6598 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 54, NO.
6, NOVEMBER/DECEMBER 2018
Methanol as an Ageing Marker for In
Service Transformers
Charles E. Bare, II , Member, IEEE, and Stanley Y. Merritt, Life Senior Member, IEEE
Abstract—Measurement of transformer remaining useful life
has long been a goal for responsible asset management. Most testing
laboratories offer furan concentration testing as a suitable method.
The interpretive method of choice is usually the Chendong equa-
tion, expressed in practical terms as degree of polymerization of
the paper with new paper at about 1000 and end of life at around
300. Typical mill transformers have thermal insulation ratings ex-
pressed as 55 °C rise for plain kraft or 65 °C, which corresponds
to thermally upgraded kraft paper (TUP). It has been determined
that TUP does not produce furans and, thus, provides a false indi-
cator of the cellulose breakdown. There are several recent papers
that have demonstrated that a measurement of methanol (MeOH)
may be a better method to determine ageing of the TUP insulation
and also better for transformers with plain kraft paper insulation.
The objective of this paper is to provide an overview of the reasons
why furans should not be used as the basis for measuring aging
of thermally upgraded paper, why MeOH should be so used, and
to compare actual furans and MeOH test data for service aged
transformers in a process industry application
Index Terms—Cellulose insulation, dissolved gases, dissolved gas
analysis (DGA), furanic compounds, methanol (MeOH), polymer-
ization, thermally upgraded kraft paper (TUP).
I. INTRODUCTION
ANY and probably most mill substation transformers are
M rated for a 65 °C rise of average winding temperature
over a 30° ambient. Using the thermal model of IEEE standard
C57.91-2011 the resulting hotspot temperature will be 110 °C.
The only insulating paper that is rated for 110 °C is thermally
upgraded paper such as “Insuldur” or “Thermo ZA.” There are
good reasons to use thermally upgraded paper other than the
temperature rating, particularly since its oxidation consumes
water and neutralizes acid.
Insuldur has performed impressively in this investigation [1].
It contains additives which consume water by reacting chem-
ically with it, and organic bases which partially neutralize the
acids. This increases its lifetime by a factor of about three com-
pared to Kraft.
Manuscript received April 6, 2017; revised September 1, 2017; accepted
September 15, 2017. Date of publication January 30, 2018; date of current
version October 12, 2018. Paper 2017-PPIC-0263.R1, presented at the 2017
Annual Pulp, Paper, and Forest Industries Technical Conference, Tacoma, WA,
USA, Jun. 18–23, and approved for publication in the IEEE TRANSACTIONS
ON INDUSTRY APPLICATIONS by the Pulp and Paper Industry Committee of the
IEEE Industry Applications Society. (Corresponding author: Charles E. Bare,
II.)
The authors are with Highground Services, Inc., Franklin, VA 23851 USA
(e-mail:,cbare@highgroundservices.com; smerritt@highgroundservices.com).
Digital Object Identifier 10.1109/TIA.2018.2799188
0093-9994 © 2018 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
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1) Thermal upgrading of insulation [2]: In the late 1950’s
transformer manufacturers developed thermally upgraded pa-
pers (TUP). In 1962, NEMA officially recognized TUP in stan-
dard TR-1-1962 by establishing another temperature rise limit
of 65 deg. C. for oil-immersed transformers using TUP. Today
65 deg. C. rise transformers are the norm in North America.
There are two types of thermal upgrading processes.
1) Modification of the cellulose chains specifically at OH
groups by cyanoethylation and acetylation.
2) Addition of chemicals to protect the cellulose from oxida-
tion: This is primarily achieved with nitrous compounds
such as urea, melamine, dicyandiamide, and polyacry-
lamide.
In order to extend the life of the cellulose insulation used in
power transformers, it has become common since the late 1950’s
to chemically upgrade the thermal resistance of the material [3].
The majority of chemicals used for this treatment contain nitro-
gen atoms. The long term life of some of these heat stabilized
papers has been found to be up to 10 times longer than standard
papers.
It has long been accepted that a different interpretation of
furan concentration must be applied to thermally upgraded paper
as compared with plain kraft. There is a modified Chendong
equation for thermally upgraded paper.
Studies at . . . (major testing laboratory) . . . . have consistently
shown that 90–95% of samples from transformers with ther-
mally upgraded insulation have less than about 100 mg/L of
2-furfural [4]. However, for a similar population study of oils
from service aged transformers with Kraft paper insulation, the
95% norm was 2057 mg/L.
The amount and type of furanic compounds is different for
Kraft and Thermally Upgraded Kraft paper (TUP).
Recently, however, several technical papers have been pub-
lished that support the belief that at temperatures near the rated
value of 110 °C, there is actually no furan produced by aging of
thermally upgraded paper.
