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A Study on Transformer Oil (Mineral Oil)

Prepared By

Sunil Nannaware
R&D- ITR











Definition:

A mineral oil or liquid petroleum is a liquid by product of the distillation of petroleum to
produce gasoline and other petroleum based products from crude oil. A mineral oil in this
sense is transparent, colorless oil composed mainly of alkenes (typically 15-40 carbons)
and cyclic paraffins, related to petroleum jelly (also known as white petroleum). It has
density of around 0.8 g/cm
3
. Mineral oil is available in light & heavy grade.
Mineral oil application in the electrical equipments falls under the category of liquid
di-electrics
Mineral oil is commonly referred as Insulating oil or Transformer Oil. Though it
is widely used not only in the transformers but also in variety of electrical equipments it
is still referred as transformer oil. Because of this reason referring electrical quality
mineral oil as transformer oil may lead to confusion. But this terminology is so
commonly used in the electrical industry that veterans will find this bit funny. In order to
avoid any confusion regarding the application of mineral oil we will refer mineral oil as
insulating oil.

In addition to the mineral oil there are other liquids which are used in the electrical
equipments for the same application. We will group all this under one umbrella of
insulating liquids.









Organic Inorganic
- pure water
- -liquefied
gases
Mineral oils Synthetic oils
-Silicone oils
-Chlordiphenyles
-high molecular
weight hydrocarbon
-Tetrachlroethylene
Insulating liquids
Transformer Oil: Properties of Naphthenic and Aromatic Fractions
Functionally most electrical insulating fluids are considered to be equivalent and they are
handled as such.
Chemically most electrical insulating fluids are not equivalent. While the differences
normally do no defeat the prescribed functions of the fluids they do affect the way they
function. Transformer fluids vary in composition from nearly pure compounds to mixture
that is too complex to fully describe. Due to this complexity we will first understand
about functional group of the transformer oil. Such as properties, processing, purification
& transport of insulating oil. Then in next section we will under stand chemistry behind
the transformer oil.




Physical properties:

Aniline point: The aniline point (temperature) of a insulating oil indicates the solvency
of the oil for some materials that are in contact with oil. A high aniline point indicates the
aromaticity and a lower solvency for some material (e.g. rubber)

Test method: ASTM D-611-01b

























Relative density (specific gravity)

The relative density of oil is the ratio of the weights of equal volumes of the oil and
water, tested at 15C. the relative density is significant in determining the solubility for
use in certain applications, in cold climates, ice may form in equipment exposed to
temperatures below freezing. When considered along with other oil properties, relative
density can be an indicator of the quality of the oil.

Discussion:
Relative density (RD) or specific gravity is dimensionless quantity, as it is the ratio of
either densities or weights.


RD =
substance
/
reference

Where RD is relative density, substance is the density of the substance being measured
and reference is the density of the reference (by convention , the Greek letter rho,
denotes density)

If the substance relative density is less than one then it is less dense than the reference
and vice versa. If the reference is water than substance with relative density (or specific
gravity) less than one will float in water. For example an ice cube with relative density of
about 0.91 will float. A substance with relative density greater than one will sink.
The specific gravity (relative density) of insulating oil influences its heat transfer rates. In
extremely cold climates, an upper limit of 0.895 is placed on the specific gravity (relative
density) of insulating oil. If oil contains any moisture, the resulting ice from the freezing
of the moisture in the oil filled apparatus should not float on the surface (specific gravity
of ice is approximately 0.915). Floating ice on oil can cause a flashover of conductors
extending above the oil level. Oils of different specific gravity (relative density) may not
mix when added to each other, and precautions are taken to guard against this possibility.

Test Method: ASTM D-1298-85

Scope
1.1 This practice covers the laboratory determination, using a glass hydrometer, of the
density, relative density (specific gravity), or API gravity of crude petroleum,
petroleum products, or the mixture of the petroleum and non petroleum products
normally handled as liquids.
Values are measured on a hydrometer at a convenient temperatures, readings of the
density being reduced to 15C, and readings of the relative density (specific gravity)
and API to 60F, by means of international standard tables. By means of these same
tables, values determined in any one of the three systems of the measurement are
convertible to equivalent values either of other two so that measurement may be made
in the units of local convenience.


Terminology:
Density: for the purpose of this practice, the mass (weight in vacuum) of liquid per unit
volume at 15C. When reporting results, explicitly states density in mass & volume along
with reference temperature.
API Gravity:
A special function of relative density (specific gravity) 60/60F, represented by
API Gravity, Deg = (141.5/sp.gr 60/60F) - 131.5
No statement of reference temperature is required, since 60F is included in definition.






































Color:
Insulating oil should have a light color and be optically clear so that it permits visual
inspection of the assembled apparatus inside the equipment tank. Any change in the color
of oil overtime is an indication of deterioration or contamination of oil.
The color test is performed by visually comparing the color of the oil to a color chart
provided by most oil manufacturers. The scale on these charts range from 0.5 to 8.0 with
new oil has color of 1.0 or less. When exact match is not found and sample color falls
between two standard colors, the higher of the two colors is reported. New oil will appear
to be clear to light straw color, while red to black oil indicates sludge or other
contamination.




Test method: D1500
This test method covers the visual determination of the color of wide variety of petroleum
products such as lubricating oils, heating oils, diesel fuel oils and petroleum waxes.
Significance of use:
Determination of the color of petroleum products is used mainly for the manufacturing
control purpose and is an important quality characteristic since color is readily observed
by the user of the product. In some cases the color may serve as an indication of the
degree of refinement of the material. When the color range of the particular product is
known, a variation outside the established range may indicate possible contamination
with another product. However color is not always a reliable guide to product quality and
should not be used indiscriminately in product specifications.
Interfacial tension:
The interfacial tension of mineral oil insulating fluid is related to deterioration of the
sample. The mineral insulating oil is essentially a non-polar saturated hydrocarbon;
however, when the sample undergoes oxidative degradation there are formed oxygenated
species such as carboxylic acids, which are hydrophilic in nature. The presence of these
hydrophilic materials in the insulating fluid can affect the chemical (acidity), electrical
(dielectric strength), and physical (interfacial tension) properties of oil. In this procedure
one measures the surface tension of the oil against that of water, which is highly polar.
The more nearly the two liquids are alike in their polarity the lower the value of surface
tension between them. Thus the higher the concentration of hydrophilic materials in the
insulating fluid, the lower will be the interfacial tension against water. One method
measures the size of a drop of water that is formed below the surface of the oil (ASTM D
2285) however, if one desires more accurate values it is recommended that ring method
described below used.

The details of the entire procedure for determining the interfacial tension (IFT) of oil
against water by the ring method are given by ASTM 971 standard and are only briefly
mentioned here. The device used to determine the IFT is a tension meter based on Du
Nuoy principle. A sample of oil is carefully floated on the top of a layer of water and
force necessary to pull a platinum ring upward from below the water level through the oil
is measured by using a calibrated torsion wire. The force is measured at the point at
which the ring breaks free of the water layer as it is being pulled upward through the oil
layer. The platinum ring is made to precise dimensions. Since this test is very sensitive to
trace contaminates, one must be very thorough in the handling the sampling device, the
sample, and the instrument. There are correction factors that have to be taken in to
consideration relating to the dimensions of the ring and the densities of the water and
sample. The results are given in units of dynes/cm or the numerically equivalent units of
milliNewtons/meter (mN/m).

Significance:
The magnitude of the IFT is inversely related to concentration of hydrophilic degradation
products from the deterioration of the oil. Since the hydrophilic materials are usually
highly polar and thus not very soluble in the non-polar oil, the presence of these species
can results in the sludge formation. These materials that remain dissolved in the oil can
affect the desired electrical properties of the oil. There is usually inverse relationship
between the neutralization number of an oil and its IFT. As an oil sample undergoes
oxidative degradation, its neutralization number will increase while its IFT value will
decrease. It should also be recognized that a decrease in the IFT does not imply that the
acidity must also be high, since there are other non-acidic contaminants that could be
present in the oil that are hydrophilic and will lower the IFT but not raise the acidity. An
example of such situation might be that of a free breathing transformer near salt water
where a salt water mist might be able to enter the unit. Such event will not affect the
acidity but would affect IFT & dielectric strength of the oil.




