779 - CIGRE - Field Experience With Transformer Solid Insulation Ageing Markers

A2/D1
Technical Brochure
Field experience with transformer

solid insulation ageing markers
Reference: 779
October 2019
TB 779 - Field experience with transformer solid insulation ageing markers
Field experience with
transformer solid insulation
ageing markers
JWG A2/D1.46
Members
J. JALBERT, Convenor and

CA L. HERNANDEZ ES
Secretary
M.L. COULIBALY* FR M.C. LESSARD CA
B. DIGGIN* IE L. LEWAND US
C. LESAINT* NO J. LUKIC RS
L. MELZER* SE R. MAINA IT
Z. WANG* GB M.A. MARTINS PT
S. BHUMIWAT NZ R. MERTENS BE
H. DING GB J. VAN PETEGHEM BE
S. EECKHOUDT BE C. REHOREK GB
K. FUTKUTARO JP M. RYADI FR
D. HEPBURN GB F. SCATIGGIO IT
* Task Force Leader
Corresponding Members
C. BEAUCHEMIN CA S. MATHARAGE GB
M. GRISARU IL M. RODRIGUEZ CA
Copyright © 2019
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ISBN : 978-2-85873-481-8
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ISBN : 978-2-85873-481-8
Executive summary
The irreversible ageing of transformer solid insulation is one of the factors determining its lifetime.
However, it is difficult to obtain paper samples from in-service transformers. For that reason, chemical
markers in oil, which are related to the paper’s ageing, are used to indicate the ageing state of paper
insulation. Markers such as water, carbon oxide gases and furanic compounds have been used for
many decades to monitor the condition of paper insulation.
Around 2007, methanol and ethanol were first proposed as potential paper ageing indicators.
Methanol is generated mainly from cellulose (the main constituent of paper insulation) and ethanol,
from levoglucosan (a major by-product of the pyrolysis of cellulose). Therefore, it was suggested that
methanol be used to indicate normal paper ageing occurring under normal operating temperatures,
and ethanol to indicate abnormal paper ageing occurring due to localized high temperatures. The main
advantages of using methanol over conventional ageing indicators are its ability to indicate the early
stages of paper ageing and the possibility of indicating ageing of thermally upgraded paper.
Furthermore, research has suggested that methanol production could be directly related to cellulose
chain scission. Even though a standard for measuring alcohols of low molecular weight, including
methanol and ethanol, is yet to be published, many transformer users around the world have already
been measuring the methanol and ethanol content of their transformer oil samples. However, most of
them struggle to interpret the results of these novel ageing indicators.
This brochure aims to provide readers with up-to-date information on ageing markers for solid
insulation and to address the challenges faced by transformer users due to the partitioning nature of
these markers. Furthermore, some additional studies related to alcohol markers, including round-robin
tests and early development of interpretation models for methanol in transformers, are included in the
brochure.
Chapter 1 describes the scope of this work.
Chapter 2 looks into the design and operational aspects which generally affect the partitioning of
chemical markers in transformers.
Chapters 3 and 4 include a brief review of transformer insulation, its ageing phenomena and state-of-
the-art information on paper ageing indicators, with the main focus on novel ageing indicators
methanol and ethanol. Reviews on the ageing of cellulose insulation and furanic compounds were
previously conducted by CIGRE working groups and presented in CIGRE brochures No. 738 and No.
494, respectively.
Following the first publication proposing to use methanol as an ageing marker just over a decade ago,
many universities, institutes and utilities around the world have conducted studies on methanol and
ethanol. However, due to the lack of a standard procedure, these laboratories used in-house
techniques to measure these chemical markers in oil. Due to the low concentration levels, methanol
and ethanol in transformer oil are commonly measured by the headspace gas chromatography
technique, using either a mass spectrometry detector or a flame ionization detector. However,
measurement procedures can vary largely between laboratories. Therefore, it is important to conduct
a comparison of laboratories to verify the accuracy of their measurement procedures. Chapter 5
presents the results of two round-robin tests carried out with up to nine laboratories. In addition to
different detection limits from one laboratory to the next, it was noted that inaccurate calibration
samples could be largely attributed to measurement errors.
Partitioning phenomena of ageing markers has always been a challenge for diagnosis. Once the
ageing indicators are generated from paper insulation, there is a back and forth migration between the
oil, the paper and the headspace of transformers needs to be taken into consideration. The
partitioning process can be affected by various factors such as temperature, the condition of the oil,
and the condition of the paper. Hence, Chapter 6 focuses on several studies looking at the impact of
various factors on the partitioning of paper-ageing indicators.
Even though it has been over four decades since the introduction of furanic compounds as paper
ageing indicators, defining limits for these chemical markers and the corresponding intervention
actions have always been a challenge due to the different design and operational aspects of
transformers. The recommendation in CIGRE brochure No. 494 on furanic compounds was to group
assets with similar designs and obtain normal and abnormal levels for the subsets.
5
Chapter 7 focuses on several field case studies including data from scrapped transformers. In
addition to details on the transformers, whenever available, it also includes measurement results for
chemical markers, the reasons for scrapping and the findings of the forensic studies.
Finally, Chapter 8 presents the development of a methanol interpretation model to predict the average
DPv of paper insulation by measuring methanol in oil. The model was constructed by combining the
results obtained from laboratory studies and partitioning studies, taking into account transformer
design aspects.
6
Table of Contents
Executive summary ............................................................................................................. 5
1. Introduction.............................................................................................................. 13
1.1 Background and scope ........................................................................................................................... 13
2. Transformer design aspects ................................................................................... 15

2.1 Design information .................................................................................................................................. 15
2.1.1 Classes and types of power transformers .......................................................................................... 15
2.2 Main design concepts ............................................................................................................................. 15
2.3 Main active materials............................................................................................................................... 16
2.4 Design aspects influencing the amount of active materials ................................................................ 16
2.5 Loading and operation ............................................................................................................................ 16
2.6 Design aspects influencing the generation of ageing markers ........................................................... 17
2.7 Correlation between ageing markers and design types ....................................................................... 17
2.8 Summary .................................................................................................................................................. 19
3. Transformer materials ............................................................................................. 21

3.1 Main cellulosic insulation ....................................................................................................................... 21
3.2 Main insulating liquids ............................................................................................................................ 22
3.3 Cellulosic insulation ageing factors ...................................................................................................... 22
4. State-of-the-art ageing markers .............................................................................. 27

4.1 CO and CO2 Gases .................................................................................................................................. 27
4.2 Furanic compounds ................................................................................................................................ 28
4.2.1 Introduction ........................................................................................................................................ 28
4.2.2 Generation mechanisms .................................................................................................................... 29
4.2.3 Stability of furanic derivatives ............................................................................................................ 30
4.2.4 Partitioning of furanic derivatives ....................................................................................................... 30
4.2.5 Correlation between 2-FAL and DPv ................................................................................................. 31
4.3 Methanol and Ethanol ............................................................................................................................. 32
4.3.1 Origin of methanol and ethanol .......................................................................................................... 33
4.3.2 Stability of methanol and ethanol in oil .............................................................................................. 34
4.3.3 Partitioning of methanol and ethanol between insulation paper and oil ............................................. 35
4.3.4 Laboratory ageing experiments ......................................................................................................... 36
4.4 Kinetic studies on relating paper ageing to the production of methanol ........................................... 38
4.5 Other generation sources of cellulose markers.................................................................................... 45
4.6 In-service experience with methanol and ethanol ................................................................................ 45
4.7 Summary .................................................................................................................................................. 47
5. Round robin on alcohol measurements ................................................................. 49

5.1 First RRT .................................................................................................................................................. 49
5.1.1 Results ............................................................................................................................................... 49
5.1.2 Summary ........................................................................................................................................... 51
5.2 Second RRT ............................................................................................................................................. 51
5.2.1 Results ............................................................................................................................................... 51
5.2.2 Summary ........................................................................................................................................... 54
7
6. Influence of different factors on ageing marker measurement ............................ 55

6.1 Two-temperature rig for partitioning studies ........................................................................................ 57
6.2 Water partitioning in a model system and service-aged materials ..................................................... 58
6.3 Acid partitioning ...................................................................................................................................... 59
6.4 Partitioning of furanic derivatives and alcohols ................................................................................... 60
6.5 Partitioning in synthetic ester ................................................................................................................ 61
7. Field Experience ...................................................................................................... 65

7.1 Case Studies ............................................................................................................................................ 65
8. Interpretation model using methanol ..................................................................... 71
9. Summary and Outlook............................................................................................. 73

9.1 Summary .................................................................................................................................................. 73
9.2 Outlook ..................................................................................................................................................... 73
10. References ............................................................................................................... 75
8
Figures and Illustrations

Figure 2-1: Principles of core-form transformers, from [3] ..................................................................................... 15
Figure 2-2: Principles of shell-form transformers, from [3] ..................................................................................... 16
Figure 2-3: Total cellulose weight in kilograms as a function of rating for a mixed population of GSU transformers,
net transformers and reactors.. .............................................................................................................................. 18
Figure 2-4: Total cellulose weight in kilograms as a function of rating for a close up of the population in Fig. 2-3. 18
Figure 2-5: Total paper weight for winding conductor insulation in kilograms, as a function of rating for the studied
transformer population. .......................................................................................................................................... 18
Figure 2-6: Ratio between total cellulose weight and the sum of total oil and cellulose weight for the studied
transformer population. .......................................................................................................................................... 19
Figure 3-1: Illustration of sample cellulosic insulation for transformers .................................................................. 22
Figure 3-2: Simplified degradation mechanism for transformer paper-oil insulation .............................................. 23
Figure 3-3: Degradation of insulating paper as a function of temperature ............................................................. 24
Figure 3-4: Chemical structure of cellulose molecules .......................................................................................... 24
Figure 3-5: Correlation between paper DPv and tensile strength [1] ..................................................................... 25
Figure 4-1: Chemical structure of furanic compounds [20] .................................................................................... 28
Figure 4-2: Mechanism proposed for the generation of 2-FAL[24] ........................................................................ 29
Figure 4-3: Stability of furanic derivatives at 110°C [19] ........................................................................................ 30
Figure 4-4: Effect of various factors in the partitioning of 2-FAL between oil and paper [31] ................................. 30
Figure 4-5: 2-FAL measurements obtained from 12 countries [20]........................................................................ 31
Figure 4-6: Typical 2-FAL concentrations in different countries and different types of transformers [20] .............. 32
Figure 4-7: Variation of methanol and ethanol in an inhibited mineral oil aged at 130°C [58] ................................ 34
Figure 4-8: Stability of (a) methanol and (b) ethanol in transformer oil (replotted from[40]) ................................... 34
Figure 4-9: Variation of methanol in a synthetic ester liquid during a stability experiment conducted at 130°C .... 35
Figure 4-10: Temperature correction factor (CfM) for various chemical indicators [47] .......................................... 35
Figure 4-11: Variation of methanol and 2-FAL in oil against the number of ruptured bonds obtained from
laboratory ageing experiments conducted with (a) ordinary Kraft paper (b) thermally upgraded paper at
temperatures ranging from 60°C to 120°C [40]...................................................................................................... 36
Figure 4-12: Variation of methanol and 2-FAL in (a) gas-to-liquid (GTL) oil and mineral oil against the number of
ruptured bonds in paper measured during an ageing experiment conducted at 120°C [63] .................................. 37
Figure 4-13: Variation of methanol in (a) synthetic ester and mineral oil against the number of ruptured bonds in
paper measured during laboratory ageing experiments conducted at 80°C, 100°C and 120°C [46] ..................... 37
Figure 4-14: DPv vs. 2-FAL and vs CH3OH (MeOH) of cellulose-based materials versus ageing time (days) and
temperature in mineral oil at 105°C and 122°C ..................................................................................................... 37
Figure 4-15: DPv, 2-FAL and CH3OH (MeOH) vs. ageing time for cellulose-based materials in natural ester at
130°C .................................................................................................................................................................... 38
Figure 4-16: Variation of methanol measured in transformers and reactors in (a) Canada [40], (b) France,Italy,
Ivory Coast and Romania [43], (c) France [54] and (d) United Kingdom [64] ........................................................ 45
Figure 4-17: Concentration of methanol in several in-service transformers before and after temperature correction
[55]. ....................................................................................................................................................................... 46
Figure 4-18: Markers, acidity and moisture content versus the number of transformers [74] ................................ 47
Figure 5-1: Prepared samples with a tolerance of ±10%. ...................................................................................... 50
Figure 5-2: Oxidized oil samples. .......................................................................................................................... 51
Figure 5-3: Standard A Results ............................................................................................................................. 52
Figure 5-4: Standard B Results ............................................................................................................................. 53
Figure 5-5: Oxidized oil sample results .................................................................................................................. 53
Figure 6-1: Total water content vs. relative moisture in paper (left) [85] and mineral oil (right) [86] ....................... 55
Figure 6-2: Equilibrium curves for water in new impregnated insulation with Nynas Nytro 10X and Munksjø paper
.............................................................................................................................................................................. 56
Figure 6-3: Moisture saturation limit vs. temperature for mineral oil with varying acid number content.The NV
values correspond to the total acid number and acid number reduction due to water rinsing: TANTOTAL/TANLMA
[87]. ....................................................................................................................................................................... 56
Figure 6-4: Two-temperature rig ............................................................................................................................ 57
Figure 6-5: Water partitioning for aged systems at four different temperatures (40, 60, 80 and 100˚C). ............... 58
Figure 6-6: Water correction factor for a mineral oil system comparison using [76] and [56]................................. 59
Figure 6-7: Variation in acidity with temperature for a model system (left) and a service-aged system (right) ...... 59
Figure 6-8: Furanic derivatives and alcohols in oil vs. large chamber temperature. Linear plot (left) and lin-log
(right). .................................................................................................................................................................... 60
Figure 6-9: CfM Equilibrium curves obtained for various chemical markers [44, 56]. ............................................. 60
Figure 6-10: Dependence of chemical indicator concentrations in oil,a) CH3OH and b) 2-FAL, with the number of
chain scissions of an ordinary Kraft cellulose specimen under different ageing conditions. .................................. 61
Figure 6-11: Methanol and water correction factors for a synthetic ester and cellulose system [48] ..................... 62
Figure 6-12: Perrier-Lukic equilibrium curves for paper and pressboard in mineral oil [93, 94] ............................. 63
Figure 6-13: Perrier-Lukic equilibrium curves for paper and pressboard in natural esters [93, 94] ........................ 63
Figure 7-1: Partial discharge measurements using bushing test taps, PD levels of 0.95nC and 1.35nC .............. 65
Figure 7-2: Suggested paper sample locations in a HV pancake winding ............................................................. 66
9
Figure 7-3: Shell form transformer ......................................................................................................................... 66

