2019 IEEE 20th International Conference on Dielectric Liquids (ICDL), Roma, Italy, June 23-27, 2019

Effect of molecular structures of insulating oil on

Stray Gassing
Hiroko Tomita Takashi Ito
Lubricants Company Lubricants R&D department, Lubricants Company
JXTG Nippon Oil and Energy Corporation JXTG Nippon Oil and Energy Corporation
Tokyo, Japan Yokohama, Japan
tomita.hiroko@jxtg.com ito.takashi.223@jxtg.com

Abstract— Reports from all over the world indicate that
transformer oils can release large amounts of flammable gasses
even at moderate operating temperatures. This phenomenon is
termed ‘stray gassing’. However, there have been few studies on
the relationship between the molecular structures of the oil and
stray gassing. In this report some molecular structures were
selected because they represent each carbon-type composition.
They were subjected to stray gassing tests. It was found that the
structures of each compound have different gas patterns under
the stray gassing test conditions.
Keywords—stray gassing, insulating oil, molecular type
I. INTRODUCTION
For many years, dissolved gas analysis (DGA) has been the
most important tool for judging the condition of transformers
worldwide. DGA is the study of mainly dissolved flammable
gasses such as carbon dioxide, carbon monoxide, hydrogen,
methane, ethane, ethylene or acetylene in insulating oils. It can
be used to detect early signs of problems with transformers,
including overheating, hotspots, partial discharge, and arcing.
Recently it has been reported all over the world that a large
amount of flammable gasses have been generated from
transformers thought to be performing at moderate temperature
s. This phenomenon is termed ‘stray gassing’. The stray gasses
are formed by chemical reactions at the transformer’s normal
operating temperatures, but the cause of stray gassing has not
been identified. This stray gassing phenomenon makes it
difficult to identify the cause of problems within transformers.
Numerous studies on this phenomenon have been reported, but
few studies have been done on about the relationship between
the molecular structures of the oil and stray gassing. For this
study, some model compounds were selected and tested in
order to understand the influence of the molecular structure of
the oil on stray gassing.
types. In this report some molecular structures were selected
because they represent each carbon-type composition. In
Table1 it shows the relationship between test samples and these
carbon-type compositions of oil. They were subjected to the
stray gassing test. Paraffin test samples containing 13 ~ 16
carbons were selected. Iso-Paraffinic and naphthenic test
samples with 16 carbons were also selected. The test samples
of iso-paraffinic carbon types were selected because they have
many branches, and because of the expectation of definitive
results.
B. Test methods
The test was performed under ASTM D7150-13 (Standard
Test Method for the Determination of Gassing Characteristics
of Insulating Liquids Under Thermal Stress) Method A. It is
known that the amount of oxygen in the oil can affect the
results of stray gassing tests. The amount of generating gasses
under air-purged conditions is larger than under nitrogen-
purged conditions. On the other hand, it is difficult to delete the
influence of the air even though under the nitrogen-purged
conditions. It is easier to find the stray gassing characteristics,
when oxygen concentration in the oil is higher. Therefore all
tests were performed under air-purged conditions. The test
method was as follow.
(1) 100 ml oil samples were air-purged and the air flow speed
was 200 ml/min for about 20 min.
(2) The test samples were sealed in syringes and aged for164
hours at 120 °C.
(3) After aging, DGA was performed on the oils.
In this study, two tests were performed for each sample. There
was not a big difference between two test results. So the
averages of the test results were reported.
TABLE I. TYPE OF TEST SAMPLES

Type Molecular types Test samples

II. STRAY GASSING TEST Normal-paraffine tridecane, tetradecane,
compounds pentadecane, hexadecane
A. Samples Paraffinic Iso-paraffine 2,2,4,4,6,8,8-heptamethylnonane
carbon types compounds 2,6,10,14-tetramethylpentadecane
Mineral oil is composed of hydrocarbons. There are n-decylcyclohexane,
numerous carbon compounds of structures and complex Naphthenic Alkyl-substituted n-undecylcyclohexane,
isomers and it is impossible to know the specific chemical carbon types naphthenic compounds n-dodecylcyclohexane,
composition and ratios. Generally mineral oil is divided into n-tridecylcyclohexane
three main carbon-type compositions. They are paraffinic n-decylbenzene,
Aromatic Alkyl-substituted
n-dodecylbenzene,
carbon types, naphthenic carbon types and aromatic carbon carbon types aromatic compounds
n-pentadecylbenzene