Quality index system:
Dividing the interfacial tension (IFT) by the Neutralization number (NN) provides a
numerical value that is an excellent means of evaluating oil condition. This value is
known as the oil quality index (OQIN) or Myers Index Number (MIN). a new oil, for
example has OQIN of 1500.

OQIN= IFT/NN. 1500= 45 (typical new oil)/0.03 (Typical new oil)






































Flash Point:
The flash point is the minimum temperature at which heated oil gives of sufficient vapor
to form a flammable mixture with air. It is an indicator of volatility of the oil.
Test Method: ASTM D-92 (Cleveland open cup method)
Significance:
1. Flash point measure the tendency of the sample to form a flammable mixture with
air under controlled laboratory conditions. It is only one of number of properties
that must be considered in assessing overall flammability hazard of material.
2. Flash point is used in shipping and in safety regulations to define flammable and
combustible material.
3. Lower flash point can reveal the presence of highly flammable substances in the
oil.
4. Flash point assumes significance after an arcing fault inside the transformer.

Test Equipment for Flash Point:
1. Cleveland Open Cup:





2. Approximately 75 ML oil needs to be taken in Cleveland cup
3. Prepare the sample
4. Prepare the Kit with appropriate settings

5. The flame is dipped for every 3 degree (or any value) starting from 105C till the
flash point occurs. The flash is then recorded.

















S K value:
Nominal Value: -4 to 8.

S K value is defined as the increase in the volume of concentrate sulphuric acid on adding
a given test sample. It signifies the degree of the refinement of oil. This test is under
consideration.
The effect of S K value on other characteristics properties like resistivity. The dissipation
factor, stability test like accelerated ageing and oxidation stability, have been studied in
various oil refinery laboratories. However there exists no correlation between an
increases in S K value, but is still lower than that under specification. A similar effect of
SK value on the stability characteristics does not specify any co-relating trend. These
results have been collected by research laboratories.
The present trend in the manufacture of transformer oil is based on the achieving the best
performance and the stability characteristics specified in above. The indigenous TOFS
available are paraffinic in and nature and require greater refining. This results in
eliminating some anti oxidants in oil.

Pour Point:
The pour point is the lowest temperature at which oil will just flow. A low pour point is
important, particularly in cold climates, to ensure that the oil will circulate and serve its
purpose as an insulating and cooling medium. It may be useful for identifying the type
(naphthenic, paraffinic) of oils.
Testing Method: D 97
Nominal Values: -5C,-30C, -40C.






















Viscosity :
The viscosity of insulating oil is measured by timing the flow of a known volume of oil
through a calibrated tube. Viscosity is not significantly affected by oil contamination or
deterioration, but may be useful for indentifying certain types of service aged oil.
Viscosity has an important influence on the heat transfer characteristics of oil. High
viscosity decreases the cooling efficiency of the oil. High viscosity will also affect the
movement of parts in electrical equipment, such as circuit breaker, switchgear, tap
changers, pump and regulators. Viscosity is the factor in determining the conditions for
oil processing & cellulose Impregnation time.
Testing method: ASTM D88-94, ASTM D-445, ASTM D- 2161

Poiseuilles Law:

Where
V = volume of oil within the capillary.
r = average equivalent capillary.
P
0
= external pressure P
e
+ pressure created by capillary action.
P
i
= Internal pressure.
L = the depth of impregnation increasing with time.
= Viscosity.

Capillary equitation:





Where:
= Contact angle of oil.
r = average equivalent capillary radius.
T= Surface tension of the oil.
= Viscosity.










Oxidation stability:

Uninhibited oils must be free of additives, either natural or synthetic those are used to
improve oxidation stability. This includes but is not limited to 2-6 ditetiary phenol, 2-6
diteriary-butyl cresol, or metal deactivators such as benzotriazole and its derivatives.
Inhibited oils are insulating oils, which have been supplemented with either 2-6 ditetiary
butyl phenol or 2-6 ditetiary-butyl cresols or any other specified and acceptable oxidation
inhibitor. If an additive other than 2- 6 ditetiary-butyl phenol or 2-6 ditetiary cresol is
used, appropriate limit values for oxidation stability tests should be agreed to by the
purchaser and seller. If more than one additive is added than many stringent limits for
oxidation stability would apply.
Pour point depressants, gassing tendency improvers, additives for corrosive sulfur and
static electrification (metal passivators), antifoaming agents and other additives.
All additives should be specifically identified or at minimum identified by class of
compounds such as metal passivators if the specific information is proprietary.

Oxidation stability (ASTM D2112-01a):
This test method is rapid test for evaluating the oxidation stability of new insulating oil
that contains the synthetic oxidation inhibitor 2-6 DBPC or 2-6 DBP. The test measures
the length of time required for the oil sample to react with a given volume of oxygen
when a sample of oil is heated and oxidized under test condition.

Oxidation stability (ASTM D2440-99)
This method determines the resistance of mineral insulating oils to oxidation under
prescribed accelerated aging conditions. Oxidation stability is measured by the propensity
of oils to form sludge and acid products during oxidation. The test method is applicable
to new oils, both inhibited and uninhibited.



















Anti oxidants:

Mineral oil insulating fluids undergo oxidative degradation in the presence of oxygen to
give a number of oxidation products. The final products of oxidation are acidic materials
that can affect the characteristics of the insulating oils as well as cause damage to
components of the electrical units. Oxygen is a diradical species and the reactions of the
oxidative process are complex but they do involve free radical reaction. One way to
prevent these types of the reaction is to incorporate an oxidation inhibitor that will
interrupt and terminate the free radical process oxidation. Phenolic materials are quite
good for this purpose and two most commonly used inhibitors are 2-6 di tertiary-butyl
phenol (DBP) and 2-6 ditetiary butyl 4 methyl phenol or 2-6 di tertiary-butyl-Para-
cresol (DBPC).

Natural Inhibitors:
New insulating oil as normally refined contains small amounts of certain chemical
compounds that act as oxidation inhibitors. These naturally occurring materials retard oil
oxidation until such time as they expended. The rate at which the inhibitors in the oil are
used up is dependent upon the amount of oxygen available, soluble contaminants in the
oil, catalytic agents in the oil and temperature of the oil. In modern transformers, either
sealed to exclude air and moisture or protected by inert atmosphere, the benefits of the
inhibitors can be extended over many years. As the inhibitors are exhausted, the rate of
oxidation and the deterioration of oil increase. Reclaiming processes, such as acid
refining or clay treating can restore the oil so that it has most of its original
characteristics, but this has no effect upon restoring the usefulness of the natural
inhibitors occurring in the oil. In fact, both fullers earth and activated alumina remove
the natural inhibitors and the reclaimed oil has no resistance to oxidation. To overcome
this undesirable condition, synthetic oxidation inhibitors are used to extend the life of
reclaimed oil.

Significance:
The presence of inhibitors in the oil will increase the useful life of the oil with respect to
oxidative degradation in the presence of oxygen. As the oil is exposed to this type of
oxidative degradation, the oil is protected as long as there is inhibitor present. However,
as the process proceeds the inhibitors will be used up and when it is gone the oil will
degrade at much higher rate. Thus the determination of the amount of inhibitors present
in the oil can be used to estimate useful life of the oil. It can also be used to determine
whether or not new oil has been properly inhibited prior to its use. As inhibitor is used up
its concentration can be monitored and additional inhibitor added as needed to maintain a
proper concentration in the unit. Typical values for fresh oil are in the range of 0.25 to
0.35% DBP or DBPC by weight.

Due to chemical structure transformer oil oxidized easily. The oxidation process involves
chemical reaction between oil, oxygen and metallic compounds. The results of these
reactions are the formation of oil degradation by products, mainly acids, which may
affect the dielectric properties of the oil. Conservator type or breathing transformers
allow oxygen present in the ambient air to be absorbed by the oil. This oxygen and high
temperatures facilitates the oxidation process within the oil.
Antioxidants slow down the oxidation process by trapping the oxidation byproducts such
as free radicals and stop the spreading of the degradation of the oil. During this process,
the inhibitors are consumed, to the point where all the remaining inhibitors have trapped
free radicals. At this point the reaction will once more continue freely.