Figure 7-4: HV pancake winding ............................................................................................................................ 66
Figure 7-5: Winding hotspot at the top end of a 400-kV winding in a 1,000-MVA 400/275-kV transformer scrapped
after only 19 years in service ................................................................................................................................. 67
Figure 7-6: Ageing series winding conductor insulation in a 240-MVA 400/132 kV autotransformer scrapped after
48 years of service ................................................................................................................................................ 68
Figure 8-1: a) Solid-insulation ratios for various core-type transformers; b) Paper weight vs. oil weight for various
core-type transformer [56]. .................................................................................................................................... 71
Figure 8-2: Methanol prediction model for core-type transformers [56]. ................................................................ 71
Tables
Table 2-1: Commonly Used Definitions for Power Transformer Classes, Based on [2] ......................................... 15
Table 3-1: Main Cellulosic Solid Materials Used for Power Transformer Insulation ............................................... 21
Table 3-2: Main Insulating Liquids for Power Transformer Insulation .................................................................... 22
Table 4-1: Main Degradation By-products of Cellulosic Insulation ......................................................................... 27
Table 4-2: Causes of Specific Furanic Compounds for Kraft Paper [21] ............................................................... 28
Table 4-3: Yield of Furanic Compounds from Various Components in Paper [18] ................................................. 29
Table 4-4: Constant Coefficients Suggested by Various Researchers .................................................................. 31
Table 4-5: Key Literature Related to Methanol and Ethanol in Transformer Oil ..................................................... 33
Table 4-6: Generation of Methanol and Ethanol from Various Paper Components and Ageing By-products of
Paper [40] .............................................................................................................................................................. 33
Table 4-7: Results of the Kinetic Studies Conducted at Temperatures below 120°C with Thermally Non-upgraded
Kraft Paper ............................................................................................................................................................ 41
Table 4-8: Results of Kinetic Studies Conducted at Temperatures below 120°C with Thermally Upgraded Kraft
Paper ..................................................................................................................................................................... 42
Table 4-9: Results of Kinetic Studies Conducted at Temperatures above 130°C with Thermally Upgraded and
Thermally Non-upgraded Kraft Paper .................................................................................................................... 43
Table 5-1: Random Sample Verification Results ................................................................................................... 49
Table 5-2: Standard A Results............................................................................................................................... 50
Table 5-3: Standard B Results............................................................................................................................... 50
Table 5-4: Transformer Oxidized Oil Results ......................................................................................................... 51
Table 5-5: Standard A Results............................................................................................................................... 52
Table 5-6: Standard B Results............................................................................................................................... 52
Table 5-7: Oxidized Oil Results ............................................................................................................................. 53
Table 6-1: Correction Factors for Water and Ageing Markers in Mineral Oil or Synthetic Ester ............................ 62
Table 7-1: Transformer Parameters ...................................................................................................................... 65
Table 7-2: Oil Analysis ........................................................................................................................................... 65
Table 7-3: DPv Results Taken during Teardown ................................................................................................... 67
Table 7-4: Ageing Markers of Scrapped 1,000-MVA Transformer ......................................................................... 68
Table 7-5: Ageing Markers of Scrapped 240-MVA Transformer ............................................................................ 68
Table 7-6: Transformer Parameters ...................................................................................................................... 69
Table 7-7: DGA Data before Removing Transformers from Service ...................................................................... 69
Table 7-8: Ageing Markers for the Six Transformers ............................................................................................. 69
Table 8-1: Methanol Threshold Level and Its Condition [56].................................................................................. 72
Equations
Equation 3-1 .......................................................................................................................................................... 24
Equation 3-2 .......................................................................................................................................................... 24
Equation 3-3 .......................................................................................................................................................... 25
Equation 4-1 .......................................................................................................................................................... 31
Equation 4-2 .......................................................................................................................................................... 31
Equation 4-3 .......................................................................................................................................................... 35
Equation 4-4 .......................................................................................................................................................... 36
Equation 4-5 .......................................................................................................................................................... 38
Equation 4-6 .......................................................................................................................................................... 38
Equation 4-7 .......................................................................................................................................................... 39
Equation 4-8 .......................................................................................................................................................... 39
Equation 4-9 .......................................................................................................................................................... 39
Equation 4-10 ........................................................................................................................................................ 39
Equation 4-11 ........................................................................................................................................................ 39
Equation 4-12 ........................................................................................................................................................ 39
10
Equation 4-13 ........................................................................................................................................................ 40

Equation 4-14 ........................................................................................................................................................ 40
Equation 5-1 .......................................................................................................................................................... 49
Equation 6-1 .......................................................................................................................................................... 58
Equation 8-1 .......................................................................................................................................................... 71
Equation 8-2 .......................................................................................................................................................... 72
Equation 8-3 .......................................................................................................................................................... 72
11
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1. Introduction
1.1 Background and scope
This report discusses field experience with new ageing markers for cellulosic insulation materials in
mineral-oil-filled power transformers and reactors and measuring the degree of polymerization (DPv)
of samples taken from transformers during repairs, refurbishment or scrapping. Some examples of
results obtained with other types of liquid are also presented, for comparison purposes only.
Power transformers are key components of any energy production, transmission and distribution
network. Their insulation systems, composed mainly of cellulose/oil, can undergo degradation as a
result of chemical reactions involving pyrolysis (initiated by thermal stress), oxidation (initiated by the
presence of air) and hydrolysis (initiated by the presence of water and acids). Combinations of these
chemical reactions cause the insulation to age and reduce the degree of polymerization in particular,
leading to a loss of the cellulosic insulation’s mechanical properties and impacting a transformer’s life
expectancy.
In many countries, most of the transformers in service are reaching or have already exceeded their
expected end of life. Thus, transformer users are dealing with an ageing population and must develop
a transformer reinvestment program. Information on the condition of the insulation of these
transformers, particularly cellulosic materials, can be used as a key parameter in assessing the
condition of a transformer fleet and selecting the best reinvestment option (repair/refurbish/replace).
In assessing cellulosic insulation ageing conditions, the key characteristic to be evaluated by direct
measurement is the degree of polymerization determined by viscosimetry (DPv). DPv is directly linked
to the mechanical properties of cellulose. When new, cellulosic insulation has a DPv of around 1,000
to 1,200 before the vapor phase process and about 900 afterwards. Cellulose approaches its end of
life with a DPv around 200, corresponding to 20% (CIGRE brochure No. 323) [1] or 35% (IEC 60076-
7) of retained tensile strength [2]. However, DPv and/or tensile strength cannot be directly measured
while transformers are in service due to the non-accessibility of the cellulose-based materials.
Sampling can be done when transformers (no longer in service) have to be repaired, refurbished,
scrapped/replaced or have their windings dismantled, which provides access to critical solid insulation
components that are not otherwise accessible. Another option is to place samples of insulating
material in a basket accessible via a panel on the lid, which can then be withdrawn for the purpose of
testing DPv, mechanical properties or other characteristics during a suitable transformer outage.
To overcome this disadvantage, insulation ageing status could be assessed by analyzing the
degradation by-products of cellulosic materials released in oil. Conventional methods involving the
analysis of furanic compounds (2-FAL) and dissolved gases (CO and CO2) in oil can be applied to the
monitoring of cellulosic insulation[1]. These methods have been used for several decades and are
very useful in transformer monitoring, but they present some limits.
Moreover, in order to apply ageing markers and transformer ageing models more accurately, certain
transformer design information, such as the quantities of oil and solid insulation (paper and board), is
required. Knowing that the quantity of insulating materials is directly linked to transformer design, the
use of ageing marker models can be significantly improved by comparing their concentrations
dissolved in oil with the quantity and the nature of the materials involved.
The main topics discussed in this paper are as follows:
▪ Identification of transformer design information relevant to ageing marker models (e.g., ratio of
transformer oil, paper and board, also the type of solid insulation, type of insulating liquid, type
of cooling system, type of preservation system, thermal characteristics, etc.)
▪ Consideration of the effect of oil sampling temperature on marker concentrations, taking into
account transformer design
▪ Field case study to evaluate the correlation between existing chemical markers and
paperboard DPv, taking into account transformer design information and, if applicable,
transformer operation and maintenance records
▪ Marker limitations and determination of their specific application (remaining life assessment
and/or diagnostics)
▪ Recommendations on insulation system end-of-life criteria, based on ageing markers
▪ Comparison with other diagnostic techniques, where applicable
13
14
2. Transformer design aspects

Prior to making a specific transformer diagnosis based on ageing markers, an understanding of how a
transformer is designed, including the quantity of materials involved in an actual device, is crucial.
2.1 Design information