Test data for thermally upgraded paper in inhibited oil at
105, 122, and 130 deg C. shows no detectable 2 FAL even
though significant depolymerization occurred [5]. By contrast,
significant concentration of methanol was measured.
The authors were able to find four research papers, which re-
ported aging tests of thermally upgraded paper in oil, which pro-
duced no detectable furans at temperatures from 105 to 170 °C
(see Table I). The authors were not able to find any research
reports of ageing tests, which did produce detectable furans at
these temperatures.
BARE, II AND MERRITT: METHANOL AS AN AGEING MARKER FOR IN SERVICE TRANSFORMERS
TABLE I
SUPPORTING RESEARCH PAPERS
II. TYPICAL LIQUID SCREEN AND DISSOLVED GAS
ANALYSIS (DGA)
A typical liquid screen test report from a reputable laboratory
on a mill transformer with thermally upgraded paper will show
furans at less than 10 ppb and may, therefore, conclude that
loss of useful life is less than a year. The authors have seen
this from three well-known test laboratories. In light of the
current literature, it seems more likely that the reason no furans
were found is that thermally upgraded paper does not produce
furans in measurable quantities as a degradation product and
the absence of furans does not provide reliable indication about
condition of the paper.
The DGA will usually show CO or CO2 or both at concentra-
tions higher than the levels of concern stated in IEEE Std. C 57
104, thus, raising the question of overheating of the cellulose.
It is more likely that the high levels are due to the fact that TUP
produces much more Co + CO2 than plain kraft.
The (CO + CO2 ) content with a percent DP retention value
of 45% was roughly 1.1 ml/g paper for the Kraft insulation
paper but roughly 5.3 ml/g for the Thermo-ZA, a difference by
approximately a factor of 5 [6].
Fortunately, methanol appears to be a better marker than fu-
rans. CIGRE has a working group to assess the use of methanol
as a marker since it is produced by both plain kraft paper and
thermally upgraded paper. A report of this working group is
included as [7].
CONDITION ASSESSMENT
Presented by: Mohamed Ryadi (EDF-R&D)
Principal investigators: Jocelyn Jalbert, Marie-Claude Lessard,
and Mariela Rodriguez-Celis (Hydro-Québec-IREQ)
“Is there enough experience to consider a measurement of
methanol (MeOH) as a new marker for early stage paper degra-
dation in transformers?”
Many papers promoting the use of methanol as a marker for early
stage paper degradation have been written since 2007. These funda-
mental papers described different laboratories ageing studies, which
validate the reliability of methanol (MeOH) as a chemical marker for
cellulose paper degradation. Indeed, it has been demonstrated that
MeOH can be produced from both standard and thermally upgraded
Kraft papers under different ageing conditions. The authors demon-
strated the direct relationship between the scission of the glycoside
bond of the cellulose chain and the MeOH generation.
In the particular transformer application, Hydro-Québec and
Électricité de France now use this marker on a regular basis for
the residual life estimation and the diagnostic of cellulose abnormal
ageing. For example, Hydro-Québec experienced a cooling problem
on an OFAF transformer insulated with Insuldur thermally upgraded
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6599
paper. After the analysis of the cellulose chemical markers: ∼100 ppb
of 2-furfural (2-FAL) was found compared to ∼650 ppb of MeOH.
Based on the 2-FAL concentration, the cellulose insulation seems
to be well preserved but the MeOH concentration revealed that the
cellulose has suffered from this lack of cooling.
In 2007, EDF performed analysis by measuring MeOH content
in oil of some transformers in order to detect units with signs of ther-
mal ageing. A follow up during two years of one suspected unit, a
transformer equipped with standard Kraft paper insulation, showed
a relatively high level of methanol and 2-FAL. Indeed, the methanol
concentration was higher than 1000 ppb and more than 2000 ppb of
2-FAL were found. The post-mortem analysis performed by measur-
ing the degree of polymerization (DPv) of 40 paper samples coming
from different areas of the winding gave an average DPv of about
300. A correlation between DPv of paper samples and the chemical
markers concentrations, previously observed, was confirmed.
“What are the known drawbacks and advantages related to the
MeOH utilization when comparing to 2FAL?”
The advantages of using MeOH over 2-FAL are the direct relation-
ship with the cellulose chain scission no matter the insulation paper
is a standard or a thermally upgraded Kraft paper. The early detec-
tion in the transformer oil helps to follow the trend at the beginning
of the transformer operation and/or determine abnormal ageing oc-
curring with the cellulose insulation. It has been also demonstrated
that MeOH is a stable compound over the transformer temperature
operation range.
Like moisture in oil, MeOH is highly influenced by the oil tem-
perature and in the future, it will be very important to correct the
concentration at a given temperature to obtain the real trend. How-
ever, at a less extend, 2-FAL is also temperature dependent.