Methods to determine inhibitor content in the oil.
1. Infrared spectrophotometery (IR)
2. Gas chromatography (GC)
3. High performance liquid chromatography (HPLC)

Common antioxidants:
Butylated hydrooxtoluene (BHT), also known as butylhydroxytoluene, is lipoholic
(fat-soluble) organic compound that is primarily used as anti oxidant.
BHT is prepared by the reaction of p-cresol with isobutylene (2-methylpropene)
catalyzed by sulfuric acid.

CH
3
(C
6
H
4
) OH + 2CH
2
= C (CH
3
)
2
((CH
3
)
3
C)
2
CH
3
C
6
H
2
OH
Alternatively, BHT is prepared from 2-6 ditetiary butyl phenol by hydroxymethylation or
aminomethylation followed by hydrogenolysis.




The species behaves as a synthetic analogue of vitamin E; primarily acting as a
terminating agent that suppresses auto oxidation, a process whereby unsaturated (usually)
organic compounds are attacked by atmospheric oxygen. BHT stops autocatalytic
reaction by converting peroxy radicals to hydro peroxides. It affects this function by
donating one hydrogen atom.
RO
2
.
+ ArOH ROOH + ArO.
RO
2
.
+ ArO. - - NON RADICAL PRODUCTS

Where R is alkyl or aryl and where ArOH is BHT or related Phenolic antioxidants. One
BHT consumes two peroxy radicals.

2-6 Di-tert-butylphenol
2-6 di-tert-butylphenol is an organic compound with the structural formula 2-6
((CH3)3C) 2C6H3OH. This colorless solid alkylated phenol and its derivatives are use
industrially as UV stabilizer and antioxidant for hydrocarbon based products.


Oxidation stability determination:
There are three ASTM tests that will help in establishing the performance of transformer
oil relative to oxidation stability: ASTM D 1934, D2112 and D2420

ASTM D1934
In the procedure found in ASTM D1934, a 300 mL volume of oil, contained in the 400
mL beaker is aged for 96 hours in circulating-air oven controlled at 115C with or
without presence of catalyst. It is particularly useful as a check on the continuity of
production. It is applicable to unused oils. The properties of acid content (D974),
dissipation factor (D924), and resistivity (D1169) are commonly used as criteria for
judging the oxidation stability of relative samples.

ASTM D2112
ASTM D2112 is intended as a rapid method for the evaluation of the oxidation a stability
of new mineral insulating oils containing synthetic oxidation inhibitors. This test is
considered of the value in checking the oxidation stability of new mineral insulating oil
contained 2, 6- diteriary-butyl Para cresol or 2,6 diteriary butyl phenol in order to
control the continuity of this property from shipment to shipment.
The test specimen is agitated by rotating axially at 100 rpm at an angle of 30 from the
horizontal. Under an initial oxygen pressure of 90 psi in a copper bomb with a glass test
specimen container and copper catalyst coil in the presence of water at a bath temperature
of 140C. The time for an oil to react with a given volume of oxygen is measured;
completion of test is indicated by a specific drop in pressure.
An acceptable value for oils run per ASTM D2112 is 195 minutes for new oil which
when inhibited by supplier is inhibited to a level of 0.3% DBPC.

ASTM D2420
Oxidation stability is measured by the tendency of oils to form the sludge and acid
products during aging. The test method is applicable to new oils, both uninhibited and
inhibited.
ASTM D2440 involves aging of 25 ml of oil in the presence of 300 mm of polished
copper wire. Oxygen is bubbled through the oil in the glass container which is in an oil
bath at 110C. Two oil samples are oxidized for 72 and 164 hours or 500 hours
respectively. After prescribed aging periods, the samples are filtered to collect the sludge
formed. The sludge is weighed and the acid content of the filtrate measured.











Stages Of oil Oxidation:
































Water Content (ASTM D1533):

Water in oil appears as an unwanted substance. It is accepted that water in microscopic
amounts & not liters is cause of more electrical break down than any other impurity.
Moisture causes hazard not only to the insulating qualities of oil but also to the
insulations that are immersed in oil.

Water may be introduced in the oil by leaking gaskets, poor handling or form the
insulating paper and oil degradation. As the paper degrades, it produces carbon dioxide
and water and as the insulating degrades, water acids, sludge and other polar compounds
are formed. So its presence is inevitable in the normal service of life of the transformer.

Water is polar liquid having high permittivity or dielectric constant it is therefore
attracted to areas of strong electric field. This sees the internal moisture distributed not
uniformly, but in fact potentially concentrating in most dangerous parts of the system.

The dielectric strength of the paper insulation decreases significantly when its water
content increases. Similarly dielectric breakdown voltage of the oil is also affected by
relative saturation of the oil.

It is important to note that water is continuous state of movement between oil and the
paper insulating system. This is caused by internal temperature variation due to load and
ambient conditions.

Maximum loading while retaining the reliable operation is function of the water content
in the oil. For example, dry transformer (<0.5% moisture) is less susceptible to water
vapour bubbles formation. In this case emergency loading at hot spot temperatures below
180C is possible with little risk of bubble formation. In contrast a wetter transformer
with 2% moisture in the paper runs the risk of bubble formation with hot spot
temperature as low as 130C under the same conditions. A more long term problem is
that excessive moisture accelerates the aging of the paper insulation almost
proportionally. Insulating paper with 2% moisture ages three times faster than paper with
the 1% moisture.













The destructive effect of the water:
Expansion of the paper insulation, altering the mechanical pressure on the
component.
Loss of insulating ability.
Accelerating paper aging i.e. triggering decomposition of the fibers in the paper.
Increased corrosion of the core & tank.
Progressive consumption of oil additives.

This may occur due to:
During the high load currents and at high ambient temperatures, dielectric
breakdowns can results from the reduced oil strength with high absolute amount
of water.
With sudden high loads, water can boil of conductor surface and the vapour
bubbles can cause failures as they rise to the top.
During the cool down period after high load, the relative saturation of the oil will
increase. At its extreme at 100% relative saturation, water will precipitate out &
greatly reduce dielectric strength of oil.

If the oil is oxidized to any extent, any water coming in to the transformer will partially
be absorbed in to the oil decay products (it is this fact which causes old or highly
oxidized oil to dissolve more water than the new oil). As the decay products build up in
the oil, the surface tension of the water or the interfacial tension between the oil & the
water is lowered dramatically. This heavier decay molecule will then recirculate
throughout the entire transformer and will find its way in to the paper insulation, or in to
areas of high electrical intensity thus reducing the insulation strength. The water saturated
oil decay molecule has a preference for the coolest parts of the transformer (bottom
leading to corrosion) and areas of highest di-electrical stress (leading to arching)

Water may be present in four possible forms they are,
Free water that is water that has settled out of the oil in a separate layer. It is
water indicated by low dielectric breakdown voltage.
Emulsified water- or water that is suspended and has not yet settled out in to free
water (indicated by caramel colored oil. A high power factor value indicates
the possible presence of this suspended water trapped in oil decay products.
Dissolved in the oil.
Chemically bounded water- water which is chemically attached to the insulating
paper and which is released when oxidized.

Detection of water in mineral insulating oil:

The detection of the water in oil is performed in the laboratory is most commonly
performed by analytical technique called Karl Fischer titration described in ASTM 1533
or IEC 60184. Both methods employ coulometric titration technique involving the
reduction of an iodine-containing reagent. This methods are used to determine the
amount of water in oil sample on weight-to-weight basis or more popularly known as
PPM (parts per million).



The concepts of solubility and relative saturation can some times be difficult to
understand, but it is an important concept when accessing the dryness of the transformer.
Solubility is defined as total amount of water that can be dissolved in the oil at specific
temperature. The solubility of water is not constant in oil but changes due to temperature.
As temperature increases, the amount of water that can be dissolved in the oil also
increases. The increase is not linear but exponential in function. For example, at 10C
36ppm of water that can be dissolved in the oil, where as when temperature is 90C,
amount of water that can be dissolved in the oil in increases to 600 ppm. Following table
shows the list of calculated solubility limit for that particular temperature. If the water
content is more than the limit at that particular temperature than there is greater
possibility that free or emulsified water is available in the oil.