2.1.1 Classes and types of power transformers
Power transformers are used for different purposes and can generally be classified as generator step-
up transformers, transmission and interconnection transformers, distribution transformers and “special
transformers.” Special transformers include industrial transformers, phase shifters and HVDC
transformers. Shunt reactors are to be regarded as one of the “special types” of transformers. In this
study, series reactors have not been included due to the extremely low number of such units installed.
The physical size of transformers varies greatly, depending on rating and voltage class. The largest
units may have a total weight around 550 tonnes, while small distribution transformers weigh less than
1 tonne.
It is common to separate power transformers into large, medium and small transformers. Although
there are no clear definitions of these categories, IEC 60076-7 [2] defines them as follows: small-
power transformers, distribution transformers, often defined as 2,500 kVA and below, medium-power
transformers, which are between 2,500 kVA and 100 MVA, and large-power transformers, which are
larger than 100 MVA, as seen in Table 2-1.
Table 2-1: Commonly Used Definitions for Power Transformer Classes, Based on [2]
Group Rating Comment

Small-power Power transformers with no attached radiators, coolers or
tubes, including corrugated tank irrespective of rating
Distribution Max 2,500 kVA
2,500 kVA – 100 MVA 3-phase
Medium-power
< 33.3 MVA 1-phase
> 100 MVA 3-phase
Large-power
>33.3 MVA 1-phase
2.2 Main design concepts

Within these classes, different fundamental design concepts exist. The two most common transformer
design concepts are core form and shell form, with core form being the predominant concept. Both
concepts have their respective strengths and preferred applications. In a nutshell, core-form
transformers are built with the windings around the core, whereas shell-form transformers are
designed with the cores built around the windings. Both the winding design and core design are
fundamentally different for these concepts, as shown in Figures 2-1 and 2-2.
Figure 2-1: Principles of core-form transformers, from [3]
15
Figure 2-2: Principles of shell-form transformers, from [3]
Shunt reactors too can be designed according to these two concepts. However, there are very few
manufacturers worldwide today using the shell-form concept for shunt reactors.
2.3 Main active materials

The main materials in a power transformer are the magnetic-core steel (which guides the flux through
the windings in a controlled manner), copper winding conductors, oil (which provides insulation as well
as cooling) and solid insulation, mostly cellulose-based. The solid insulation can be separated into
paper, used to insulate winding conductors, cleats and leads, and pressboard, used to provide
mechanical support and distances in electrically stressed parts of the design. In some transformers,
wood is used as an alternative to pressboard in some components. However, the location of the wood
in the transformer is not subjected to temperatures high enough to contribute to the generation of
ageing markers to the same degree as winding paper would be. However, some older transformers
may have wooden packers on the core, which can reach high temperatures when in service. As these
materials are used in different parts of the transformer, they are subjected to very different
temperatures.
2.4 Design aspects influencing the amount of active materials

In general, the larger the transformer, the more active the material. However, the relative share of
active materials depends not only on the voltage and rating for the various transformer classes and
types, but also on the specifications and applications. Evaluation of losses, sound level requirements,
transport limitations, specified insulation levels and maximum temperature rises are some of the
specification-driven aspects that influence the relative weighting of the materials. For example, the
higher the loss evaluation, the more core steel and the more copper, and consequently the more
paper, is used in the design. In the same way, the higher the specified insulation level, the more solid
insulation is required.
Different types of windings have different relative amounts of paper and pressboard. Disc windings,
layer windings, and windings with or without enamelled conductors all have different relative amounts
of paper and pressboard.
The relative amount of active materials also differs by manufacturer and time period. For example,
transformers manufactured during the 1960s and 1970s by certain OEMs have a larger amount of
paper insulation for the same design than units built by other manufacturers. This does not reflect any
difference in quality or functionality, merely the design philosophy and how the insulation system is
built.
2.5 Loading and operation

From an operations point of view, GSU and shunt reactors are normally fully loaded. However,
interconnection transformers tend to be less than half loaded due to N-1 network stability rules of
operations and the fact that transformers are sometimes taken out of service to control substation
short-circuit levels at peak load.
Shunt reactors always operate at their rated load, with small variations due to voltage variances on the
grid. Industrial transformers often have strongly varying load cycles with periods of high overload.
16
Load profiles such as the dynamic nature or pattern of the load, whether cyclical or not, affect the
temperature profile experienced by a transformer during its lifetime and thus the production of ageing
markers. Temperature is in fact the dominant factor determining ageing.
Real operation scenarios also include factors like cooling system, ambient temperature, and country
and region climate.
2.6 Design aspects influencing the generation of ageing markers

In addition to loading profile and ambient temperature, other design-specific aspects influence the
generation of ageing markers. For instance, the cooling system/mode specified should be taken into
account. Owing to differences in hotspot factor and in top oil rise, the hot spot temperature with ONAN
cooling may be higher than the hot spot temperature with ODAF or OFAF cooling for transformers with
both ratings. For example, a transformer may operate in ONAN cooling mode with a hot spot
temperature may be higher than for ODAF at a higher load.
There may also be differences in design and construction for some older transformers, manufactured
before the 1980s. In general, these have higher hot spot factors than more modern designs, but this is
not always the case.
In addition, over the lifetime of a transformer, during which the “loss” of ageing indicators such as
gases, methanol and 2-FAL can occur, different behaviors are expected for sealed tanks and free-
breathing transformers. Gaskets, seals and breathers may also contribute to the entry of moisture that
can affect the concentration and type of markers.
Although it is not a design aspect, it is also worth mentioning that a transformer sometimes undergoes
work such as maintenance (which can include degassing or oil regeneration) or be opened up for
other operations (repair work and oil treatment during service). These activities will effect changes in
the concentration of ageing markers and hence make the lifetime assessment incorrect if they are not
properly taken into account.
2.7 Correlation between ageing markers and design types

The ratio of cellulose to total insulation is considered to be the key parameter for the partitioning of
ageing markers. Although there are different types of transformer classes, the cellulose-to-total-
insulation ratio is expected to be different even among transformers in the same class. We also
assume that the main locus of ageing marker production is the hot spot region, corresponding
approximately to the top 10% of the winding height.
In order to verify this assumption, variations in this ratio in relation to different design aspects were
studied. The population under study consists of 65 core-form transformers from two manufacturers
with ratings in the 70–765 kV and 20–1,150 MVA ranges, as well as 10 shell-form transformers with
ratings in the 138–525 kV and 187–1,120 MVA ranges.
Total cellulose weight as a function of rated power for a mixed population of GSU transformers, net
transformers and reactors is shown in Figure 2-3, and for the lower ratings a more detailed
presentation is shown in Figure 2-4. These figures show that cellulose weight does not increase
linearly with rated power, but with the square root of rated power. The spread of cellulose weight for a
given rating is also large: more than 100% in some cases. This can be understood in the light of the
discussions presented in the previous chapters. The influence of the specifications and design
concept is considerable and will influence any attempts to make a quantitative evaluation of insulation
ageing based on the concentration of ageing markers in oil.
17
 Core and  Shell forms
Figure 2-3: Total cellulose weight in kilograms as a function of rating for a mixed population of GSU
transformers, net transformers and reactors.
Figure 2-4: Total cellulose weight in kilograms as a function of rating

for a close up of the population in Fig. 2-3.
Figure 2-5 shows the amount of paper only (i.e., the winding conductor insulation) as a function of
rating for the total population studied. The same trend as in Figures 2-3 and 2-4 can be observed
here; there is no clear correlation between rating and paper weight and the spread is also large—in
this case, more than 300% for units of the same rating.
Figure 2-5: Total paper weight for winding conductor insulation in kilograms, as a function of rating for the studied
transformer population.
18
When the ratio between total paper weight and the sum of total paper weight and oil weight is plotted
as a function of rated power (Figure 2-6), the same pattern can be seen again but even more
markedly. There is no obvious correlation between the parameters, and the spread is large.
● Core and  Shell forms.
Figure 2-6: Ratio between total cellulose weight and the sum of total oil and cellulose weight for the studied
transformer population.
All units in the population are of “modern design”: i.e., designed in the last 10 years. However, in
comparing this equipment with older designs from various manufacturers, the same pattern as
discussed above was observed, with a weak correlation to rated power and voltage, and a large
spread between units of the same rating.
2.8 Summary
It has been shown that differences in concept, specification-related design, operation and type of
transformer have a large impact on the amount of cellulose in a transformer. No strict correlation
exists between rated voltage or power and the cellulose ratio in the transformer. The cellulose ratio
spread is large (up to 300% or more) between units with the same rating. This means that for a given
unit, is impossible to establish a reference or normal level for the concentration of ageing markers in
oil. As a result, an assessment based on ageing markers cannot be quantitative or, for instance, serve
as a decision-making factor for taking the transformer out of service. Instead, it should be regarded as
an indicator for the “end of life” or “consumed life” of an insulation system, preferably in combination
with other diagnostic methods to ensure a reliable assessment of the transformer’s condition. In
general, no matter if it is a core- or shell-type transformer, ratios for cellulose to total insulation—i.e.,
cellulose plus liquid—vary by 5% to 25%, irrespective of ratings and voltages.
19
20
3. Transformer materials
3.1 Main cellulosic insulation
Due to their affordable cost and beneficial properties, cellulose-based materials are by far the most
common solid insulation used in power transformers in combination with insulating liquids. Made from
pure cellulose, they have excellent electrical characteristics (good performance in electric fields) and
oil impregnation characteristics, as well as good mechanical properties. In addition, they are capable
of being adapted to specific oil-filled power transformer applications (molded, wrapped, bent, sawn,
ground, milled, etc.). Table 3-1 outlines the main cellulosic insulation used in power transformers.
Some of these insulation systems are illustrated in Figure 3-1.
Table 3-1: Main Cellulosic Solid Materials Used for Power Transformer Insulation
Solid insulation1 Thermal class2 Composition Material description

(°C) and characteristics
Paper (conductor wrapping, soft 105 Sulphate wood pulp IEC 60554-3-1: 1.1-
paper bushing) 1.4
Crepe paper (lead insulation, 105 Sulphate wood pulp IEC 60554-3-3: 3.1 -
shield rings, RIP bushings). 3.2
Extensible, allows higher wire
diameter.
3
Thermally upgraded paper 120 Sulphate wood pulp IEC 60076-14
(TUP/TUK)
Pressboard 105 Sulphate wood pulp IEC-60641-3-1
Radial spacers (in the winding) 105 Sulphate wood pulp IEC 60641-3-1: B.3.1
Cylinders and strips (between 105 Sulphate wood pulp IEC 60641-3-1: B.3.1
windings)
Angle rings, caps, snouts, lead 105 Sulphate wood pulp IEC 60641-3-1:
exit insulation (moldable) B.4.1/5.1
Laminated wood 105 Pressboard laminated with IEC 60763-3-1
casein glue, phenolic glue or
polyester resin
Wood clamping rings and plates 105 Beech veneer IEC 61061-3-1: C1R /
bonded with phenolic resins C2R C3R / C4R
Laminated pressboard 105 Beech veneer, wood veneer, IEC 61061-1
phenol-formaldehyde resin
Pressboard clamping rings and 105 Sulphate wood pulp IEC 60763-3-1:
plates bonded with casein or LB.3.1.A1/LB3.1A2
polyester resins
1
Solid insulation in transformers also includes non-cellulose-based materials, e.g. Bakelite, glass fibre, aramid, etc. 2 According
to IEC 60085. 3TUP/TUK: Cellulose-based paper which has been chemically modified to reduce its rate of
decomposition/degradation, according to IEC 60076-2. [4]. Stabilizing agents, such as nitrogen compounds, are used to
thermally upgrade the paper. A paper is considered as thermally upgraded if it meets the life criteria defined in ANSI/IEEE
C57.100, has 50% tensile strength retention after 65,000 hours in a sealed tube at 110°C or meets any other combined
time/temperature requirement defined by the equation in [4]. Kraft papers or crepe papers can be both thermally upgraded.
21
Kraft paper Laminated wood
Cap sectors with snouts Laminated pressboard
Figure 3-1: Illustration of cellulosic insulation for transformers
3.2 Main insulating liquids