978-1-7281-1718-8/19/$31.00 ©2019 IEEE

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 III. RESULTS
A. Commercial insulating oil
For reference, the test was performed with a commercial
insulating oil that is widely used in Japan. Figure 1 shows the
result for this oil. This oil did not release large amounts of
gases and this result testified that this oil did not generate any
stray gasses. There have been no reports of stray gassing with
this oil in Japan.
Fig. 1. The result of commercial insulating oil in Japan
Fig. 2. The result of normal-paraffine
Fig. 3. The result of iso-paraffine
2
Fig. 4 Oxidization of iso-paraffinic compounds
B. Normal-paraffinic compounds
Table1 shows four normal-paraffinic compounds. Fig. 2
shows the results of stray gassing tests for those samples. No
matter the number of carbons, the tendencies of generating
gasses were same.
As Fig. 1 shows, the amount of H2 generated by the
commercial insulating oil was about 100 ppm. But as Fig. 2
shows, the normal-paraffinic compounds generated around 600
ppm H2. The normal-paraffinic compounds generated larger
amounts of H2 than the commercial insulating oil. The normal-
paraffinic compounds also generated larger amounts of CO
and C2H4 than the commercial insulating oil. Focusing on C2H4,
we see that the commercial insulating oil generated 8 ppm
while the normal-paraffinic compounds generated around 100
ppm.
It is thought that these results are related to the oxidation of
secondary carbons. It is typically said that secondary carbons
are oxidized more easily than primary carbons[1]. The
secondary carbons of normal-paraffinic compounds, which are
most prone to oxidation, are located next to the primary
carbon. That is why two C units gasses were generated.
C. Iso-paraffinic compounds
Table1 shows two iso-paraffinic compounds. Figure 3 shows
the results of the stray gassing test for iso-paraffinic
compounds and the result for hexadecane for comparison. In
Fig. 3, we see that the gas patterns for the two iso-paraffinic
compounds were different. But these compounds had
something in common, in that both generated larger amounts of
CH4 and C3H6 compared to hexadecane. Those iso-paraffinic
compounds have many more tertiary carbons than do normal-
paraffinic compounds such as hexadecane. It is said that
tertiary carbon is more prone to oxidation[1]. Figure 4 shows
the image of the oxidation of iso-paraffinic compounds. These
tertiary carbons were the first point to be broken by the
oxidation and resulted in generating one or three C units gasses.
D. Alkyl-substituted naphthenic compounds
Table1 shows four alkyl-substituted naphthenic compounds.
The results for those compounds are shown in Fig. 5. In this
figure, they show the same gas patterns so it does not matter
which ones were used to substitute the naphthenic compounds.
Compared to hexadecane, they emit smaller amounts of CH4
and C2H6. They are saturated hydrocarbons and they are said to
be generate by oxidization[2]. To focus on CH4 and C2H6,
Figure 6 shows the sum of amount of CH4 and C2H6 released
by each alkyl-substituted naphthenic compound. The sum of
CH4 and C2H6 released by the alkyl-substituted naphthenic
compounds were much smaller than that released by
 Fig. 5 The result of Alkyl-substituted naphthenic compounds
Fig. 6. Sum of CH4+C2H6(Alkyl-substituted naphthenic compounds)
hexadecane. It has been reported that alkyl-substituted
naphthenic compounds have lower oxidation stability.
However, they generated only smaller amounts of CH4 and
C2H6. As mentioned above, stray gassing tests are similar to the
oxidation test, but alkyl-substituted naphthenic compounds
generated an unexpectedly lower amount of gasses compared
to normal-paraffinic compounds. Therefore these results were
contrary to the tendency to oxidate. This phenomena is the
characteristic of alkyl-substituted naphthenic compounds.
E. Alkyl-substituted aromatic compounds
Table1 shows the three alkyl-substituted aromatic compounds
that were tested and Fig. 7 shows the results of the stray
gassing test for these compounds along with those for
hexadecane for comparison. As Fig. 7 shows, the three alkyl-
substituted aromatic compounds showed the same gas patterns.
The amounts of the saturated hydrocarbons were smaller than
that of hexadecane same as alkyl-substituted naphthenic
compounds. Figure 8 shows the sum of CH4 and C2H6 for each
alkyl-substituted aromatic compound. The alkyl-substituted
aromatic compounds generated much smaller amounts of
saturated hydrocarbon gas than did hexadecane. Alkyl-
substituted aromatic compounds are known to be stable and
resistant to oxidation. These results are reasonable for the
tendency to oxidation.
3
Fig. 7 The result of Alkyl-substitued aromatic compounds
Fig. 8. Sum of CH4+C2H6 (Alkyl-substitued aromatic compounds)
IV. THE PROOF OF PLACE OF C-C BOND BREAKING
A. Analysing phenomena
DGA detects only low-molecular-weight gases such as those
whose molecules have from one to three carbons. It is difficult
to understand why these low-molecular-weight gasses were
released by the oil. To understand the stray gassing, GC/MS
analyses the gasses which have a larger molecular weight than
the gasses detected by DGA. The results of DGA and GC/MS
are not enough to know phenomena. By introducing the
Gaussian process, it is easier to infer why these gasses were
emitted from oil. The Gaussian process can calculate which C-
C bond is easy to break and also the C-C bond energy. In this
paper, these methods helped to support the thesis of oxidation.
B. Result of the Gaussian chemical modeling and GC/MS.
In Table2, three samples were selected from each types. From
the Gaussian process results, there are weak C-C bonds which
are highlighted. From 2,2,4,4,6,8,8-heptamethylnonane,
GC/MS detected some ketone and alkene which have fewer
carbons. And in n-tridecylcyclohexane’s result of GC/MS,
cyclohexane and cyclohexanone were detected. From n-
dodecylbenzene, toluene and benzaldehyde were detected.
These GC/MS results prove that weak C-C bonds were
broken. It could be also said that weak C-C bonds were the
first point to break and generate low-molecular gasses
 TABLEϩ RESULTS OF GC/MS AND GAUSSIAN