The solubility of the mineral oil can be calculated using.

Log S
0
= -1567/K+7.0895

Where: S
0
is the solubility of water in mineral oil.

K is the temperature in Kelvin (C+273)
Relative saturation (RS) is the actual amount of the water measured in the oil in relation
to the solubility level at that temperature. Relative saturation is expressed in units of %, is
the concentration of the water (W
C
) in the oil relative to the solubility (S
0
) or
concentration of the water the oil can hold at the measurement temperature.

RS = W
c
/S
0
(100%)
Where: W
C
is in ppm.
S
0
is in ppm.

A simple example illustrates that the dielectric breakdown voltage of the insulating oils
is proportional to the relative saturation of water in the oil than it concentration in the
ppm. The humidity is controlled in this example so that concentration of the water is held
constant at 30 ppm. The first dielectric breakdown is measured at 100C. at this
temperature the solubility of the water is 772 ppm. The relative saturation of water in oil
is therefore about 4% (30ppm/772 ppm*100), and the dielectric breakdown voltage of
well filtered oil is quite high. The temperature is now reduced to room temperature or
about 22C. The solubility of water in the oil is about 60 ppm. And relative saturation is
50%. The dielectric breakdown voltage would be expected to be about half of what as
when relative saturation was very low. If the temperature is cooled to 0C, the results of
the dielectric breakdown voltage should be quite low as solubility of the water at 0C is
22 ppm. As the water content is higher than this water in oil starts to emulsify & begins
to condense. During all this water content is not changed.

We will now discuss the above point along with the relative saturation & its effect in
details.
Break Down Voltage (BDV):
The dielectric break down is the minimum voltage at which electrical flashover occurs
in the oil. It is a measure of the ability of oil to withstand electrical stress at power
frequencies without failure. A low value for the dielectric breakdown voltage generally
serves to indicate the presence of contaminants such as water, dirt or the conducting
particles in the oil.
Before moving ahead one should really understand that how break down happens in
the oil? In next few paragraphs we will try to explore this based on the work done by M,
Butcher.
Over the years, many models have been proposed to explain the mechanism of liquid
breakdown. Establishment of clear and effective model is difficult in part due to various
characteristics of liquid dielectrics. The physical nature of the liquids (it is extremely
difficult to get pure liquid), high density, viscosity, quality, thermal and electrical
properties, compared to gases adds multiple dimensions to problems associated with
developing model.
Many models begin with some form of charge injection at the electrode /liquid
interface where current injection at an area of fields leads to the formation bubble or low
density region. Inside the bubble, electron avalanches occurs producing current pulses, if
they fail to completely cross the gap; multiple impulses eventually lead to final
breakdown. How the formation of a bubble or low density region in the liquid develops is
still not completely understood since there are several ways to generate a bubble.
Explanations include pre-existing bubbles or dissolved gas, local heating of the liquid due
to energy injection, cavitations caused by fluid motion and electrical stress on the liquid
molecules.

Theories of liquid breakdown:

Liquid breakdown does not consist of a single comprehensive theory for breakdown that
is unanimously accepted for describing dielectric liquid break down phenomena. There
are several reasons for lack of a single theory. The complex nature of liquids makes the
theoretical analysis more difficult than gases. Liquid quality is a critical issue. It is very
difficult to create a pure liquid compared to pure gas. It is generally accepted that liquid
purity plays a very important role in the development final breakdown. The predominant
of liquid breakdown is the bubble theory, followed by the suspended particle and
electronic theories.

Bubble theory:
The bubble theory is based on a combination of gaseous and liquid components for
breakdown. In general it requires the formation of a bubble near the electrode tip. Then
after a bubble is present an electron avalanche or amplification process begins. The
avalanche is triggered either by the injection of more charges in to the vapour phase or by
field ionization occurring in the bubble due to the field enhancement caused by a region
of lower permittivity.
Several methods of bubble formation such as local heating, cavitation, or electrical
stress may occur simultaneously to one degree or another in liquids. The mechanism that
dominates is controlled by the properties of the fluid at the time of the test. The primary
mechanism discussed is localized energy injection. Partial discharges inject hot
electrons into the liquid and cause local heating and vaporization. Hot electrons are
electrons with energy in excess of the thermal energy. The vaporization phase change
consumes most of the energy of the pulse.
T.J Lewis put forth a mechanical model for bubble formation. His model for the
formation of a bubble or low density region comes from mechanical properties of the
fluid.


Fig. Illustration of crack development at the cathode surface.
a) Pre breakdown conditions.
b) Crack develops at the surface of the cathode
c) Jet of electrons from the cathode surface act as an extension of the cathode
and severely distorts the local field.
d) An array of the secondary cracks develops in the radial field.

Figure illustrates the process of mechanically creating a low density/bubble region in a
liquid dielectric. The mechanical stress placed on liquid molecule by very large electric
fields near break down 10
8
to 10
9
V/m, enhances the thermal generation ruptures or holes
throughout the liquid not just at the electrode/liquid interface. These holes in the liquid
will provide weak spots in the molecular structure of the liquid and allow a crack in the
liquid to form at the cathode surface. The crack is now low density or even vacuum
region, occasionally referred as a vacuole where electrons can be injected. The vacuole
does not require a vaporization of the liquid to form, it formation due to mechanical stress
instead of energy injection. Vacuole allows breakdown to develop in low density region,
the same as bubble created by another process. When electron is injected in crack it
becomes the extension of cathode, similar to newly formed micro protrusion. The
enhanced field will repeat the process.
It was experimentally observed that in many liquids, breakdown strength depends
strongly on applied hydrostatic pressure, suggesting that a change of phase of the medium
is involved in the breakdown process, which in other words means that a kind of vapor
bubble formed is responsible for breakdown. The following processes have been
suggested to be responsible for the formation of vapor bubble.
a) Gas pockets at the surface of the electrodes.
b) Electrostatic repulsive forces between space charges which may be sufficient to
overcome the surface tension.
c) Gaseous products due to the dissociation of liquid molecules by electron
collisions; and
d) Vaporization of the liquid by corona type discharges from the sharp points and
irregularities on the electrode surface.
Once bubble is formed it will elongated (log and thin) in the direction of the electric
field under the influence of electrostatic forces. The volume of the bubble remains
constant during elongation. Breakdown occurs when voltage drop along the length of the
bubble becomes equal to minimum value on the Paschens curve for the gas in the
bubble. The break down field given as
( )
( )
1
2
1 2 h
0
1 2 0
2 2
V 1
E 1
(2rE ) r


+
(

= (
`

(
)
(3.2)

where is the surface tension of the liquid,
1
is the permittivity of the liquid,
2
is the
permittivity of the gas bubble, r is the initial radius of the bubble assumed as a sphere and
b
V is the voltage drop in the bubble (corresponding to minimum on the Paschens curve).
From this equation it can be seen that the breakdown strength depends on the initial size
of the bubble which in turn is influenced by the hydrostatic pressure and temperature of
the liquid. But this theory does not take into account the production of the initial bubble
and hence the results given by this theory do not agree well with the experimental results.