Liquid dielectrics are used as an electrical insulating medium, as a cellulose impregnation fluid and for
heat transfer. The main insulation liquids used in power transformers are listed in Table 3-2.
Table 3-2: Main Insulating Liquids for Power Transformer Insulation
Liquid insulation Thermal class1 Materials description and

(°C) characteristics
Mineral oil
Inhibited 105 IEC 60296
Uninhibited 105 IEC 60296
Ester
Synthetic 130 IEC 61099
Natural 130 IEC 62770
Blended - -
Silicone
Silicone 155 IEC 60836
1
IEC 60085, IECPT63012
3.3 Cellulosic insulation ageing factors

Cellulose insulation in a transformer has two important roles: to provide good electrical insulation to
withstand high voltage stresses, and to provide sufficient mechanical strength to withstand high load
current, fault current or short-circuit current. In spite of having good electrical and mechanical strength,
degradation or ageing does occur in cellulose and its end of life is reached sooner or later. Heat is the
major parameter that affects the mechanical strength of cellulose by breaking its glycosidic bonds.
Heat is generated in spite of normal loading. Cellulose overheating can also occur when the oil loses
its cooling function or when the oil ducts inside the windings are partially blocked by sludge. Figure 3-2
presents an example of a simplified degradation mechanism for transformer insulation. Figure 3-3
presents the effect of thermal degradation for different temperatures, after heating the papers for 20
seconds [5].
The main degradation mechanisms are the following:

▪ Pyrolysis or thermo-kinetic degradation: The cellulose is degraded by heat generated by the
load current or fault current, without the influence of water, oxidation or any other agent which
may initiate the decomposition. Many by-products are generated by this pure pyrolysis at high
temperatures (levoglucosan, CO, CO2, furanic derivatives, alcohols, water, etc.). Since the
cellulose is immersed in oil, interaction with oil components does occur and the last molecules
can be converted to other substances (e.g., sludge, acid, etc.).
▪ Hydrolysis: Water is the primary component affecting cellulose ageing. Because of the
hygroscopic nature of cellulose and its fibre structure (capillaries), water molecules
accumulate between the cellulose chains and thus promote thermohydrolytic degradation.
Water forms as a reaction product during both thermo-kinetic degradation of the cellulose and
22
the ageing of oil. The moisture present at the beginning of the ageing process, as well as the
water formed by the reactions of the cellulose and oil, cause additional decomposition of the
chain molecules, apart from the thermo-kinetic degradation. The water continuously causes
fresh molecular cleavage and thus has the negative property of constantly accelerating the
cellulose ageing process. For a new transformer, the water level in cellulose is around 0.5%
after this process and can rise to 5% over its lifetime. For example, a 4% water level in
cellulose contributes to increasing its degradation rate by a factor of 20, compared to cellulose
with an initial water level of 0.5% [1]. This process is auto-accelerated.
▪ Oxidation: In a free-breathing transformer or a sealed transformer with deteriorated sealing
systems, oxygen inside the transformer reacts with unstable hydrocarbons in the oil to form
oxidation by-products (peroxide, alcohols, ketones, acid, etc.). Oxidation by-products then
accumulate at the oil-paper interface (the surface of the paper immersed in the oil). At a
certain level, these by-products or so-called “sludge” are formed and then accumulate in the
oil ducts inside the windings, causing a partial blockage of the oil ducts and preventing the oil
from fulfilling its role in cooling the cellulose. Heat occurring inside the oil ducts accelerates
the generation of oxidation by-products, which further increases the dielectric dissipation
factor and dielectric loss.
Figure 3-2: Simplified degradation mechanism for transformer paper-oil insulation
23
Figure 3-3: Degradation of insulating paper as a function of temperature
Cellulose is a polymeric chain of anhydrous-ß-glucose joined by glycosidic bonds. The degree of

polymerization is the average number (n) of glycosidic rings per cellulose macromolecule. See Figure
3-4 (IEC 60450)[6].
Figure 3-4: Chemical structure of cellulose molecules
The degree of polymerization is directly related to the mechanical properties of cellulose and is the
most important parameter in assessing the ageing status of cellulose insulation in transformers. When
new, the DPv (initial) is around 1,000 to 1,200 before the vapor phase drying process, decreasing to
about 900 after the process. Approaching its end of life, DPv can reach values around 200 to 250,
corresponding to a remaining tensile strength of about 35% to 50%, respectively (Figure 3-5).
The reduction in DPv value during ageing, from DP0 (initial DPv) to DPt (DPv measured at instant t) is
characterized by cellulose molecule chain scission (). Chain scission determines the cellulose ageing
rate.
DP0
 1 Equation 3-1
DPt
The ageing of cellulose insulation by chemical degradation is described by the Arrhenius model.
 EA
1 1
  A  e RT  t Equation 3-2
DPt DP0
R: molecular gas constant (8,314 J mole-1 K-1)
T: absolute temperature (K)
A (pre-exponent value): constant, depending on the chemical environment
EA: activation energy
24
Figure 3-5: Correlation between paper DPv and tensile strength [1]
The activation energy of the reaction is the amount of energy needed to start the reaction. It is the
minimum energy needed to form an activated complex during a collision between reactant molecules.
Many studies in the literature provide energy values around 111 kJ/mol. (see summary in [7]). Based
on the chemical degradation equation from the Arrhenius model (3-2), the lifetime assessment
equation for cellulose insulation can be obtained:
1 1
 EA
· e  year 
DPt DP0
Expected Life  RT Equation 3-3
A · 24 · 365
DP0 = 1,000 – 1,200; DPt: defined by the user according to selected safety margins for the
transformer.
However, the drawback in using direct DPv measurement for the diagnostic is the non-accessibility of
cellulose-based materials in service. Indirect methods involving the analysis of cellulose degradation
by-products in oil could allow for ageing status monitoring.
25
26
4. State-of-the-art ageing markers

Even though DPv or tensile strength measurement can indicate the ageing state of paper insulation, it
is difficult to obtain paper samples from a transformer in service for these measurements. Therefore, it
is common to measure cellulose degradation by-products in oil and correlate with the ageing state of
paper insulation. Table 4-1 summarizes the main chemical markers used to predict the ageing state of
cellulose insulation.
Table 4-1: Main Degradation By-products of Cellulosic Insulation
Degradation by-products Standard method of determination Type

2-FAL (2-Furfuraldehyde) IEC 61198 Furanic compounds
CO, CO2 IEC 60567 Dissolved gas
Water (H2O) IEC 60814 Moisture content
CH3OH/CH3CH2OH (new markers) IEC 630251 Alcohols
1
To be published later.
Many scientific papers, conferences, brochures, etc. have been published on the use of existing
cellulose ageing markers. Prior to describing the use of the new markers, this chapter provides a brief
review of existing markers along with their use and limits.
4.1 CO and CO2 Gases

The invention of the Bucholz relay in the early 20th century can be considered the first step toward
the use of gas generation as a fault detection method for transformers [8]. The identification and
quantification of these gases collected in the relays provided further insight into the faults generated in
the transformers. Orsat analysis, infrared spectrophotometry, gas chromatography and thermal
conductivity detection were among the methods used to measure these fault gases [9]. Later, with the
development of vacuum extraction methods, it became possible to measure the gases dissolved in
transformer oil, which drastically reduced fault detection time compared to the analysis of gas
collected from the relay [10]. In addition to vacuum extraction, other methods such as the stripping
method and headspace method are also used to extract gases dissolved in transformer oil [11].
Dissolved gas analysis (DGA) measurement can be interpreted by different methods, including the
key gas method, ratio methods such as the Dornenburg method, Rogers’s method and trilinear
schemes such as the Duval triangle methods [12, 13].
Carbon monoxide and carbon dioxide generation from paper ageing is a phenomenon known to the
transformer industry since the early 1930s [14]. However, measurement of these gases as a condition
monitoring tool has been widely practised only since the early 1970s, leading to the inclusion of these
two gases in the first international standards on the interpretation of dissolved gas measurements [12,
15]. The current IEC standard 60567 [11] recommends a CO2/CO ratio between 3 and 10 as an
accepted range for a normal transformer. Furthermore, it states that a ratio below 3, together with CO
levels of about 1,000 ppm, could be an indication of a paper-related fault, and that a ratio greater than
7, with CO2 levels above 10,000 ppm, could be an indication of mild overheating [13]. On the other
hand, the equivalent IEEE standard suggests that a CO2/CO ratio of more than 7 is normal. It also
emphasizes the requirements of CO2>5,000 ppm and CO>500 ppm in order to ensure an improved
certainty factor [12]. However, experiments have shown that the concentration of these gases and
hence the ratio can be affected by temperature-dependent partitioning between oil and paper [16]. In
addition, CO and CO2 in transformers are not generated exclusively by paper ageing. These gases
can be generated from long-term oil oxidation and overheating of wooden blocks, hindering the use of
these gases as ageing indicators [13]. Furthermore, absorption of CO2 from the atmosphere is also a
major issue that could affect prediction accuracy for free-breathing transformers.
27
4.2 Furanic compounds

4.2.1 Introduction
Furanic compounds were first identified as transformer paper-ageing indicators in the early 1980s
[17]. Six furanic compounds, namely 2-furfural (2-FAL), 2-acetylfuran (2-ACF), 2-furoic acid, 5-methyl-
2-furfural (5-MEF), 2-furfurylalcohol (2-FOL) and 5-hydroxymethyl-2-furfural (5-HMF), shown in Figure
4-1, were identified as potential paper ageing indicators. Of these furanic compounds, 2-FAL is used
more than the others due to its greater stability in oil and availability at higher concentrations than the
others in transformers [18, 19].
Figure 4-1: Chemical structure of furanic compounds [20]
Furthermore, a diagnostic model, shown in Table 4-2, was proposed as a result of the observation of
changes in furanic compounds over time with the presence of known conditions [21]. Nevertheless,
years of service experience have shown that 2-FAL has a higher relative abundance in oil than the
other furanic compounds [21].
Table 4-2: Causes of Specific Furanic Compounds for Kraft Paper [21]
Compound Observed cause

5-HMF Oxidation
2-FOL High moisture
2-FAL General overheating or normal ageing
2-ACF Rare; causes not fully determined
5-MEF High temperatures
Various measurement techniques such as wet tests, thin-layer chromatography, colorimetry, gas
chromatography and high-performance liquid chromatography have been used to measure furanic
compounds in oil [20]. Of these techniques, liquid chromatography—which has detection limits in the
parts-per-billion (ppb) range—is most commonly used as it is cheaper and less complex than the
other techniques [22].
Furanic compounds are not exclusively generated by cellulose but also by other components of paper
and paper ageing by-products [23]. Individual ageing of various components in paper and paper
ageing by-products, as shown in Table 4-3, shows that hemicellulose components (pentosan) could
be the main contributor to 2-FAL production, followed by cellulose, levoglucosan and lignin [23].
28
Table 4-3: Yield of Furanic Compounds from Various Components in Paper [18]
Weight 2-FAL 5-HMF 2-FOL 5-MEF 2-ACF

(g) (ppm) (ppm) (ppm) (ppm) (ppm)
Cellulose 0.5 176 15.5 14 12 5
Pentosan 0.5 600 ND ND 4 2
Lignin 0.5 1.1 0.4 1.1 0.2 1
Levoglucosan 0.3 28 12 14 0.8 0.2
4.2.2 Generation mechanisms
Figure 4-2 shows two mechanisms proposed for the generation of 2-FAL: hydrolysis and pyrolysis of
cellulose [23, 24]. Under the first mechanism, the hydrolysis of glucose units would result in the
formation of an epoxide or enol, which would then undergo internal rearrangements followed by
further dehydration and elimination of formaldehyde to yield 2-FAL. The second mechanism is the
pyrolysis of levoglucosan (1,6-anyhydro-β-D-glucopyranose) through several bond rearrangements
together with further dehydration and elimination of formaldehyde (or hydrogen and carbon monoxide)
to yield 2-FAL.
Figure 4-2: Mechanism proposed for the generation of 2-FAL[24]
29
4.2.3 Stability of furanic derivatives

