Effect of Transformer Materials on Stray

Gas Generation

By

Mrs. L. Bergeld, Mr C.Y. Toh, Mr J. Weesmaa,

Dr B. Pahlavanpour, Mr J. Nunes

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 EFFECT OF TRANSFORMER MATERIALS ON STRAY GAS GENERATION
Mrs. L. Bergeld, Mr J. Weesmaa - Nynas AB, 149 82, Sweden
Mr C.Y. Toh, Nynas, 138 543 Singapore
Dr B. Pahlavanpour, Nynas Naphthenics Ltd, UK
Mr J. Nunes, Nynas Ltd, BRAZIL
Abstract

Dissolved Gas Analysis (DGA) is a widely used tool for understanding the condition and processes
ongoing inside a transformer. Increased levels of certain gasses in the transformer oil can be
measured and interpreted according to guidelines. By the analysis of amounts of hydrogen, volatile
hydrocarbons and carbon oxides dissolved in the insulating oil dielectric and thermal faults can be
detected at an early stage.

Additionally there will be gas generated in a transformer without faults which occur during normal
conditions. This gas generation is often called “stray gassing” and is caused by different chemical
processes ongoing at normal temperatures in the transformer. The main driving factors for increased
gas generation in transformers are temperature and presence of oxygen. Stray gassing is often
evaluated via standardized stray gassing tests, like the ASTM D 7150 method, where the oil is aged in
glassware at 120°C. The temperature is chosen to speed up reactions in order to reduce the testing
times even though most transformers operate at much lower temperatures.

In this study focus is on stray gas generation due to interaction between oil and other common
materials that are used in transformers. Most OEMs test their materials and their compatibility with
oil, however sometimes materials are used in the construction without compatibility testing. This
study is based on real cases with excess gas generation which have, later in laboratory tests, shown
that unsuitable materials can generate gases in contact with oil and make DGA interpretations more
complex.

The study first looked at a comparison between inhibited and uninhibited mineral insulating oils with
respect to how different transformer materials have impact on the results, and later focus on how
inhibited mineral oil behaves together with various transformer materials.

Background

Insulating oil in transformers is slowly degraded with time by both normal and abnormal operations.
Fast degradation is usually related to very high temperatures which break down the hydrocarbons in
the oi.l This among other things lead to generation of so called “dissolved gases”. The rate of
generation and distribution of these gases can be analysed (dissolved gas analysis, DGA) to provide
an indication of the transformer´s condition. However insulation oils can also at normal transformer
operating temperatures give rise to small amount of gases without any thermal or electrical faults in
the transformer. This behaviour is called stray gassing and can include gasses such as hydrogen,
hydrocarbons and carbon oxides. In practice there are also other factors in addition to temperature
that can impact on gas generation. Effects on stray gassing, when insulation oil is in contact with
other transformer materials like cellulose, coatings, paint, glue and metals are described in IEC
60599:99 [1]. Moderate stray gassing is not harmful to the transformer and is often seen as the
baseline of gases. In rare cases higher stray gassing can mask the gases formed by faults in a
transformer. Also, if enough gas is generated in the transformer and gas bubbles are formed, there
might be a risk of partial discharges occuring, due to lower insulation. Additionally, the initial function of a
material might change if reacting with others.

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There is a wide range of materials used in a transformer and this study is only looking at a few,
including: naphthenic mineral oil, galvanized steel, iron, varnish, paints, carton, glue, tapes and
paraffin.

Stray Gas Measurement

Testing of oil alone can be done using ASTM D7150 [2] or via a modified version of the method, some
of which are described in Cigré Technical Brochure 296 [3]. Both ASTM and Cigre methods use a
glass syringe filled with filtered/vacuum degassed oil purged with either air or nitrogen. The oil-filled
syringe is aged at 120°C for 164 h (ASTM) or according to Cigré TB 296 for 16 and/or 164h,after which
the oil is analyzed for dissolved gas concentrations with standard DGA measurements, such as ASTM
D3612C [4] and IEC 60567 [5]. The gases measured are: H2 (hydrogen), O2 (oxygen), N2 (nitrogen), CO
(carbon monoxide), CO2 (carbon dioxide), CH4 (methane), C2H6 (ethane), C2H4 (ethylene), C2H2
(acetylene), C3H8 (propane) and C3H6 (propylene).