III. ACTUAL MILL EXPERIENCE
The mill established a goal of an objective measurement of
aging, which would serve as an early indicator, and would allow
real-time tracking of aging progression. The first approach was
based on furans because at that time the authors were not aware
of the problems with furans as a marker for TUP.
IV. PARAPHRASED FROM A 2016 REPORT BY A MAJOR
TESTING LABORATORY
Furanic Compound Diagnostics (most recent sample): New insula-
tion with a high degree of mechanical strength will typically have a
Degree of Polymerization (DP) of 1000-1300. “Middle Aged” paper
is approximately 500 and paper with less than 250 is in its “Old
Age.” Severely degraded insulation with a DP of 150 or less will
have very little mechanical strength and may result in a transformer
failure. The above estimations are based on a study by Chendong of
GSU transformers filled with mineral oil. Estimated Average Degree
of Polymerization
(DP): >1003 Estimated Operating Age of the Equipment: <1.0
Diagnostics: DGA Key Gases/Interpretive Method: PER IEEE
C57.104-2008 (most recent sample) Hydrogen within condition 1
limits (100 ppm). Methane within condition 1 limits (120 ppm).
Ethane within condition 1 limits (65 ppm). Ethylene within condi-
tion 1 limits (50 ppm). Acetylene within condition 1 limits (1 ppm).
Carbon Monoxide within condition 1 limits (350 ppm). TDCG within
condition 1 limits (720 ppm).
Carbon Dioxide: Condition 2 Indications of overheated cellulose
insulation (2500 ppm).
1) DP: >1003 Estimated Operating Age of the Equipment: <1.0
 6600 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 54, NO. 6, NOVEMBER/DECEMBER 2018
2) Carbon Dioxide: Condition 2 Indications of overheated cel-
lulose insulation (2500 PPM).
How can both of these statements apply to the same trans-
former at the same time?
A literature search was undertaken to discover the basis for
these conflicting statements.
1) The first statement mentioned previously is based on the
measured furan concentrations of less than 10 ppb.
2) The second statement mentioned previously is based on
ANSI/IEEE Std. C 57.104.
3) There is a growing body of the literature (see references),
which supports the following arguments.
a) If a transformer is rated for 65° rise the insula-
tion is thermally upgraded paper, which is produced
by a pulping process, which impregnates the pa-
per with a nitrogenous compound usually dicyan-
diamide. Most modern transformers use thermally
upgraded paper which entered general use about
50 years ago.
b) The referenced process of analysis is based on plain
kraft paper, which could be used in a 55 °C rise
transformer but not in a 65 °C transformer.
c) Some degradation products of plain kraft paper are
(CO +CO2 ), H2 0, methanol, and furans.
Generally, CO formation shows temperature dependence and
in cases of absence of a severe fault (no acetylene0 is mainly
derived from the insulating fluid [8]. The C02 content in-
dicates degradation of solid insulation. As a consequence, a
growing trend ratio of CO2 /CO seems to be a better indicator
of solid insulation degradation than carbon oxide alone. The
usually used range of 3–10 should be further specified and
in the case of closed-type transformers, revised. For closed
type systems, or transformers working on a steady high load,
ratios of 0.6 to 5 often have been observed with no fault
indication
d) Some degradation products of TUP are (CO + CO2 )
in quantities about 5 times that for plain kraft, NH3 ,
methanol, but not furans and not H2 O. H2 0 is con-
sumed and not produced. If any furans are produced
they are very quickly consumed by the NH3 .
e) So the high (CO + CO2 ) and the low furans are
both simply due to the fact that the insulation is
TUP and neither can be relied on as an indicator of
life remaining or life used. See [8] quoted above.
The same body of the literature shows that methanol is pro-
duced by degradation of both plain kraft and TUP and is stable
in the transformer mineral oil environment. It presents extensive
reports that co-relate methanol concentration with mechanical
strength of the paper. It is not possible to dismiss use of the
methanol marker for life estimation as unproven or too novel to
consider. At least two major testing laboratories, one in Europe
and one in the USA can test oil samples for methanol.
V. READING LIST OF RELATED PAPERS
A reading list of papers related to the use of methanol as a
chemical marker of insulating materials degradation is given as
[9]–[17].
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VI. WHAT ACTIVITY EXISTS IN THE U.S. REGARDING USE OF
METHANOL AS AN AGING MARKER?
1) What is IEEE doing? The Insulation Life Committee of
the Transformer Society is addressing the issue.
2) What is ASTM doing? There is a working group on stan-
dards for evaluating methanol concentration.
3) What are the testing laboratories doing? The authors have
found only one laboratory, which tests for methanol. They
have been willing to sub contract methanol testing from
another laboratory.
VII. INTERPRETATION
There are no recognized standards for correlating methanol
level with DP and remaining useful life. There are some CIRED
papers with data on which one could base a conclusion.