Stability of furanic compounds in transformer oil was investigated at temperatures ranging from 80°C
to 120°C [19, 25-27]. It was shown that furanic compounds are stable up to about 80°C. However, a
reduction in furanic compounds was observed at temperatures above 110°C, as shown in Figure 4-3
[23, 27].
Figure 4-3: Stability of furanic derivatives at 110°C [19]
4.2.4 Partitioning of furanic derivatives

In an oil-paper system, the concentration of the furanic compounds measured in oil is the quantity left
in the oil after being partitioned between oil and paper. Typically, furanic compounds are absorbed
more readily into paper than in the oil. Various partitioning coefficients have been proposed for furanic
compounds at different temperatures [25, 28]. Apart from temperature, partitioning of furanic
derivatives can be affected by other compounds in the system such as moisture and acids [25, 29,
30]. Figure 4-4 shows the effect of some of these factors in 2-FAL partitioning between oil and paper
[31]. It shows that 2-FAL partitioning between oil and paper is:
 greatly influenced by paper humidity
 less influenced by temperature, unless it is in conjunction with an acidic oil
 different for each furanic compound (particularly for 5-HMF and 2-FAL)
 influenced by the type of paper
Figure 4-4: Effect of various factors in the partitioning of 2-FAL between oil and paper [31]
30
4.2.5 Correlation between 2-FAL and DPv

A logarithmic relationship in the form of equation 4-1 was suggested by many researchers to relate
the concentration of 2-FAL with the DPv of paper [17, 32, 33]. Table 4-4 summarizes some of the
constant coefficients suggested by researchers.
𝐿𝑜𝑔10 [2 − 𝐹𝐴𝐿] = 𝐴 − 𝐵 × [𝐷𝑃𝑣] Equation 4-1
In the above equation, [2 − 𝐹𝐴𝐿] and DPV represent the concentration of 2-FAL and the DPv of paper,
respectively. The terms A and B are constant coefficient values.
Table 4-4: Constant Coefficients Suggested by Various Researchers
2-FAL concentration A B
unit
Burton [17] mg/g paper 0.714 0.0036
Shroff [33] mg/l 97.08 0.1239
Chengdong [32] mg/l 1.51 0.0035
Pahlavanpour [34] µg/kg 4.4394 0.0046
In addition, other relationship formulations have also been developed, such as the one shown in
Equation 4-2 developed by DePablo, which is based on the theory of cellulose chain scission [35].
7100
𝐷𝑃𝑣 = Equation 4-2
[2 − 𝐹𝐴𝐿] + 8.88
In the above equation, [2 − 𝐹𝐴𝐿] and DPv represent the concentration of 2-FAL in oil and the DPv of
paper.
Nevertheless, these relationships do not agree with each other for most DPv values, and it is also
impossible to use a single model for all transformers as they differ in many respects, including design
and loading conditions. Furthermore, a statistical study with more than 30,000 2-FAL measurements
obtained from 12 European countries, plotted in Figure 4-5, has also shown a large variation in 2-FAL
measurements regardless of transformer age [20]. Fig. 4-5 shows that very low concentrations of 2-
FAL (e.g., 0.01 & 0.02 mg/kg) are detected at any transformer age, from 2 to 40 years in operation.
The substantial variation in 2-FAL data is understandable, given that they are raw measurements
without any corrections being applied for their partitioning effect, transformer design, loading
conditions, oil reclaiming, etc.
Figure 4-5: 2-FAL measurements obtained from 12 countries [20]
Consequently, it is common to use other methods to monitor the condition of a transformer, such as a
comparison of furanic derivatives concentration using a threshold value based on statistical analysis
of a large population or a trend analysis of furanic derivatives concentration over time [36]. Based on
a set of in-service measurements obtained during the early 1980s, it was suggested that for an oil-
filled transformer with an oil: paper mass ratio of 20:1, 2-FAL concentrations on the order of 0.5 ppm
can be considered significant, while concentrations above 1 ppm give cause for concern [17]. Later, in
31
2002, Canadian researchers proposed deeming 2-FAL concentrations from 1.0 to 2.0 ppm to be a
cause for concern and concentrations greater than 10 ppm as an end-of-life indication [37]. However,
a recent statistical approach based on a post-mortem analysis of scrapped transformers in the UK
has shown that 2-FAL concentrations of about 2 to 3 ppm could be an indication of reaching end of
life for a transformer [38].
A CIGRE working group (WG D1.01 (TF 13)) investigating 2-FAL found that there are distinct typical
2-FAL levels for different transformer types since transformer size and voltage rating can affect the
oil:paper ratio and hence the quantity of 2-FAL produced [20]. Figure 4-6 shows the typical 2-FAL
concentrations calculated for different countries and types of transformers.
Figure 4-6: Typical 2-FAL concentrations in different countries and different types of transformers [20]
After nearly four decades of experience with 2-FAL, it has not yet been possible to agree on a
universal value or range describing the condition of paper insulation for various reasons, including
indicator partitioning and stability. Therefore, CIGRE working group WG D1.01 (TF 13) recommended
subdividing any database into subsets comprising similar equipment in regard to 2-FAL generation
and analyzing each subset to obtain normal and abnormal levels by percentile [20]. A similar
investigation conducted by an IEEE working group into furanic compounds also concluded that the
best possible approach for furanic compound analysis would be to compare relative furanic test
results between transformers that have similar design, construction and service histories [36].
4.3 Methanol and Ethanol

Even though alcohols were observed during the laboratory pyrolysis of cellulose [39], the use of
methanol and ethanol in transformer oil as paper ageing indicators was first proposed in 2007 by
Jalbert et al. [40]. In their first paper, they demonstrated that the cellulose 1,4-β-glycosidic bond
scission is directly linked to methanol generation. It was suggested that methanol be used to indicate
normal paper ageing that occurs under normal operating conditions and ethanol be used to indicate
unusual paper ageing that occurs in abnormal conditions [5]. The main advantage of methanol over
conventional ageing indicators is its ability to indicate the early stage of paper ageing [40]. A standard
method for measuring methanol and ethanol in transformer oil is under development. Various GC-MS
and GC-FID methods are used to measure methanol and ethanol in transformer oil, with detection
limits from several parts per billion up to hundreds of parts per billion [41-45]. Some of the key
milestones in the development of methanol and ethanol as paper ageing indicators are shown in
Table 4-5.
32
Table 4-5: Key Literature Related to Methanol and Ethanol in Transformer Oil
Identification of methanol and ethanol as chemical indicators related to paper

[5, 40]
insulation in transformers
Development of a method to measure methanol/ethanol in transformer oil [41, 43, 44]
Investigations into the stability of methanol and ethanol [40, 46]
Investigations into the partitioning of methanol and ethanol between oil and paper [46-48]
Laboratory ageing experiments with mineral oil [40, 47, 49-63]
Methanol/ethanol measurement in transformers in service [40, 51-54, 64]
Post-mortem analysis related to methanol/ethanol [55]
Interpretation model [56]
4.3.1 Origin of methanol and ethanol
Ageing of paper components and paper-ageing by-products in oil at 130°C for 168 hours has shown
that methanol can be generated largely from cellulose, hemicellulose of hardwood and lignin
components [40]. However, since electrical insulation paper is made from softwood, the contribution
from hardwood hemicellulose was overlooked. Furthermore, as lignin has higher thermal stability and
lower availability than cellulose, it was suggested that cellulose could be the main contributor to
methanol generation from paper. On the other hand, ethanol was largely generated from
levoglucosan, a pyrolysis by-product of paper ageing. This finding led to the suggestion of using
ethanol as an indicator to indicate abnormal paper ageing that occurs at high temperatures [5, 57].
Table 4-6 shows the model compounds and the generation of methanol and ethanol from these
components during their ageing process.
Table 4-6: Generation of Methanol and Ethanol from Various Paper Components and Ageing By-products of Paper [40]
Components of Kraft Model compound studied CH3OH CH3CH2OH

paper (ppb/g component) (ppb/g component)
α-cellulose Microcrystals from cotton linters 8,940 640
Whatman paper No. 41 1,730 1,080
Lignin Alkali kraft lignin 153,200 <D.L.1
Hemicellulose from Mannan isolated from <D.L. 5,390
softwood Saccharomyces cerevisiae
Hemicellulose from Xylan isolated from birch 227,500 14,770
hardwood
Major by-product from D-(+)-glucose <D.L. 620
α-cellulose hydrolysis
Major by-product from 1,6-anhydro-β-D-glucopyranose 1,750 3,8630
α-cellulose pyrolysis (levoglucosan)
Oil only 440 430
1
Detection limit.
Nevertheless, it was reported that certain oil types could produce non-negligible amounts of methanol
and ethanol during ageing [58, 59]. Figure 4-7 shows the production of methanol and ethanol from an
inhibited mineral oil [58]. At high acidity values, methanol and ethanol in oil increased up to 1 ppm and
2 ppm, respectively.
33
Concentration (mg/kg)
Figure 4-7: Variation of methanol and ethanol in an inhibited mineral oil aged at 130°C [58]
4.3.2 Stability of methanol and ethanol in oil

The stability of methanol and ethanol in new mineral oil was investigated at temperatures ranging
from 70°C to 130°C [40]. Oil samples prepared with about 3 mg/kg of methanol and 1.5 mg/kg of
ethanol were conditioned at different temperatures. The variations in methanol and ethanol in oil are
plotted against the conditioning period in Figure 4-8. Methanol in oil was almost constant throughout
the conditioning period at both 70°C and 90°C. However, a reduction was observed at higher
temperatures of 110°C and 130°C. Ethanol, on the other hand, was constant at all temperatures
except at 130°C, at which its initial concentration was reduced by nearly 30%.
Figure 4-8: Stability of (a) methanol and (b) ethanol in transformer oil (replotted from[40])
Another experiment conducted with synthetic esters has shown that methanol in esters may be
unstable at high temperature (130°C) [46]. Figure 4-9 shows the concentration of methanol in two
synthetic ester samples conditioned at 130°C, with and without methanol being added prior to the
experiments. A drastic reduction in methanol concentration was observed in the sample conditioned
with methanol added prior to the experiment. It was suggested that the esterification of methanol
could have resulted in the reduction of methanol in esters.
34
Figure 4-9: Variation of methanol in a synthetic ester liquid during a stability experiment conducted at
130°C
4.3.3 Partitioning of methanol and ethanol between insulation paper and oil
It has been shown that partitioning of methanol and ethanol between oil and paper may depend on a
range of factors, including the type of oil, condition of oil and temperature [46, 47]. In oil-paper
insulation with mineral oil, more methanol stays in the paper than in the oil. Laboratory experiments
have shown that at room temperature, an oil–paper system with mineral oil (20:1 oil-to-paper ratio)
could have 90% of the methanol accumulated in the paper, whereas in synthetic esters this level
could be as little as about 40% [46]. Another experiment has shown that when partitioning between oil
and paper, more methanol can migrate into aged oil than into new oil [48].
Like other polar compounds, methanol and ethanol migrate from paper into oil with increasing
temperature [47, 48]. Figure 4-10 shows the temperature correction factors (Cf M) obtained for different
chemical indicators in a large-scale experiment conducted with model transformers [47]. Three model
transformers were first aged at a high temperature to produce chemical indicators. After the ageing
process, transformers were conditioned at different temperatures from 20°C to 90°C, allowing enough
time at each temperature for the chemical indicator to reach the equilibrium state. The temperature
correction factor CfM at each temperature was obtained according to equation 4-3. From the graph, it
is clear that the concentration of water is largely affected by the temperature of the methanol and
ethanol. Accordingly, applying a temperature correction for the methanol and ethanol measurement is
an important factor for condition monitoring.
[𝑀]20 °𝐶
Cf𝑀 = Equation 4-3
[𝑀]𝑇𝑠
In the above equation, Cf𝑀 indicates the temperature correction factor whereas [𝑀]20 °𝐶 and [𝑀]𝑇𝑠 are
the concentration of any ageing indicator at 20°C and the measured temperature, respectively.
Figure 4-10: Temperature correction factor (CfM) for various chemical indicators [47]
35
4.3.4 Laboratory ageing experiments