Later this theory was modified, and it was suggested that only incompressible bubbles
like water globules can elongate at constant volume, according to the simple gas law
pv = nRT. Under the influence of the applied electric field the shape of the globule is
assumed to be approximately a spheroid. These incompressible bubbles reach the
condition of instability when , the ratio of the longer to the shorter diameter of the
spheroid is about 1.85, and the critical field producing the instability will be:

1
0
1 1 2
600 H E G
R


(
=
(


(3.3) where =surface tension, R= initial radius of
bubble,
1
= permittivity of the liquid dielectric,
1
= permittivity of the globule,
( )
1
1 2
2
2
1 cosh
1
1
1
G

(
(
=
(

(

And
1
2
3
2
1
H 2 2 1

| |
=
|
\


For a water globule having R=1 m with
1
43dyne/cm and 2.0 = = (transformer oil),
the above equation gives a critical field
c
E 226 / Kv cm = which is approximately the
maximum strength obtained for commercial oils.
In the case of gas bubbles the equation for the critical field is rewritten as

( )
( )
1
1
1 2 4 1
1 2
2
c
1 2 1 2
8A B
E 600 G cosh
3
R


(
(
(
=
(
(




Where,
( )
2
3 2
1 2
2 1
A= 1
B=2 1





G, and R are as above for liquid globules, and

( )
1
3
5 2
1 2 -1
3
27
1 PR
cosh
3 2B

(
=
`
(

) (


Where P is the hydrostatic pressure. (Equations 3.2-3.4 are in c.g.s. units). The
expressions are quite complicated, and the breakdown voltages were obtained using a
computer. Results thus obtained showed good agreement with the experimental results in
n-hexane. This theory suggests that sub-microscopic particles (diameter 100-250 A) and
bubbles greatly influence the maximum electrical strength attainable in commercial
liquids. The critical condition is reached when cavities are formed due to zero pressure
conditions given by

c vp es s h
P P P P P , = = + + (3.5) where,
c
vp
es
s
h
P coulombic pressure,
P vapour pressure inside the cavity,
P electrostatic pressure,
P pressure due to surface tension, and
P hydrostatic pressure.
=
=
=
=
=



From this condition, an expression has been obtained for the maximum breakdown
strength of pure liquids which was found to be in good agreement with the experimental
results.
In general, the cavitation and bubble theories try to explain the highest breakdown
strengths obtainable, considering the cavities or bubbles formed in the liquid dielectrics.

Thermal Mechanism of Breakdown

Another mechanism proposed to explain breakdown under pulse conditions is thermal
breakdown. This mechanism is based on the experimental observations of extremely
large currents just before breakdown. These high current pulses are believed to originate
from the tips of the microscopic projections on the cathode surface with densities of the
order of
2
1A/cm . this high density current pulses give rise to localized heating of the oil
which may lead to the formation of the vapor bubbles. The vapor bubbles are formed
when the energy exceeds
7 3
10 W/cm . when a bubble is formed, breakdown follows,
either because of its elongation to a critical size or when it completely bridges the gap
between the electrodes. In either case, it will result in the formation of a spark.
According to this mechanism, the breakdown strength depends on the pressure and the
molecular structure of the liquid. For example, in n-alkanes the breakdown strength was
observed to depend on the chain length of the molecule. This theory is only applicable at
very small lengths
( )
100 m and does not explain the reduction in breakdown strength
with increase gap lengths.


Suspended particle theory:

In commercial liquids, the presence of solid impurities cannot be avoided. These
impurities will be present as fibers or as dispersed solid particles. The permittivity of
these particles ( )
2
will be different from the permittivity of the liquid( )
1
. If we
consider these impurities to be spherical particles of radius r, and if the applied field is E,
then the particles experience of force F, where

( )
2 1 3
2
1 2
1
F= grad E
2 2
r


+

(3.1)

This force is directed towards areas of maximum stress, if
2 1
, for example, in the
case of the presence of solid particles like paper in the liquid. On the other hand, if only
gas bubbles are present in the liquid, i.e.
2 1
, the force will be in the direction of areas
of lower stress. If the voltage is continuously applied (d.c) or the duration of the voltage
is long (a.c), then this force drives the particles towards the area of maximum stress. If
the number of particles is large, they become aligned due to these forces, and thus form a
stable chain bridging the electrode gap causing a breakdown between the electrodes.
If there is only a single conducting particle between the electrodes, it will give rise to
local field enhancement depending on its shape. If this field exceeds the breakdown
strength of the liquid, local breakdown will occur near the particle, and this will result in
the formation of gas bubbles which may lead to be breakdown of the liquid.
The value of the breakdown strength of the liquids containing solid impurities was found
to be much less than the values for pure liquids. The impurity particles reduce the
breakdown strength, and it was also observed that the larger the size of the particles the
lower were the breakdown strengths.

Electronic breakdown theory:

A review of this theory is discussed by Lewis. He discussed the conditions necessary for
cathode and anode initiated process. In general, it is unlikely for electrons injected in to
the liquid to produce significant ionization in the liquid state to develop an amplification
process. Cathode initiation assumes that electrons are injected into the as a column of
electrons emitted from micro-protrusion on the cathode. The electrons will collide with
the molecules locally heating the liquid through collisional impacts. The heating of the
liquid reduces the density allowing future electrons to obtain more energy from the field
before colliding with another molecule. The impacts that ionize a molecule will leave two
slow electrons to drift in the field. The build up of low energy electrons at the front of the
streamer marks the onset of spherical expansion under the columbic forces of the
consequent cloud of negative charge. The streamer will expand and appear thick and
bushy as it propagates across the gap. The lower density of the region the faster electron
amplification will occur. The obvious extreme of this process is the formation of an
avalanche within a bubble.
Anode initiation of break down requires a rapid charge development mechanism.
Assuming that holes emitted from the anode via resonance tunneling from molecule to
molecule, requires that the intermolecular distance be as small as possible to achieve high
probabilities for tunneling. High density regions are required to maintain minimal
molecular spacing. Tunneling establishes a hole propagation pathway through the liquid.
These pathways will trace hole through the liquid to the electrode, and should appear as
thin filamentary structures in the liquid. The path left by the propagation of the hole
through the liquid will be ideal return path for a complementary electron to propagate in
the opposite direction. The electrons prefer the lower density region created by passing
hole through liquid. Energy transfer via collisions that heat the fluid will be detrimental
to hole propagation since the density of the liquid will be reduced, reducing tunneling
probabilities.





c. Stressed Oil Volume Theory

In commercial liquids where minute traces of impurities are present, the breakdown
strength is determined by the largest possible impurity or weak link. On a statistical
basis it was proposed that the electrical breakdown strength of the oil is defined by the
weakest region in the oil, namely, the region which is stressed to the maximum and by
the volume of oil included in that region. In non-uniform fields, the stressed oil volume
is taken as the volume which is contained between the maximum stress ( )
max
E contour
and 0.9 ( )
max
E contours. According to this theory the breakdown strength is inversely
proportional to the stressed oil volume.
The breakdown voltage is highly influenced by the gas content in the oil, the
viscosity of the oil, and the presence of other impurities. These being uniformly
distributed, increase in the stressed oil volume consequently results in a reduction in the
breakdown voltage. The variation of the breakdown voltage stress with the stressed oil
volume is shown in Fig. 3.4.












400
300
200
100
0
10
-2
1.0

10
2
10
4
10
6
Stressed oil volume (cc)

Breakdown
Stress
(KV/cm)

Fig 3.4 Power frequency (50 Hz) a.c breakdown stress as function of
stressed oil volume

one minute withstand voltage

With steady voltage rise

3.4 CONCLUSIONS

All the theories discussed above do not consider the dependence of breakdown strength
on the gap length. They all try to account for the maximum obtainable breakdown
strength only. However, the experimental evidence showed that the breakdown strength
of a liquid depends on the gap length, given by the following expression,
n
b
V Ad = Where,
d=gap length,
A=constant,and
n=constant,always less than 1.


The breakdown voltage also depends on the nature of the voltage, the mode in which the
voltage is applied, and the time of application. The above relationship is of practical
importance, and the electrical stress of given oil used in design is obtained from this.
During the last ten years, research work is directed on the measurements of discharge
inception (starting) levels in oil and the breakdown strengths of large volumes of oil
under different conditions.
It may be summarized that the actual mechanism of breakdown in oil is not a simple
phenomenon and the breakdown voltages are determined by experimental investigations
only. Electrical stresses obtained for small volumes should not be used in the case of
large volumes.


Di electric dissipation factor:
This measure of the quality of oil. Low DDF indicates the good oil with low dielectric
losses and low level of soluble polar ionic or colloidal contaminants.
All kinds of dielectric or insulation materials and systems can be characterized by its
inherent polarization phenomena. Which in frequency domain can be expressed by a
capacitance C and a magnitude of power dissipation (di electric loss) as quantified by
dissipation or loss factor tan delta. Where as these quantities within a wide frequency
range are of at most interest for new materials or even for the quality control of well
known materials on receipt of delivery. These tests are generally performed at the
frequencies for which equipment/product is designed. Such tests are in general made in
dependence of test voltage applied both magnitudes, capacitance and dissipation factor
shall be essentially constant with increasing voltage as insulation system are linear
systems and any tip-up of the tan delta with voltage level called ionization knee is
preliminary indication of partial discharge within the system.