TEST SAMPLES 2,2,4,4,6,8,8- N-TRIDECYLCYCLOHEXANE N-DODECYLBENZENE

HEPTAMETHYLNONANE

Weak
GAUSSIAN Weak
point
CHEMICAL point
MODELING
Weak
point

C-C BOND
358.4KJ/MOL 386.7 KJ/MOL 446.9KJ/MOL
ENERGY

DETECTED
MOLECULES BY
GC/MS

generate during stray gassing test. Regarding the C-C bond

energy, Table2 also shows C-C bond energy. The bigger the V. CONCLUSION
C-C bond energy is, the harder it is to break and generate small (1) This paper showed the effect of each composition of
amount of gasses. This was proved through the use of the mineral oil on stray gassing.
Gaussian Process is meet to the tendency of T.C.G. comparing
the three samples in Fig.9. The tendency of T.C.G. was (2) Normal-paraffinic compounds generated larger amounts
effected by CO and CH4. As noted above, CH4 and C2H6 were of CO and C2H4 than did a commercial insulating oil.
generated by oxidation. But C2H6 did not generate from (3) Iso-paraffinic compounds generated larger amounts of
2,2,4,4,6,8,8-heptamethylnonane because construction of this CH4 and C3H6 than did normal-paraffinic compounds.
sample are difficult to generate two C units. In this figure, the
result of stray gassing test of three samples are shown. (4) Alkyl-substituted naphthenic compounds and alkyl-
2,2,4,4,6,8,8-heptamethylnonane’s weak C-C bond energy is substituted aromatic compounds released smaller
the smallest among those samples, and the C-C bond is easy to amounts of CH4 and C2H6.
break. This result was reasonable to assume that they break to (5) To understand stray gassing phenomena, focusing on the
generate low-molecular gasses. That is why 2,2,4,4,6,8,8- C-C bond energy would be helpful to understand the
heptamethylnonane emitted bigger amount of T.C.G.. which kind of gas would generate and introducing the
Introducing the GC/MS and Gaussian process is useful to Gaussian process and GC/MS are adequate to supporting
detecting larger molecules and that will helps to understand this approach.
cause of stray gassing.
REFERENCES
[1] Leslie R. Rudnick; Lubricant Additives: Chemistry and Applications,
Second Edition (Chemical Industries)㸪Chemical Industries/124(2009)
[2] Takashi Ito; The effectiveness of Composition in Insulating oil on Stray
Gassing Test, 36th Technical Meeting on Insulating Oil Section, The
Japan Petroleum Institution
[3] Electric Technology Reserch Association; Transformer repair guidelines
Electric Technology Reserch65th No.,30(2009)

Fig. 9 The result of stray gassing test