Laboratory ageing experiments have shown that methanol can be used as an early ageing indicator
for transformer insulation with various oil and paper types (oil types include mineral oil, gas-to-liquid
oil and ester-based oil; paper types include both thermally non-upgraded and thermally upgraded
Kraft paper) [40, 50, 52, 54, 59-63].
Figure 4-11 shows the variation of methanol and ethanol in oil against the number of ruptured bonds
(NS) (calculated according to equation 4-4) for laboratory ageing experiments conducted with different
amounts of initial water content in paper. Regardless of the water content in paper, the concentration
of methanol in oil increased linearly with paper ageing during the early stage of paper ageing.
Furthermore, the concentration of methanol in oil was higher than the concentration of conventional
paper ageing indicator 2-FAL, confirming the suitability of methanol as an early ageing indicator for
transformer paper insulation. The difference between methanol and 2-FAL further increased for
ageing experiments conducted with thermally upgraded paper.
𝐷𝑃(0)
𝑁𝑆 = ( − 1) Equation 4-4
𝐷𝑃(𝑡)
In the above equation, 𝐷𝑃(0) is the initial DPv of paper and 𝐷𝑃(𝑡) is the DPv of paper at any given time
t. NS is the number of ruptured bonds in the paper.
Figure 4-11: Variation of methanol and 2-FAL in oil against the number of ruptured bonds obtained from
laboratory ageing experiments conducted with (a) ordinary Kraft paper (b) thermally upgraded paper at
temperatures ranging from 60°C to 120°C [40].
Figures 4-12 and 4-13 shows the variation of methanol in alternative insulation liquids, including a
gas-to-liquid (GTL) oil and a synthetic ester, against the number of ruptured bonds in paper compared
to mineral oil. Methanol in GTL oil varied similarly to methanol in mineral oil. However, for similar DPV
36
levels, the concentration of methanol in synthetic ester was higher than in mineral oil, which was
found to be due to a difference in their partitioning between oil and paper [46].
Figure 4-12: Variation of methanol and 2-FAL in (a) gas-to-liquid (GTL) oil and mineral oil against the number of
ruptured bonds in paper measured during an ageing experiment conducted at 120°C [63]
Figure 4-13: Variation of methanol in (a) synthetic ester and mineral oil against the number of ruptured bonds in
paper measured during laboratory ageing experiments conducted at 80°C, 100°C and 120°C [46]
Methanol increases linearly during the early stages of paper ageing. However, methanol production
slows (or levels off) during the later stages of paper ageing [40, 46, 50, 59, 65]. For mineral oil, the
reduction was observed when the DPv of paper reached 200. In ester liquids (or in synthetic ester
liquids), the slowing down (or levelling off) occurs earlier during the paper ageing process, as shown
in Figure 4-13. It has been suggested that the reduction could be due to a change in the partitioning
coefficient with ageing [59]. In addition, it has also been proposed that methanol is consumed either
through hydrolysis [46, 63] or other reactions. There may be a difference in the rate of production of
methanol in ester liquids compared to mineral oil. Other laboratory experiments conducted at 105°C
and 122°C have shown similar results, as shown in Figure 4-14, where methanol is detectable at an
early stage of cellulose degradation and is a better indication for thermally upgraded paper than 2-
FAL.
Figure 4-14: DPv vs. 2-FAL and vs CH3OH (MeOH) of cellulose-based materials versus ageing time (days) and
temperature in mineral oil at 105°C and 122°C
37
Figure 4-15: DPv, 2-FAL and CH3OH (MeOH) vs. ageing time for cellulose-based materials in natural ester at 130°C
In natural ester (Figure 4-15) at 130°C with air headspace conditions, early-stage cellulose
degradation can be observed with methanol generation during the first steps of ageing. This
observation is valid for Kraft paper, TUK and mineral oil. However, a decrease in CH3OH content is
then observed, despite the reduction of DPv in natural ester. This decrease in CH3OH could be linked
to the interaction between ester and methanol molecules.
4.4 Kinetic studies on relating paper ageing to the production of

methanol
Ageing experiments with different components found in paper and paper ageing by-products have
shown that methanol production may be directly related to the chain scission of cellulose. Therefore,
we would expect to see a close kinetic correspondence between cellulose degradation and methanol
production.
Kinetic studies related to chain scission in cellulose dates back to 1930, when Ekenstam first
proposed the zero-order kinetic model shown in the following equation, based on a statistical study
[66].
1 1
ln (1 − ) − ln (1 − ) = 𝐾𝐷𝑃 𝑡 Equation 4-5
𝐷𝑃(𝑡) 𝐷𝑃(0)
In the above equation, KDP is the rate of paper ageing, DP(0) is the initial DPV of paper and DP(t) is the
DPV of paper at a given time, t.
When both DP(t) and DP(0) are large numbers, Ekenstam’s model can be simplified to the zero-order
equation shown in equation 4-6, which is more commonly used to study the kinetics related to paper
ageing [24, 67].
1 1
− = 𝑘𝐷𝑃 𝑡 Equation 4-6
Even though Ekenstam’s model is adequate to represent the early stage of paper ageing, the model
deviates from real trends in the later stage of paper ageing, which would eventually result in an
underestimation of paper lifetime [62]. In addition to Ekenstam’s model, other kinetic models proposed
by Emsley [68], Ding and Wang [69] and Calvini [67] can be used to model chain scission in cellulose
through the later stage of paper ageing.
Emsley’s model shown in equation 4-7 incorporates two rate constants: the initial rate of chain
scission and the rate of change in the initial rate constant. This model makes it possible to track chain
scission through the later stage of paper ageing and beyond the DPV of 200.
38
1 1 𝑘1
− = (1 − 𝑒 −𝑘2 𝑡 ) Equation 4-7
𝐷𝑃(𝑡) 𝐷𝑃(0) 𝑘2
In the above equation, DP(0) is the initial DPV of paper and DP(t) is the DPV of paper at a given time, t.
The constant k1 is the initial rate constant, and k 2 is the rate of change of initial rate constant k 1.
Calvini later proposed an update for Emsley’s model, as shown in equation 4-8, in order to satisfy the
boundary conditions at t=0 and t=∞ [70].
1 1 1 1 𝑘1
− =( − ) (1 − 𝑒 −𝑘2 𝑡 ) Equation 4-8
𝐷𝑃(𝑡) 𝐷𝑃(0) 𝐿𝑂𝐷𝑃 𝐷𝑃(0) 𝑘2
In the above equation, DP(0) is the initial DPV of paper, DP(t) is the DPV of paper at a given time t, and
LODP is the experimentally determined levelling-off of the DPV. The constant k1 was introduced as the
initial rate constant of hydrolysis, and k 2 is the rate of change of initial rate constant k 1.
In addition, Calvini also proposed a new model, shown in equation 4-9, which seeks to give the model
a physical meaning [70]. The model considers different types of regions on paper, presence of weak
links, amorphous and crystalline regions.
1 1 𝐷𝑃(0) 0 (1
𝑆= ( -− )=( − 1) = 𝑛𝑤 − 𝑒 −𝑘𝑤𝑡 ) + 𝑛𝑎0 (1 − 𝑒 −𝑘𝑎 𝑡 ) + 𝑛𝑐0 (1 − 𝑒 −𝑘𝑐𝑡 ) Equation 4-9
𝐷𝑃(𝑡) 𝐷𝑃(0) 𝐷𝑃(𝑡)
1 1
For the above equation, S can be expressed as either scission per monomer unit ( - ) or
𝐷𝑃(0)
scissions per initial cellulose chain ( − 1), which is also the number of ruptured bonds (NS).
𝐷𝑃(𝑡)
0
Furthermore, the constants 𝑛𝑤 , 𝑛𝑎0 and 𝑛𝑐0 are the initial number of weak links, glycosidic bonds
available in the amorphous region and glycosidic bonds available in the crystalline region,
respectively. 𝑘𝑤 , 𝑘𝑎 and 𝑘𝑐 are the corresponding rate constants.
Later, Jalbert proposed a modification [59] to Calvini’s model, stating that the contribution from the
weak links is negligible in the investigated paper type and that the opening of bonds in the crystalline
regions is in the early stages. The new model shown in equation 4-10 is a combination of the first-
order process and a pseudo-zero process for the scission of bonds in the amorphous and crystalline
regions.
𝐷𝑃(0) 𝐷𝑃(0)
( − 1) = ( − 1) (1 − 𝑒 −𝑘𝑎𝑡 ) + 𝑛𝑐0 𝑘𝑐 𝑡 Equation 4-10
𝐷𝑃(𝑡) 𝐿𝑂𝐷𝑃
In the above equation, DP(0) is the initial DPV of paper, DP (t) is the DPV of paper at a given time t, and
LODP is the experimentally determined levelling-off of the DPV. The constant ka is introduced as the
initial rate constant of hydrolysis, and k 2 is the rate of change of initial rate constant k 1. Furthermore,
𝑛𝑐0 and 𝑘𝑐 represent the initial number of glycosidic bonds in the crystalline region and the rate
constant for the same region.
In addition to the above-mentioned methods, Ding and Wang proposed another model for chain
scission, taking a slightly different approach that includes the percentage of DP V loss for cellulose
degradation, as shown in equation 4-11.
𝐷𝑃(𝑡) ∗
Equation 4-11
ω𝐷𝑃 = (1 − ) = ω𝐷𝑃 (1 − 𝑒 −𝑘𝐷𝑃𝑡 )
𝐷𝑃(0)
In the above equation, 𝑘𝐷𝑃 is the rate constant, ω𝐷𝑃 is the accumulated DPV loss of cellulose, and ω∗𝐷𝑃
is the capacity of the DPV degradation reservoir.
The rate constants obtained for paper ageing using any of the proposed models can then be used in
Arrhenius plots to calculate the activation energy, and the pre-exponential factor can be calculated
[71].
−𝐸
𝑘 = 𝐴𝑒 𝑅𝑇 Equation 4-12
In the above equation, k is the rate of degradation, A is the pre-exponential factor, E is the activation
energy, T is the temperature, and R is the gas constant.
39
Several experiments have been conducted to relate the activation energy of the chain scission of
paper to methanol production [46, 59, 61, 62]. These kinetic studies were conducted with both
thermally non-upgraded Kraft paper and thermally upgraded Kraft paper through a series of laboratory
ageing experiments at temperatures ranging from 60°C to 210°C. The kinetics of paper ageing were
obtained through one of the models discussed earlier, and the rate of methanol production was
obtained via either a zero-order reaction or a first-order reaction mechanism as shown in equations 4-
13 and 4-14, which are analogies to Ekenstam’s simplified model and Emsley’s model.
𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑓𝑟𝑜𝑚 𝑝𝑎𝑝𝑒𝑟 = 𝐾𝑀𝑒𝑂𝐻 𝑡 Equation 4-13
In the above equation, KMeOH is the rate of methanol increase.