Method

This study followed the instructions in ASTM D7150. The oil was first filtered and thenstripped for
30 minutes with air in a 250 ml flask, to get saturated with the gas. After this pre-treatment, the fluid
was transferred (30ml) to the ageing vessel, which in this case was a glass, metal stopper sealed
syringe and then aged at 120°C for 164/168 hours. Finally the aged oil was analysed for DGA gases in
accordance with the standard method, using a head space gas chromatograph with argon
atmosphere in the vial. A reference syringe was prepared for each sample and not heated.

Figure 1: Prepared Glass Syringes

The first study looked at uninhibited and inhibited naphthenic mineral oil with respect to
compatibility with galvanized steel, iron and varnish. The second study looked at inhibited
naphthenic mineral oil in combination with two paints, cardboard, glue, two tapes and paraffin.

After looking at the combination of mineral oil and other materials a modification to ASTM D7150
was made - a small piece of material was placed inside the syringe used for ageing. The material
samples were cut into suitable sizes and the glue and paint were applied on a glass surface and left to
dry before testing.

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Results

Figure 2: Stray Gas Generation in Inhibited and Unhibited Transformer oil

The higher oxidation resistance in inhibited transformer oils is represented by the gas formation in
the graph (Figure 2). The H2, CH4 and C2H4 levels are all, as expected, higher in the uninhibited
transformer oil sample. The O2 level decrease in the uninhibited sample could be explained by its
consumption during oxidation. It should be noted that this result is not valid for all types of oils,
since it is dependent on the quality and oxidation stability of the oils and it would not be enough to
classify only as inhibited or uninhibited.

The next step was to look at gas behaviour in relation to some commonly used materials within a
transformer. Both inhibited and uninhibited oils were used for this experiment and the results from
combinations with galvanized steel (Zink), iron and varnish on glass can be seen in Figures 3-5.
Generation of hydrogen and carbon dioxide increases significantly when zinc metal is present during
the ageing process for both oils, compared with Figure 2. The results in Figure 4 show that iron has
low impact on gas generation.

Figure 3: Figure 4:
Stray Gas Generation in Oil with Zinc Plate Stray Gas Generation in Oil with Iron Core
present Material present

One commonly used type of varnish was being studied next. To eliminate the risk that the
glass surface would create any gas , this sample was compared with a sample where the
varnish was applied to a piece of iron. Since that is more of a method development the
results are not shown here, but they showed that the glass had no additional effect upon gas
formation. What can be seen in Figure 4 is that the varnish has a slight effect on hydrogen
generation and the H2 hasincreased compared toFigure 2. It is appropriate here to note that there

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are several types of varnish used inside transformers and different effects from other types are to be
expected.

Figure 5: Stray Gas Generation in Air Saturated Oil with Varnish on Glass

The following material study was made with inhibited mineral oil only. Table 1 shows the gas
formation for each combination of material. The same test conditions were used except that the
duration was 168 hours instead of 164 hours as in the previous study.

Table 1:
Gas Formation in Various Materials

1 2 3 4 5 6 7 8

Oil + Oil +
Oil + Oil + Oil + Oil + Stripe Stripe Oil +
Oil Paint Paint Carton Glue permacel glass Paraffin
H2 113 125 452 39 232 508 1879 82
O2 31250 30078 10009 8444 29517 4122 7274 37739
N2 121684 118243 145134 49265 147139 110917 151690 129034
CO 277 365 2235 561 514 646 1116 274
CO2 549 848 4671 23524 1641 1960 5659 507
CH4 5 6 74 13 9 26 47 5
C2H6 ND 2 13 4 1 3 4 3

For the samples with increased level of hydrogen (3, 6 and 7) it can also be seen that the
level of oxygen is decreased. This would indicate that there is a process that is consuming oxygen
taking place in the test syringe. One exception is the sample with cardboard, here the oxygen level
decreased without any hydrogen formation. On the other hand, a large increase in CO2 is observed,

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which would be an indication on that the cellulose material is being degraded. It would be expected
to see the cellulose start to break down at these test conditions with a temperature of 120°C.