Transformer oil is a non-polar liquid with a capacitance that changes very little with
frequency. The relative permittivity,
r

, of oil is usually in a range 2,1-2,3. The dielectric


loss of oil is mainly governed by its DC conductivity that varies considerably with the
quality of the oilError! Reference source not found. As a result, measured dissipation
factor, as a function of frequency will slope downward in a straight line as shown in
fig
10
-4
10
-3
10
-2
10
-1
10
0
10
1
10
2
0,001 0,01 0,1 1 10 100 1000
Oil conductivity = 10
-12
S/m
Oil conductivity = 10
-10
S/m
Frequency [Hz]
Transformer oils Dissipation factor
(Tan )


10
-3
10
-2
10
-1
10
0
10
1
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3
mc=1.5%, =2e-12 S/m
mc=3.5%, =2e-12 S/m
mc=1.5%, =2e-10 S/m
d
i
s
s
i
p
a
t
i
o
n

f
a
c
t
o
r

(
t
a
n

)
frequency, [Hz]
50 Hz
60 Hz
High oil conductivity
Lower moisture content
in paper
Good oil conductivity
High moisture content in paper
















Corrosive sulfur:

INTRODUCTION
Corrosive sulfur and the effect that it has in transformer systems can be significant. The
extent of the corrosion damage caused by sulfur, if left unchecked, can be so severe as to
cause failure of the apparatus. The problems with corrosive sulfur have been recognized
for quite some time. As early as 1948, F.M. Clark and E.L. Raab issued a report on the
subject for method development within what is known now as ASTM Committee D 27
and eventually became ASTM Method D 1275. Sulfur is found in many materials of
transformer construction including the copper, paper insulation, gaskets and oil. Not all
sulfur is considered corrosive but the tendency to operate transformers at substantially
higher temperatures can aggravate an already present corrosive sulfur condition or
convert stable compounds into reactive ones that will cause damage.

PRESENCE OF SULFUR IN MINERAL OIL
There are different types of sulfur compounds found in refined transformer oil but not all
types are considered to be corrosive or reactive. Elemental sulfur and sulfur compounds
in concentrations up to 20% are present in the crude oil used to make transformer oil.
There are five basic groups of sulfur and sulfur compounds found in crude oil (see Table
1).

Sulfur and Sulfur Compounds Found in Crude Oil



Sulfur is commonly found in crude oil sources as it comprises almost 0.05% of the
earths crust. As shown in Table 1, elemental sulfur and the sulfur-containing mercaptans
are very reactive followed by sulfides. Reactive sulfur is mainly in the form of organic
sulfur compounds like R-SH, where the sulfur is attached at the end of an organic
molecule. When the molecule is more complex, for instance when the sulfur is
surrounded or contained within the molecule then the sulfur compounds are more stable
and less reactive, like in R-SS-R. Thiophenes are the most stable of all these sulfur
compounds. Some sulfur compounds can actually aid in the oxidation stability of the
transformer oil and may also act as metal passivators and deactivators reducing the
catalytic effect on oil oxidation in transformers. The goal of the refining process is to
either remove or convert many of the corrosive and reactive sulfur species (i.e. elemental
sulfur, mercaptans, and sulfides) to more stable compounds such as thiophenes in an
unsaturated ring and disulfides in a saturated form. The steps in the refining process that
aid in this effort are atmospheric distillation at various temperatures, vacuum distillation,
catalytic reaction, and hydro-treating and hydro-generation. It should be recognized that
the refining process is not always totally successful as incomplete refining may leave
small quantities of mercaptans behind or the hydrogenation process may produce
elemental sulfur as opposed to hydrogen sulfide.

After refining, there is some sulfur left but the total sulfur (comprised of the five groups
listed above) remaining in new oil product is expected to be from 0.02 % to 1%. This
information was slightly dated so the Doble Materials Laboratory analyzed several
samples from Doble annual Survey 93 and found that most oils had very low total sulfur
content as shown in Table 2.


WHAT IS CORROSIVE SULFUR?

Corrosive sulfur species are defined as all organic sulfur compounds that will react with
mercury to form sulfides, such as mercaptans. Elemental (free) sulfur is very reactive and
will react to form corrosive acids. It has been suggested that low elemental sulfur levels
(low ppm range) can cause a corrosive condition [4]. It has recently been suggested that
the definition of corrosive sulfur be narrowed to apply only to elemental sulfur whereas
those organo-sulfur compounds that react to cause a corrosive condition be termed
reactive sulfur.

REACTIONS OF CORROSIVE AND REACTIVE SULFUR

Corrosive and reactive sulfur compounds can react on contact with copper and other
metals. Copper is, by far, the least resistant metal to a sulfur attack. Effects of elemental
sulfur are even more problematic as its ability to combine with copper does not require
heat to promote the reaction. In oxygen deficient environments such as those found in
sealed, gas blanketed and sealed conservator transformers, corrosive and reactive sulfur
species combine with copper, aluminum, and other metals to form copper or cuprous
sulfide (Cu2S), aluminum sulfide (Al2S3) and other inorganic sulfides. Copper sulfide is
black, gray, green, blue, or violet in color and is sometimes confused with carbon.
Aluminum sulfide is a yellowish-gray material that can become very gray in the presence
of oxygen and water.
In the presence of an oxygen environment such as that available in sealed transformers
that have a significant leak, free breathing transformers, free breathing conservator
transformers, and other free breathing apparatus such as OCBs and LTCs, different types
of compounds are formed from the reaction of sulfur with metals. Oxygen can also
become available from the copper itself. The copper used for the windings is usually
CDA-110 (UNS-C11000) material for ETP copper which is termed electrolytic tough
pitch. This specification has a minimum copper purity requirement of 99.90% and it is
not considered an oxygen free material (<5 ppm). There is not an oxygen specification
for CDA-110 but it is usually contains about 500 ppm of oxygen or less. Copper winding
samples that the Doble Materials Laboratory has tested contained around 200-250 ppm of
oxygen. Different grades of copper can contain much higher amounts of oxygen that is
then available for use in a reaction with sulfur. Therefore, the manufacturer of the
transformer must be careful in selecting the correct grade of material for construction.
Reactions involving oxygen, sulfur, copper, aluminum, or other metals can produce
copper or cuprous sulfite (Cu2SO3), copper sulfate (CuSO4), aluminum sulfate
[Al2(SO4)3], and other inorganic sulfates. Copper sulfite is usually white to pale yellow
in color whereas copper sulfate is white or pale brown in color and aluminum sulfate is a
white material.

NONCORROSIVE TO CORROSIVE

One of the major questions is if noncorrosive sulfur species can be converted to corrosive
and reactive species in a transformer. Experience has shown that non-corrosive sulfur can
become corrosive after being exposed to elevated temperatures on hot metal surfaces and
thus produce metal sulfides. This attack would corrode the metal surfaces. To make
matters worse, the corrosion material could detach and become nuclei for discharge and
gas inception [3]. This may not be of concern with oils with low sulfur contents that pass
the corrosive sulfur test as the quantity of corrosive sulfur compounds produced may not
be sufficient enough to cause extensive damage.
The published literature does not detail if arcing in a transformer can change stable sulfur
species into reactive or corrosive forms. The Doble Materials Laboratory performed
experiments in which a voltage of 25 kV was applied to sustain an arc through Cross Oil
CrossTrans 106 transformer oil in a test cell equipped with a needle to sphere with a 0.1
inch gap. The CrossTrans 106 was found to be noncorrosive prior to testing. The arcing
produced the following gases:





The arcing did not reduce the total amount of sulfur left in the oil nor did it convert any
of the sulfur compounds already present into free sulfur. However, conversion of some of
the thiophene compounds did occur (see Table 6). The presence of sulfates and sulfites
cannot be determined by this method and it may be that those were the compounds that
were converted. This may explain the differences between the before and after test
results. What is of significant interest is the amount of unidentified volatile sulfur
compounds that were created through the arcing process. No mercaptans or sulfides
(corrosive or reactive sulfur) were formed. The lack of these sulfur species may be a
result of the energy applied through arcing that could have been so severe that any
reactive or corrosive species that were produced were instantaneously degraded and thus
none remain.