𝑘𝑎
𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑓𝑟𝑜𝑚 𝑝𝑎𝑝𝑒𝑟 = (1 − 𝑒 −𝑘𝑏 𝑡 ) Equation 4-14
𝑘𝑏
In the above equation, 𝑘𝑎 is the initial rate constant and 𝑘𝑏 is the rate of change of initial rate
constant 𝑘𝑎 .
Tables 4-7, 4-8 and 4-9 summarize the results of these kinetic studies. Results suggest that
regardless of the type of oil or paper, the activation energy for paper ageing is similar to the activation
energy for methanol production, which indicates that the two processes could be linked together.
40
Table 4-7: Results of the Kinetic Studies Conducted at Temperatures below 120°C with Thermally Non-upgraded Kraft Paper
Reference Model used for Oil type Paper Nitrogen Headspace Initial Temperatu Chain scission in cellulose Methanol production
type content (%) water re range –
Paper Methanol (%) content number of Activation Frequency Activation Frequency
ageing production data points energy factor energy factor
(kJ mol-1) (µmol g-1 h-1) (kJ mol-1) (µmol g-1 h-1)
[62] 𝑘𝐷𝑃 from 𝑘𝑀𝑒𝑂𝐻 from Nytro 10CX, Clupak 0.073 Air 1.92 60–120 (7) 107.8 ±
Ekenstam’s the zero- naphthenic HD75 106.7 ± 3.4 5.361E+12 1.5 2.226E+12
model, order inhibited 1.11 60–120 (7) 104.7 ±
shown in model,
equation 105.0 ± 3.8 2.581E+12 3.1 5.973E+11
shown in
[66] [58, 62] 0.47 60–120 (6) 104.7 ±
104.8 ± 4.0 1.703E+12 4.7 4.577E+11
Nytro 10CX, Munksjö 0.013 Air 1.89 70–120 (6) 102.1 ±
naphthenic TH70 102.2 ± 2.9 1.447E+12 6.6 6.771E+11
inhibited 1.15 60–120 (7) 104.1 ±
99.7 ± 4.2 5.448E+11 2.6 7.151E+11
0.45 60–120 (7) 104.7 ±
96.6 ± 4.4 1.460E+11 2.5 6.398E+11
Shell Diala, S Munksjö 0.013 Nitrogen 2.25 70–130 (7) 112.6 ±
paraffinic, E.G. 106.9 ± 5.6 1.977E+12 4.0 1.514E+12
uninhibited 0.62 90–130 (5) 114.1 ±
105.9 ± 12.8 5.148E+11 7.9 9.895E+11
[46] Gemini X Thermally N/A Air 0.66 80–120 (3) 111.9 3.58E+10 122.3 1.17E+15
MIDEL 7131 non- 0.79 80–120 (3) 102.0 1.19E+14 114.4 4.32E+14
[72] Diala S4 ZX-I upgraded 0.63 80–120 (3) 109.5 1.61E+10 125.2 2.61E+15
Kraft
paper
41
Table 4-8: Results of Kinetic Studies Conducted at Temperatures below 120°C with Thermally Upgraded Kraft Paper
Reference Model used for Oil type Paper Nitrogen Headspace Initial Temperature Chain scission in cellulose Methanol production
type content (%) water range –
Paper ageing Methanol (%) content number of Activation Frequency Activation Frequency
production data points energy factor energy factor
(kJ mol-1) (day-1) (kJ mol-1) (mg kg-1 day-1)
[61] K1 in Ka first- Nytro 10CX, Rotherm 1.15 Air 2.02–2.04 60-120 (7) 102.4 ± 2.9 1.237E+12 106.2 ± 2.544E+12
Emsley’s order naphthenic CE 3.7
model [73] model, inhibited 1.21–1.27 60-120 (7) 107.9 ± 3.0 5.882E+12 109.5 ± 6.569E+12
shown in 60-120 (6) 2.7
[61] 0.61–0.64 70-120 (6) 105.3 ± 5.9 1.622E+12 104.1 ± 5.803E+11
60-120 (6) 4.6
Nytro 10CX, Manning 3.9 Air 1.99 60-120 (7) 108.4 ± 4.3 9.971E+12 110.3 ± 3.433E+13
naphthenic 220 70-120 (5) 3.9
inhibited
42
Table 4-9: Results of Kinetic Studies Conducted at Temperatures above 130°C with Thermally Upgraded and Thermally Non-upgraded Kraft Paper
Reference Model used for Oil type Paper type Nitrogen Headspace Initial Temperature Chain scission in cellulose Methanol production
content (%) water range –
Paper Methanol (%) content number of Activation Frequency Activation Frequency
ageing production data points energy factor energy factor
(kJ mol-1) (day-1) (kJ mol-1) (ln Aa)
1
[59] 𝑘𝑎 from 𝑘𝑎 from Nytro 10CX, Clupak HD- 0.073 Air 1.06 130–210 (5)
Jalberts first-order naphthenic 75
model, model, inhibited, thermally
shown shown in and R-Temp non-
in [59] [61, 62] (for 190°C & upgraded 115.5 ± 8.2 27.0 ± 2.1 99.5 ± 8.7 26.3 ± 2.3
𝑛𝑐0 𝑘𝑐 𝑘𝑏 from 210°C) paper 130–210 (5)
from first-order
Jalberts model,
model, shown in
shown [61, 62] 111.3 ±
in [59] 11.9 25.6 ± 3.2 100.5 ± 9.0 25.0 ± 2.4
𝑘𝑎 from 𝑘𝑎 from Shell Diala S Densiflex- 1.8 Nitrogen 0.61 150–210 (4) 148.1 ± 33.2 ± 3.5 132.5 ± 33.1 ± 2.9
Jalberts first-order 22HCC 13.6 10.9
model, model, thermally
shown shown in upgraded
in [59, [59, 61] paper
61]
𝑛𝑐0 𝑘𝑐 𝑘𝑏 from 150–210 (4) 195.3 ± 45.5 ± 6.8 121.3 ± 28.2 ± 4.5
from first-order 25.6 16.7
Jalberts model,
model, shown in
shown [59, 61]
in [59,
61]
1
Two different oil types were used due to the non-negligible contribution to methanol formation by Nytro 10CX at temperatures above 190°C.
43
44
4.5 Other generation sources of cellulose markers

For this section, it had been planned to perform thermal ageing of other transformer cellulose parts
(wood and board). Unfortunately, the Working Group was not able to fulfill this aspect of the original
Terms of Reference.
4.6 In-service experience with methanol and ethanol

Methanol and ethanol are already being used as condition monitoring tools in many countries [40, 43,
51-53, 57, 64]. Figure 4-16 shows the variation of methanol in-service transformers and reactors. The
concentration of methanol in most of the in-service equipment is less than 1 ppm and shows a general
increasing trend. However, it was shown that oil treatment and various loading conditions could affect
the concentration of methanol in oil.
(a)
(b)
(c) (d)
Figure 4-16: Variation of methanol measured in transformers and reactors in (a) Canada [40], (b)
France,Italy, Ivory Coast and Romania [43], (c) France [54] and (d) United Kingdom [64]
45
The methanol concentration in transformers can be affected by design parameters such as the oil-to-
paper ratio, breathing types, loading conditions and maintenance (such as oil regeneration or
replacement). Figure 4-16 (b) shows transformers with concentrations that deviate from the general
trend as a result of these conditions. Some of these abnormal measurements resulting from
temperature can be corrected by applying a temperature correction factor; this was demonstrated in a
post-mortem analysis [55]. Figure 4-17 shows the variation of methanol in five transformers before and
after temperature correction. The results show that temperature correction could help achieve a better
correlation with the DPV of paper and hence a more accurate DPV prediction for transformers in
service.
Figure 4-17: Concentration of methanol in several in-service transformers before and after temperature
correction [55].
Even though the oil treatment could result in a temporary reduction in methanol, it was shown that
methanol recovery is much greater than that of the conventional paper ageing indicator, 2-FAL [53].
Three transformers that underwent a combined oil regeneration and degassing process showed nearly
89%-to-124% methanol recovery within six months, compared to 18%-to-26% recovery for 2-FAL.
Most in-service transformers have a lower concentration of ethanol than methanol [52, 56]. In
300 power transformers, the concentration of ethanol was higher than that of methanol in only 10% of
the transformers [52]. Furthermore, based on in-service experience, it was proposed that a greater
quantity of ethanol than methanol in a transformer could be an indication of paper ageing that
occurred at high temperatures. A distribution transformer that had 215 µg/kg of methanol and
585 µg/kg of ethanol was found to have abnormal paper ageing due to arcing between windings [57].
Other investigations involving roughly 200 in-service transformers (ranging from 5 kV to 400 kV) were
conducted in order to establish possible correlations between methanol markers and other
characteristics.
46
Figure 4-18: Markers, acidity and moisture content versus the number of transformers [74]
The quantitative characteristics considered are the following: transformer age (in years), power (kVA),
voltage (kV), 2-FAL (ppm), CH3OH (ppm), oil water content (ppm) and soluble acidity (mgKOH/g). The
higher the transformer identification number, the greater the age, acid number and CH3OH, 2-FAL and
water content. The water content and acid number of oil are recognized as critical parameters
influencing methanol generation. Indeed, it can be shown that CH3OH variations seem to be linked to
oil acidity and water content variations, as shown in Figure 4-18. These variations are consistent with
the fact that acid hydrolysis is the major mechanism of cellulose bond scission where methanol is
directly involved. The analyses show that methanol content is an efficient tracer with a predictive
advantage over 2-FAL.
4.7 Summary
Results (based on in-service data and/or laboratory ageing data) confirm that methanol is a promising
ageing marker for cellulose-based insulation in mineral oil, especially in early-stage detection of
insulation (cellulose) degradation and the assessment of thermally upgraded Kraft paper (TUK) ageing
status, unlike 2-FAL.
In ester liquids, the behavior and efficiency of methanol/ethanol as ageing markers, which are not the
subject of this study, need further investigation.
However, to make a comprehensive and efficient diagnosis of transformer status, the use of
methanol/ethanol as ageing markers should be combined and correlated with existing complementary
chemical tracers (CO, CO2, 2-FAL, water, etc.), and their interactions in the oil/cellulose system should
be taken into account in light of various parameters (temperature (°C), type of oils and solids,
sampling, transformer design, etc.).
47
48
5. Round robin on alcohol measurements

Before analyzing and comparing the results, it is important to ensure that all laboratories analyzed the
alcohol concentrations correctly. To that end, two round robins on both methanol and ethanol analysis
were performed by the CIGRE group. The first round-robin tests (RRT) involved six laboratories, and
the second, nine laboratories.
5.1 First RRT

Two standards with different concentration levels prepared by weight in new oil, one at a concentration
of ~200–300 ppb (w/w) (standard A) and the other at a concentration of ~1,000 ppb (w/w) (standard
B), were considered. The concentrations were verified by choosing a syringe randomly from each
concentration. Finally, oxidized oil from a real transformer was also analyzed.
Some of the participating laboratories used two different methods, referred to as methods a & b. In
general, the methods consist of extracting the gases by headspace (the oil volume in the vial differed
from one laboratory to another), separating the alcohols by gas chromatography (columns and
conditions also differed from one laboratory to another) and detection/quantification by mass
spectrometry (method a) or flame ionization detector (method b).
5.1.1 Results
Because all the prepared concentrations in syringes were not equal, the measured and prepared
values were compared using the relative error (RE).
𝒎𝒆𝒂𝒔𝒖𝒓𝒆𝒅 − 𝒑𝒓𝒆𝒑𝒂𝒓𝒆𝒅 Equation 5-1
𝑹𝑬(%) = 𝒙𝟏𝟎𝟎
𝒑𝒓𝒆𝒑𝒂𝒓𝒆𝒅
A Dixon’s Q test was performed to eliminate any outlier results. To ensure the prepared sample
concentrations had the expected concentrations, a syringe was randomly chosen from each batch and
analyzed. In Table 5-1, the results for CH3OH shows a relative error of 13% and -3.8% for standards A
and B respectively. In the case of CH3CH2OH, the relative error was less than 1% in both cases. After
this verification, the samples were sent to the participating laboratories.
Table 5-1: Random Sample Verification Results
Laboratory CH3OH CH3CH2OH

