, or the DBDS content is
below 10 mg/kg, there is no need to apply a second addition of metal passivator, due to low
probability of failure (oils are either non-corrosive or deposit traces of copper sulphide acc. to IEC
62535).

In all other cases a second addition of metal passivator should be performed

If after second addition of metal passivator, the passivator depletes rapidly from the oil (acc. to
IEC 60422 poor condition), while concentration of DBDS in the oil is above 10 mg/kg other
mitigation actions are recommended, such as removal of corrosive sulphur from the oil, or oil
change as long-term solutions.

Transformers with oils corrosive to silver (DIN 51353) can not be mitigated by addition of
Irgamet 39, as according to service experiences Irgamet 39 was found inefficient to counteract
silver corrosion.
Recommendations

Removal of corrosive sulphur from the oil, or oil change are recommended as long-term
solutions for:

Units with constant high load or frequent changes of load (usually shunt reactors and industrial
applications),

Units with frequent and intensive electrical stresses,

Units with indications of overheating (cooling defects, thermal faults -DGA),

Units with intensive oil oxidation and consumption of oxygen, and combination of these
conditions

Units with oils corrosive to silver acc. to DIN 51335 (addition of metal passivator Irgamet 39
was found not to be efficient).

The choice of technique will be dependant on the condition of transformer, criticality and cost-
benefit evaluation.
 Start fr
After re o m h ere
adin g
XXXXX
Is the oil corrosive
NO according to YES
IEC 62535 ?

Are copper conductors

YES NO
fully enamelled ?
Revised TB 378 Flow Chart
Read Note 2!!
Is there any symptom of local or
NO YES
diffused overheating from DGA ?

Is the transformer highly loaded / YES

NO
with high thermal range ?
Is the equipment
NO YES
passivated ?
Does the oil have a low oxygen content
(due to atmosphere segregation
NO YES
or
Is DBDS content in oil oxygen consumption) ?
Recommendations

> 20 mg/kg ?
or
NO Is total disulfides + YES
Is the equipment
mercaptans NO
passivated ?
content in oil YES
> 5 mg(S)/kg ? Is the equipment
YES NO
passivated ?

Was the equipment

YES passivated during the NO
1st year of service ?
As When was the After 1st year
new Equipment passivated ? of service
During 1st year
of service

Probability of copper Probability of copper Probability of copper Probability of copper

sulfide deposition: sulfide deposition: sulfide deposition: sulfide deposition:
NULL LOW MEDIUM HIGH
actions actions actions actions

No action 1) Respect the loading 1) Avoid overloading 1) Reduce the thermal stress
guide 2) Add a metal passivator by decreasing the loading
2) If a metal passivator, if not already done or or/and by improving the
keep under monitoring change/reclaim the oil cooling
passivators 3) Keep under monitoring 2) Change/reclaim the oil or
concentration passivators passivate the oil as a
concentration if present temporary action if not
already done (see note 3
under the FC)
3) Keep under monitoring
passivators concentration
if present

YES YES YES

Is passivator Is passivator After change/reclaim,
concentrations NO concentrations NO is the oil NO
stable in time ? stable in time ? still corrosive ?
Outline
Introduction

Copper Sulphide Formation Mechanism

Risk Assessment
Copper Sulphide Long Term Mitigation

Monitoring and Maintenance Procedures

Conclusions
Monitoring and Maintenance Procedures
MONITIRING
Corrosive sulphur test IEC 62535, DIN 51353 and ASTM D 1275 B

DBDS concentration IEC 62697

Elemental Sulphur and total disulphides and mercaptans

Monitoring Irgamet 39 content - IEC 60666

MAINTENANCE (Oil reclamation processes): Incomplete removal of DBDS after oil reclamation

Thorough rinse of transformer active part from residual corrosive oil, by circulating oil through heated
transformer active part

On board corrosive sulphur tests at the end of oil treatment (IEC 62535 and DIN 51353)

Optionally, determination of DBDS in the oil during or after treatment (for oils containing DBDS)

Re-inhibition with DBPC after the oil is verified as non-corrosive, according to IEC 62535 and
DIN 51353.

In case of process with reactivation of adsorbent investigate/revise procedures to avoid cross

contamination (buffer tanks, columns, storage vessels)

Verify adsorbent performance in laboratory prior on-site treatment

Outline
Introduction

Copper Sulphide Formation Mechanism

Risk Assessment
Copper Sulphide Long Term Mitigation
Monitoring and Maintenance Procedures

Conclusions
Conslusions
Metallic sulphides deposited in the paper insulation or detached from metal surfaces significantly
reduce dielectric status of transformer active part and cause, or contribute to transformer failures.
Deposits on bare metallic surfaces can also be the cause of overheating.
Postulated mechanism of copper sulphide formation involve the dissolution of copper, diffusion
and absorption of an intermediate complex in or on paper or board, and subsequent reaction with
sulphur compounds to form Cu2S and other by-products.
Electrical fields seem to promote copper sulphide formation. They may play an important role in
the initiating step of the reaction: formation of copper cations.
Detachment of fine copper sulphide particles from copper surfaces and transport to the adjacent
paper layer is also proposed.
Temperature and concentration of reactive sulphur are the main risk factors.
Oxygen determines the rate of copper-in-oil dissolution, diffusion and absorption of intermediate
copper complexes in the paper.
Copper sulphide is formed in broad range of oxygen contents, corresponding to both sealed and
free breathing transformer application.
At lower temperatures, the risks of copper sulphide formation is lower in a high oxygen
environment, while at higher temperatures (overloading conditions, localized or diffused
overheating) risks of copper sulphide formation in the paper are higher at higher oxygen levels.
Conclusions
Investigation of sources of corrosive sulphur coming from rubbers and gaskets showed that these
materials have no corrosive potential.
Most of the failed transformers and reactors that have operated with high winding temperatures
and with oils having a high concentration of reactive sulphur compounds, regardless of the
transformer preservation system.
The addition of metal passivator to the oil is still the most commonly applied, which is likely to be
related to the low cost and simplicity of its use, but it has limitations; the poor stability at elevated
temperatures, in less refined and aged oil is the most important drawback.
Rapid depletion of metal passivator from the oil and evolution of gases after metal passivator has
been added are the most common side effects (fast depletion of metal passivator in 15 % and 13%
cases of units with oil stray gassing). Gassing of the oil is not considered a fault condition and it
was recognized to level off after a time, typically one to two years.
A more radical solution involves removal of the sulphur either through changing the oil, or
removing the reactive sulphur from the oil in situ; if carried out properly, the long-term effects seem
to be good for both options.
Stringent procedures and monitoring of the corrosive sulphur on-site during reclamation have to be
performed to ensure good results.
In some cases, improved cooling or reducing the load are suggested.
Thank you for attention
Questions?