SOURCES OF SULFUR IN TRANFORMER SYSTEMS

Oil is not the only material that contains sulfur. Sulfur compounds are also present in the
gaskets, some water based glues, copper and paper insulation used in the manufacture of
transformers. Sulfur can also be introduced into the transformer through accidental means
such as through the use of incompatible hoses.

It is generally accepted that older gaskets used in transformer applications were made
from cork, cork/glyptal, and corkprene and then in more recent years, the most oil
compatible gaskets have been nitrile rubbers such as BUNA-N and a fluoroelastomer
such as VITON. Properly made nitrile rubbers (butadiene acrylonitrile) and
fluoroelastomers (fluorinated hydrocarbon) are excellent gaskets for use in transformers.
In the manufacture of these materials, sulfur is used in the curing process when the
formulations are being developed into a hardened material. The curing process is
supposed to eliminate all sulfur from the finished product. Most gasket manufacturers
assume that the sulfur is eliminated after the curing process. In some cases, the
concentration of sulfur contained in the final gasket product is not monitored. Doble
Engineering performed scanning electron microscopy/energy dispersive x-ray analysis
(SEM/EDX) analysis on numerous gaskets taken from recently manufactured
transformers. Each gasket was prepared for analysis by cleaning the outside surface with
a sulfur-free hydrocarbon solvent. The gasket was then cut lengthwise to reveal the inside
surface. The outside and inside surfaces of each gasket were coated with evaporated
graphite. The samples were then subjected to SEM/EDX analysis in which an electron
beam of the scanning electron microscope enters the bulk of a sample producing an x-ray
emittance. The x-ray peak positions, along the energy scale, identify the elements present
in the sample and can provide the percentage concentrations of each of these elements
thus providing an elemental breakdown of the material or particles. Results from two
gaskets are shown in Tables 7 and 8.


The inside of the O-ring gasket had a slightly elevated background level which indicates
that there is some organic component as well as the elemental component. Both gaskets
contained a large amount of sulfur especially the O-ring gasket. The SEM/EDX analysis
was performed on the inside surface of the gasket as well to distinguish between the
outside surface possibly being contaminated with corrosive sulfur from the oil. It is clear
that sulfur is a component of both original gaskets. The original formulations for a nitrile
rubber, fluoroelastomer or a silicone rubber, which is a polydimethylsiloxane, do not
contain any sulfur.

In discussions with elastomer manufacturers it was found that very few if any
manufacturers, (except for E.I. Dupont) were performing any chemical testing on the
finished product to determine what amount of sulfur remained if any. There also does not
appear to be any standard on what percentage of sulfur should remain in the final product.
It then becomes obvious that the onus is on the final user of the material to specify sulfur-
free or low sulfur material for use or to test it prior to use.

In light of this information, additional SEM/EDX analysis was performed on gasket
material that was available in the Doble Materials Laboratory. One sample was a
fluoroelastomer and another was a nitrile rubber produced by Parker. The results are
shown in Tables 9 and 10.


As shown in the two tables above, the fluoroelastomer shows no sulfur on the inside
surface and very little on the outside suggesting that material was cured correctly. The
opposite is true of the Parker nitrile material which shows extremely high sulfur content
on both surfaces suggesting that the sulfur was not removed after the curing process.

Water-based glues, used to secure the paper insulation during manufacture, often contain
sulfur compounds. There has been at least one known instance in which the glue used in
the manufacture of the windings has contributed to a corrosive sulfur condition.

Most coppers used in manufacturing transformer windings contain some impurities and
sulfur happens to be one, along with silver, arsenic, phosphorous, tellurium and oxygen.
The amount of sulfur that is allowed in most of the electrical grades of copper is 15 ppm
or less. In the analysis performed at the Doble Materials Laboratory on copper samples
from windings, the sulfur contents were very low at 5 ppm or less. However, there still
has to be care taken in the selection of materials used in construction so that copper with
a high sulfur content is not used.

The pulping process for electrical Kraft paper converts the wood chips to cellulose by
removing the majority of lignin (95-98.5%) and other impurities [5]. There are two basic
processes. The sulfite process is considered an acidic process and uses sulfur dioxide,
sulfuric acid and calcium bisulfite. The main process used today and the one that is used
to produce electrical grade Kraft papers is the sulfate process which is also called alkaline
pulping. Sodium hydroxide and sodium sulfide is used in what is termed the cooking
process. The cooking process under conditions of heat, pressure and chemicals (pulping
liquors) removes the lignin and impurities from the wood chips in order that only
cellulose remains. The pulping liquor is removed and recycled for use again and the
remaining cellulose pulp is washed several times to remove as much as the pulping liquor
as possible from the cellulose pulp. The Kraft process is slightly different in that the same
chemicals are used but the pulp is intentionally undercooked and results in the darker
color of the paper as well as exceptional mechanical strength. The pulp fibers in the Kraft
process do absorb some of the sulfur compounds that cannot be removed via the
washing/rinsing process [5]. The Doble Materials Laboratory performed analysis to
determine how much total sulfur remains in the finished paper products. The first analysis
performed was SEM/EDX analysis of new Kraft and thermally-upgraded (TU) Kraft
from United States manufacturers. These results are listed in Table 11 and are for the
surface of the paper only.

In addition, several different samples of Kraft paper insulation were analyzed for total
sulfur and total sulfate content. The results are present in Table 12.

As shown in Table 12, the amount of sulfur varies between various manufacturers of
electrical paper and sometimes considerably. The amount of sulfur present is fairly
significant in most of the samples. The amount of reactive or corrosive sulfur in relation
to the total is unknown although it is assumed that the amount of sulfates in the sample is
at least the minimum amount.

Accidental contamination of the transformer oil with corrosive and reactive sulfur
compounds can occur by use of incompatible materials or contaminated processing
equipment to transfer oil. For example, hoses that are made from natural rubber or
gasoline hoses both contain high amounts of sulfur that are easily transferable to the oil
that is being pumped through them. Extra care must be exercised in the selection of hoses
so that no incompatibility exists. Oil processing equipment runs the risk of being
contaminated from processing a transformer with corrosive and reactive sulfur to another
transformer that does not. The best safeguard is to check the remaining oil left in the
processing equipment prior to its next use.

As described above, several materials in the transformer will contain sulfur such as the
copper, paper and oil. In some cases, the sulfur species in question are stable or are so
tightly bound in the material that they would not be available for reactions. In other cases
some of the sulfur compounds are corrosive or reactive. In these cases, appropriate
material compatibility testing should screen out these materials before they are used in
transformer construction.

























EFFECTS OF CORROSIVE/REACTIVE SULFUR

Corrosion of the metal surfaces especially exposed copper surfaces is one of the primary
reactions of a corrosive/reactive sulfur condition. Figure 1 shows how exposed metal
surfaces can be worm-holed by a corrosive/reactive sulfur attack. Figure 2 shows NLTC
contacts that are overly contaminated with what appears to be a buildup of carbon but in
reality is copper sulfide.



The NLTC contacts shown in Figure 2 were discovered by accident. A maintenance
function involving a power transformer led to the belief that a piece of hardware had
fallen into the main tank of the transformer. A visual inspection was conducted through
the manhole of the unit and the blackened NLTC contacts were visibly apparent. This
caused the unit to be removed from the station, drained and inspected by entering through
a manhole. After draining and entering the unit, personnel wiped the NLTC contacts with
a cloth and discovered that the plating of the contacts was removed along with the black
material. This of course caused concern and an investigation was initiated in which it was
determined that copper sulfide, not carbon was the black shiny material found on the
contacts. This type of corrosion, as shown in Figures 1 and 2, could easily lead to
overheating and arcing of these components thus severely damaging or causing failure of
the apparatus. The effects of a corrosive/reactive sulfur attack on a metal conductor do
not always result in a black coating. In some cases, a silver coating or a silver
discoloration of the copper conductor surface occurs as in Figure 3.