VIII. CASE HISTORY OF LIFE MARKERS ON INDUSTRIAL
TRANSFORMERS
Below are tabulated data of aging markers, recorded over a
period of 10 years on seven industrial distribution transform-
ers, which use thermally upgraded paper. Acid number, IFT,
moisture, and DBV are impeccable and so are not shown. The
possible life markers considered were as follows:
1) CO + CO2 ;
2) furans;
3) methanol.
CO and CO2 levels in many cases exceed Condition 2 and
in some cases Condition 3 per IEEE Std. 104. Some of the
test reports concluded on this basis that severe overheating had
occurred. A judgement call was made that it is more likely
that the numbers are high because thermally upgraded paper
produces much more CO + CO2 than plain kraft paper.
Furans are essentially zero and some reports concluded that
the paper was therefore like new. It is more likely that the data
only shows that thermally upgraded paper produces essentially
no furans.
Methanol shows a measurable level which indicates that very
little life has been used. Since no published standards are known
to exist, the paper CIRED PAPER 0695 was used as a basis for
evaluation. It indicates that if methanol concentration is less
than 500 ppb then DP is more than 900. The highest methanol
concentration is less than 200 ppb so the indication is that very
little life has been used.
As a check on the use of markers it should be noted that under
actual operating conditions, the highest hot spot temperature
can be shown to be about 80 °C. The acceleration factor for
80 °C hotspot is 0.07. If end of life is taken as 50% retained
tensile strength then the acceleration factor should be applied
to 7.42 years giving a life of 106 years in the absence of water
and oxygen. The transformers have been in service for about
16 years. 16 × 0.07 = 1.14 therefore one could say that a little
more than 1 year of useful life may have been used. A caveat,
which is satisfied, is that all the factors in the liquid screen are
exemplary. Also, low oxygen must be assured and is so assured
by use of a nitrogen blanket in the headspace.
BARE, II AND MERRITT: METHANOL AS AN AGEING MARKER FOR IN SERVICE TRANSFORMERS
TABLE II
CARBON MONOXIDE (CO)
TABLE III
CARBON DIOXIDE (CO2 )
In Tables II and III, the italics indicate a point which is in Condition 2 or 3 for CO
and CO2 .
Table IV expresses condition levels of concern as defined by
IEEE ANSI Standard C 57-104.
Consistent with the research reports shown in Table I, the fu-
ran concentrations in Table V, are below 10 ppb, while the
methanol concentrations in Table VI above are in the rea-
dable low end of the linear range, and can be evaluated by
reference to reliable technical publications.
X. CONCLUSION
The CO and CO2 concentrations are in many instances in
Condition 2 or 3, justifying extreme concern per IEEE Std. 104.
A judgement call was made that the high levels were actually
due to the fact that TUP produces much more CO + CO2 than
kraft, and no special measures were taken. Similarly, the low
furan levels were not accepted as proof that the insulation was
like new. In 2016 the methanol levels on all units were tested.
Since there is not yet an ANSI/IEEE standard for evaluation,
CIRED Paper 0695 Fig. 9 was used for evaluation. This showed
that all units are at the beginning of the linear range of the
plot of DP as indicated by methanol concentration and that the
average DP is about 950. It will now be possible to track DP as
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6601
TABLE IV
C 57–104 CONDITION LEVELS FOR EVALUATION PPM
TABLE V
FURANS
TABLE VI
METHANOL (MEOH)
the transformers age in service. By comparison, even if furans
were produced the level would not rise to a significant point
until the DP had dropped to the 600–700 point many years in
the future. The goal of an objective test to confirm calculations
and to provide real-time tracking of DP has been met.
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Charles E. Bare, II (M’15) received the B.S.E.T.
degree in electrical engineering technology and the
M.E.M. degree engineering management from Old
Dominion University, Norfolk, VA, USA.
He retired from the U.S. Navy with 25 years mar-
itime experience as an Electrician and Chief Engi-
neering Officer. He is currently a consulting Main-
tenance Engineer and Project Manager with High-
ground Services, Inc., Franklin, VA.
Stanley Y. Merritt (M’78–SM’83–LSM’95) re-
ceived the B.S. and M.S. degrees in electrical engi-
neering from the University of Tennessee, Knoxville,
TN, USA, in 1949 and 1952, respectively.
He is a Consulting Engineer with Highground Ser-
vices, Inc., Franklin, VA, USA. He has specialized in
transformer life extension, short circuit and stability
studies, industrial switchgear, and motor control for
many years. He was also a Designer of marine and
aircraft power conversion products at General Elec-
tric Co., earning two U.S. patents for inverter circuits.
He is the author of numerous conference papers for the IEEE Pulp and Paper
Committee.
Mr. Merritt is a registered Professional Engineer in Virginia.