Table 1 plots the formation of hydrogen, which would be one of the first indicators that something is
reacting - it is easily seen that Samples 3, 6 and 7 behave differently compared to the others. The
paint, (Sample 3), shows an overall increase in gas formation. Samples 6 and 7 show in general a
high gas formation and the consumption of oxygen indicates that this material has a catalytic effect
on the oxidation process. Sample 7 gives an extremely high hydrogen formation. There is also a
slight increase in hydrogen level and CO2/CO ratio for Sample 5.

One note to Sample 2 (paint) is that even though no strange gassing behavior was observed, there
were pigments falling to the bottom when cooling down after the ageing process. These particles
could have an effect on the function of the transformer, and this material could be unsuitable for use
in a transformer. A second note is that Sample 8, which is a paraffin block, did not indicate any issues
regarding the gases, but it did dissolve in the oil and formed a hazy look when cooled down.

Summary

One of the very first conclusions is that there are many different materials inside a transformer and
these will all behave differently in combination with different transformer fluids, while the same
materials from different suppliers could possibly give different effects. Therefore it is important to
evaluate the exact materials that could possibly come in contact in a specific unit. This makes an
overall guide impossible, even though you, from experience, could exclude the most extreme cases.
It must also be emphasized that in most cases where stray gassing is believed to be a problem it is
not the oil in itself that causes excessive gas formation. Rather, it is the interaction of different
materials with the oil that leads to gas generation.

In order to make a correct evaluation of the dissolved gas analysis (DGA), knowledge about stray gas
behavior is needed. The standard method used for measuring stray gassing, ASTM D 7150, has
limitations in its precision, and it is easy to have variations in results between duplicated samples and
different laboratories. However, the method is useful to understand the mechanisms behind the
chemical processes involved in gas generation in real transformers. Transformers contain many
different types of materials and the insulating oil is in contact with most of them. Most chemical
reactions in the oil are mainly driven by heat, oxygen or the catalytic behavior of metals. The
chemical reaction products end up as a sum in the oil and can partly be analyzed by DGA. Pure
unused oil can, as shown in this study, generate gasses under heat stress and presence of oxygen but
the amounts of gasses produced by pure oil are very small. Stray gassing measurements on new oil
therefore are of limited value. Zinc has a major impact on hydrogen generation in both inhibited and
uninhibited transformer oils.

This study is not intended to be used as a guideline, but is presented more to highlight the
importance of knowing which materials to use in a specific unit. It also shows that even if no gas
generation is seen there could be other issues with some materials.

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References

1. IEC 60599 – Mineral oil impregnated electrical equipment in service – Guide to interpretation of
dissolved and free gases analysis 1999
2. ASTM D7150: Standard Test Method for the Determination of Gassing Characteristics of
Insulating Liquids Under Thermal Stress
3. Cigre brochure 296 – Recent development in DGA interpretation
4. ASTM D3612C: Standard Test Method for Analysis of Gases Dissolved in Electrical Insulating Oil
by Gas Chromatography
5. IEC 60567: Oil-filled electrical equipment - Sampling of gases and analysis of free and dissolved
gases - Guidance

Biography of the Presenter

Linnéa Bergeld is the Technical Manager Electrical Industry and is based in Sweden. In this
position she will be focusing on the insulating oil market and activities for Nynas. She has
been with Nynas AB since 2009 and has held the position of Head of Technical Market
Support for Asia Pacific and was based in Singpore during this time.

Linnéa received a Master’s degree in Chemistry from Karlstad University (Sweden) in 2008.