The analysis on the paper surface shown in Figure 4 was performed by SEM/EDX as
previously described. In analysis performed on paper, the SEM/EDX analysis usually
indicates a very high organic content due to the cellulose composition. In this particular
case (Figure 4), the copper-sulfur contamination that had been transferred to the paper
insulation had been significant enough to mask out most of the organic component. In
analyzing this paper, a closer examination of the surface was conducted and SEM
micrographs were produced at a magnification of 200 times. Figure 5 is a SEM
micrograph of uncontaminated Kraft paper and crepe paper.


The individual paper fibers are clearly visible in both the Kraft and crepe papers in Figure
5 with no signs of foreign material present. Even the crimping of the crepe paper is
clearly visible. When copper/sulfur or other metal/sulfur contamination of the paper
surface occurs the results can be profound as shown in Figure 6.



All the fiber surfaces and the gaps between the fibers are encrusted with a contaminating
material in Figure 6A. The contamination present on the surface of the paper in Figure 6B
has not yet progressed to the same point as in Figure 6A but there is significant
contamination present and consists of mainly copper sulfides and sulfates. The small
spherical structures in the left-hand portion of Figure 6B are composed mainly of copper
and aluminum sulfides and sulfates. In an effort to evaluate the effect that this type of
contamination has on paper insulation, dielectric breakdown strength testing, by ASTM
Method D 149, was performed on the three layers of insulation that surrounded the
copper conductor. The first layer or the one closet to the conductor was the insulation
shown in Figure 6A. The other two layers of paper insulation were also contaminated but
not to the degree of the first layer. The results of this testing is shown in Figure 7.

Layer 1, shown in Figure 7, had an extremely low dielectric strength at 80 volts/mil. As
the contamination is reduced with each paper layer further out from the conductor, the
dielectric strength increases significantly to almost as new condition (1800 volts/mil oil
impregnated). Of significant interest is the fact that the mechanical strength was not
impacted by the contamination as the DP values for all three layers ranged from 903 to
938. The silvery appearance of the paper in Figure 4 is due to the alteration of the sulfur-
bearing compound due to exposure to higher temperatures, as copper sulfide is usually
gray-black in appearance. This reaction of copper and sulfur created deposits on the first
and second layers of paper on the same sample. Because of the deposition of the copper
and sulfur, the first inside wrap became a poor insulator and instead was more
conductive. When the corrosive sulfur contamination is this severe, a failure of the
transformer is almost inevitable as in this case.




















Testing For Corrosive sulfur:

ASTM D 1275B, Corrosive Sulfur in Oil

This test ages 220 mLs of oil in contact with a copper strip in a sealed vessel for 48 hours
at 50C. The primary purpose of the test is to determine if any corrosive sulfur
compounds in the oil will react with the copper strip to turn it gray or black. It is a
subjective test in that there is a comparison of colors of the copper strip with some
colored standards and a table of descriptions listing what is corrosive and noncorrosive
(Figure 1A and 1B). The test was recently modified from just D 1275 in April of 2006 to
D 1275A and D 1275B. The B method is more rigorous then the old method D 1275 or D
1275A and was developed in response to the problem with corrosive sulfur. The issue
was that some of these oils met the requirement of the oil specifications using the old D
1275 (D 1275A) test yet became corrosive while in service and eventually caused failures
of transformers, LTCs, and reactors. ASTM D 27 committee recognized this flaw and
modified the test method to include D 1275B. This is a very routine test.


ASTM D 5623, Sulfur Speciation

The ASTM D 5623 analysis is performed by gas chromatography with sulfur selective
detection and covers the detection of volatile sulfur-containing compounds. The test
method will not identify all individual sulfur components. Detector response to sulfur is
linear and essentially quimolar for all sulfur compounds; thus, both unidentified and
known individual compounds are determined. However, many sulfur compounds, for
example, hydrogen sulfide and mercaptans, are reactive, and their concentration in
samples may change during sampling and analysis. This test can be used to isolate
specific sulfur compounds, some of which may or may not be responsible for corrosive
sulfur attack. One of the issues is that depending on the lab, the database of sulfur
compounds that can be analyzed can be small or large but usually not more than about 70
compounds. There are thousands of sulfur compounds, and this test does not have the
ability to cover them all. Certain types of sulfur compounds cannot be fully isolated and
identified. It is usually not considered a routine test and is mostly used for research
purposes.

ASTM D 4294, Total Sulfur in Oil

There are actually several ASTM tests that can be used for the detection of total sulfur in
oil. This just happens to be the one that is used by our laboratory. This test determines the
total amount of sulfur in the oil but does not determine whether or not the compounds
being detected are corrosive.
Transformer oil is made from petroleum crude that has naturally occurring sulfur.
Depending on where in the world the oil is from dictates the amount of sulfur in the
crude. The process of refining the crude to transformer oil and other products attempts to
remove reactive (corrosive) sulfur compounds by converting them to hydrogen sulfide
gas which is easily removed from the process. The refining process can also convert
some of the less stable sulfur compounds into more stable un reactive sulfur compounds
that can provide benefits in the final refined product. The amount of conversion and
removal depends on the crude and the refining process itself, as each refiner has its own
distinctive process. Most modern transformer oils have a final sulfur content of less than
1500 ppm, and some are even less than 10 ppm. This is a routine test, but it only provides
information on how much sulfur is in the oil, not whether it is deleterious or not.

ASTM D 3227, Mercaptans in Oil

Mercaptans are sulfur compounds that can be very reactive. This is a potentiometric
titration test that is used to determine the concentration of mercaptans as a class of
compounds in the oil, but it will not be able to identify specific compounds. This test is
used in the fuel and lubrication industries often and is starting to be used in the
transformer oil industry. One of the problems with mercaptans is that some of them are
highly volatile and thus not easily sampled for. It is recently not a routine test, but it is
being used more and more.



Doble Covered Conductor Deposition (CCD) Test, Doble Test

There are two other variations, one developed by ABB and the other by Siemens, which
preceded the Doble method. A variation of the Siemens method is being developed into
an IEC test. This new test is very important in that the purpose of the test not only
determines if the corrosive sulfur will attack the copper and form copper sulfide, but also
if copper sulfide formations will develop in the paper insulation. The test is conducted by
taking an abraded copper rod and wrapping new Kraft paper insulation around the rod.
Two rods are prepared for each sample, and they are placed in 20 mL headspace vials.
Oil is added and then the vials are sealed. A stainless steel needle of a particular diameter
is then pierced through the septum of one vial and left there to allow air ingress during
aging (see Figure 2A and 2B). The vials are then aged at 140C for four days. At the end
of the aging cycle, the vials are removed and the copper rods with paper retrieved. The
paper is then removed from the copper, and both are washed in a solvent to remove the
oil. The rod is inspected to determine if it has been tarnished by corrosive sulfur, and the
paper is inspected to determine if deposition has occurred. The presence of deposition in
the paper is important as most of the recent transformer failures have been due to copper
sulfide deposits in the paper causing a severe reduction in dielectric strength. The
resulting "deposition," whether heavy, moderate, or light, means that the interaction of
the copper and oil with the paper insulation over the duration of the test resulted in an
obvious deposit of copper sulfide, copper, or oil/paper degradation by-products onto or in
the paper insulation. This is becoming a very routine test.


Doble Covered Conductor Deposition (CCD+DT), Doble Test.

A CCD test with dielectric breakdown voltage is performed on the paper after aging.
During the research conducted for the development of the CCD test, it was noticed that
many oils, under the conditions of the test, actually formed deposits on and in the paper.
It was determined that if a dielectric breakdown voltage test was performed on the paper
from the copper rod, it could be used to qualify the deposits. Basically there are two
categories of deposits: those having no impact on the dielectric strength of the paper and
those that negatively affect the dielectric strength of the paper. Obviously the deposits
affecting the dielectric strength by lowering it are of concern. This is also becoming a
very routine test.

Dibenzyl disulfide (DBDS in Oil), Doble Test

DBDS is a sulfur compound found in certain transformer oils. DBDS is not thermally
stable at higher temperatures and breaks down into benzyl mercaptans which is very
corrosive and attacks the copper quite quickly. It should be remembered that DBDS is not
the only compound to cause severe copper sulfide deposition on the copper. There are
other compounds that cause corrosive sulfur attack but as of yet have not been identified.
This is now a very routine test.









































































Transformer oil analysis