Calculated Measured RE Calculated Measured RE
(ppb) (ppb) (%) (ppb) (ppb) (%)
IREQ 246 279 13.0 242 242 -0.1
IREQ 1078 1036 -3.8 1060 1052 -0.8
The participating laboratories’ concentration results are presented in Tables 5-2 and 5-3. In the case
of CH3OH for standard A, one lab (2a) using mass spectrometry obtained a result below its detection
limit. The other results showed relative errors between 2.3% and 54.7%. In the case of CH3CH2OH,
the relative error varies between -5.9 and 41.1%. In the case of standard B (Table 3), the relative error
varies between -39.6 to 36.7% and -44.3 to 51.2% for CH3OH and CH3CH2OH respectively. These
results are also compiled in Figure 5-1 with a ±10% confidence band. In this Figure, Standard A
corresponds to “Middle concentration” and Standard B to “High concentration.” The confidence bands
approximate the variation in our standard preparation. In this first RRT, we could not perform a Dixon’s
Q test because all the concentrations were prepared individually and differed somewhat.
49
Table 5-2: Standard A Results1

(ppb) (ppb) (%) (ppb) (ppb) (%)
1 240 245 2.3 236 248 5.2
2a 246 <D.L.1 n.a.2 242 < D.L. n.a.
2b 246 380 54.7 242 290 20.0
3 240 280 16.5 236 300 26.9
4 244 261 6.9 240 246 2.4
5a 328 357 8.9 398 417 4.7
5b 328 353 7.6 398 375 -5.9
6 320 410 28.3 390 550 41.1
1 Lower than the detection limit ~10 ppb (w/w). 2Not applicable.
Table 5-3: Standard B Results

(ppb) (ppb) (%) (ppb) (ppb) (%)
1 1,084 1,073 -1.0 1,067 1,075 0.8
2a 1,076 650 -39.6 1,058 590 -44.3
2b 1,076 1,470 36.7 1,058 1,600 51.2
3 1,078 1,150 6.6 1,061 1,100 3.7
4 1,072 1,099 2.5 1,055 1,105 4.7
5a 1,001 1,088 8.6 1,081 1,250 15.7
5b 1,001 989 -1.2 1,081 1,042 -3.6
6 1,015 1,350 33.0 1,094 1,280 17.0
60 60
50 50
40 40
30 30
20 20
10
Bias (%)
Bias (%)
10
0
0
-10
-10
-20
-20
-30
MeOH -30 EtOH
-40 --- Expected --- Expected
-40
-50 Middle Middle
High -50 High
-60
1 2a 2b 3 4 5a 5b 6 1 2a 2b 3 4 5a 5b 6
Laboratories Laboratories
Figure 5-1: Prepared samples with a tolerance of ±10%.
Table 5-4 shows the results of the analysis of the oxidized oil. For this analysis, the real concentration
was not known because the sample was taken from a real transformer in operation. Taking into
account the sample averages and standard deviation, the error data range can be calculated. A
Dixon’s Q test revealed that laboratories 6 and 2 are outliers with a very high concentration result,
principally for the CH3CH2OH measurement (see Figure 5-2). If we remove this outlier, a concentration
of 786 ± 126 ppb (±16%) and 200 ± 36 ppb (±18%) are obtained for CH 3OH and CH3CH2OH
respectively. These errors are of the same order as the accuracy of the standard measured at each
level.
1
Prepared samples: For IREQ, the person who prepared the samples and the analyst are different i.e. analyst didn't know the
concentrations.
50
Table 5-4: Transformer Oxidized Oil Results

Measured Measured
(ppb) (ppb)
1 783 168
2a 880 <D.L.
2b 660 210
3 510 220
4 848 201
5a 874 185
5b 871 275
6 1360 1280
1400
1400 MeOH EtOH
Mean Mean
Stdev outlier Stdev
1200
1200
outlier
Concentrations (ppb)
1000 Concentrations (ppb)

300
800
250
600 200
150
400
100
200
50
0 0
1 2a 2b 3 4 5a 5b 6 1 2a 2b 3 4 5a 5b 6
Laboratories Laboratories
Figure 5-2: Oxidized oil samples.
5.1.2 Summary
This RRT analysis reveals that alcohol measurements can be analyzed correctly with a relative error
of ±20% if we take into account the sample preparation precision of ±10% and the accuracy of the
analytical method.
5.2 Second RRT

Two batches of standards prepared by weight in ~400 mL of new oil, one standard A at ~300 ppb
(w/w) and one standard B at ~1,600 ppb (w/w), were considered. After preparation, the oil was
distributed into different syringes. The concentrations were verified by choosing a syringe randomly
from each concentration batch. Finally, oxidized oil from a real transformer was also analyzed.
5.2.1 Results
Table 5-5 compares the calculated values and measured results obtained for the second RRT in the
case of the sample with the lower concentration. Unfortunately, laboratory #2 did not receive the
samples and laboratory #3 did not analyze the CH3CH2OH. As the samples come from a single batch
preparation, the confidence bands are predetermined. These determinations are reproduced in Figure
5-3. As seen in this figure, one outlier (laboratory #7) is found for both CH 3OH and CH3CH2OH and
three laboratories (#1, #4, #9) for CH3OH. In addition, two laboratories (#4, #5) are outside the
confidence bands. For this level of concentration, the accuracy of this second RRT was better than for
the first one.
51
Table 5-5: Standard A Results

(ppb) (ppb) (%) (ppb) (ppb) (%)
1 296 160 -46.0 277 280 0.9
2 296 n.d.1 n.d. 277 n.d. n.d.
3 296 301 1.6 277 n.d. n.d.
4 296 397 34.0 277 320 15.4
5 296 227 -23.4 277 219 -21.1
6 296 227 -23.4 277 236 -14.9
7 296 700 136.4 277 530 91.0
8 296 270 -8.8 277 268 -3.4
9 296 360 21.6 277 270 -2.7
10 296 274 -7.3 277 250 -9.9
1
n.d.: not determined.
800 600
MeOH outlier EtOH
Mean outlier
700 Mean
95% CI + 500 95% CI +
600 95% CI - 95% CI -
Prepared
Concentration (ppb)
Prepared
400
500
EtOH
400 300
300
200
200
100
100
0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Laboratory Laboratory
Figure 5-3: Standard A Results
Table 5-6 shows the results obtained for the higher concentration. In this case, one outlier (laboratory
#7) is observed for CH3OH, and only two laboratories are outside the confidence bands for both
CH3OH (laboratories #4, #5) and CH3CH2OH (laboratories #5, #7) (see Figure 5-4). The accuracy is
comparable to what was observed in the first RRT.
Table 5-6: Standard B Results

(ppb) (ppb) (%) (ppb) (ppb) (%)
1 1,616 1,300 -19.6 1,514 1,800 18.9
2 1,616 n.d. n.d. 1,514 n.d. n.d.
3 1,616 1,749 8.2 1,514 n.d. n.d.
4 1,616 2,147 32.8 1,514 1,815 19.9
5 1,616 1,213 -25.0 1,514 1,196 -21.0
6 1,616 1,582 -2.1 1,514 1,597 5.5
7 1,616 3,070 89.9 1,514 2,360 55.9
8 1,616 1,677 3.7 1,514 1,620 6.9
9 1,616 1,610 -0.4 1,514 1,740 14.9
10 1,616 1,544 -4.5 1,514 1,485 -2.0
52
3500 3500
MeOH outlier EtOH
Mean Mean
3000 3000
95% C.I (+) 95% CI +
95% C.I (-) 95% CI -
Concentration (ppb)
Concentration (ppb)
2500 Expected 2500 Expected
2000 2000
1500 1500
1000 1000
500 500
0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Figure 5-4: Standard B Results
Table 5-7 compares the results obtained for the analysis of the oxidized oil. The relative error varies
from -30% to 52% for CH3OH and from -36% to 20% for CH3CH2OH. Three laboratories provided data
which lie outside the standard deviations for CH3OH (laboratories #1, #6, #7), and two laboratories did
so for CH3CH2OH (laboratories #5, #7), as shown in Figure 5-5.
Table 5-7: Oxidized Oil Results

1
Calculated Measured RE Calculated Measured RE1
(ppb) (ppb) (%) (ppb) (ppb) (%)
1 631 440 -30.3 752 800 6.4
2 631 n.d. n.d. 752 n.d. n.d.
3 631 714 13.2 752 n.d. n.d.
4 631 681 7.9 752 848 12.7
5 631 542 -14.1 752 484 -35.7
6 631 445 -29.5 752 766 1.8
7 631 960 52.2 752 900 19.6
8 631 707 12.0 752 835 11.0
9 631 600 -4.9 752 700 -7.0
10 631 590 -6.5 752 685 8.9
1
Relative error (RE) calculated using the mean value.
1200 1200
MeOH EtOH
Mean Mean
1000 95% C.I (+) 1000 95% C.I (+)
95% C.I (-) 95% C.I (-)
Concentration (ppb)
Concentration (ppb)
800 800
600 600
400 400
200 200
0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Figure 5-5: Oxidized oil sample results
53
5.2.2 Summary
For this RRT, when the outliers and data outside the confidence bands are removed, the results will
be acceptable. The laboratories showing outliers or data that are outside the confidence bands are the
same. This suggests a problem of calibration or internal standards for these laboratories.
54
6. Influence of different factors on ageing marker

measurement
In managing transformer assets, diagnostics and maintenance are very important. There is a need to
improve diagnostic methods for conventional insulation systems and to establish new methods for
new insulation systems. Cellulose-based winding insulation is subject to irreversible ageing, which
reduces its ability to withstand short circuits and mechanical stresses. Consequently, tensile strength
and degree of polymerization (DPv) decline over time due to the weakening of the paper’s mechanical
strength.
Experimental studies have established that temperature, moisture, acids and oxygen are the major
factors influencing the ageing of cellulose in transformers [31, 75-79]. Ageing of an oil-cellulose
system generates water [1], high- and low-molecular-weight acids [80], alcohols [5, 40, 53, 60] and
furanic derivatives [26, 75, 81] that can to some degree be dissolved in oil. These by-products can
potentially be used as ageing indicators. Furanic derivative levels have also been used as an indirect
[82-84] way to estimate the DPv value of winding insulation. However, these substances, i.e., water,
furanics, methanol and to some extent acids, partition between the liquid and solid insulation. Water
partitioning is by far the best-documented case.
It is well known that most of the water in a transformer resides in the cellulose, with only a small
fraction in the oil. Water distribution between the oil and cellulose is governed by water solubility in
these materials. If left undisturbed at a stable temperature, partitioning will achieve an equilibrium
where the relative humidity stays the same throughout the system if the temperature is uniform. In this
case, water vapor pressure is equal in both materials. Since water distributes well in cellulose but not
as well in oil, most of the water will end up in the cellulose. Figure 6-1: shows how the absolute
moisture in cellulose and in oil will end up at different relative humidities and temperatures. For
example, at 40% relative moisture and 40ºC, water content will be 5% by weight (or 50 mg/g) in the
cellulose and 50 ppm (or 50 µg/g) in the oil. When the temperature in the cellulose is 100ºC, water
content would be 3% by weight (or 30 mg/g).
In a transformer, the hotter parts are drier than the colder parts. Much of the water will stay stable in
the colder, thicker parts of the insulation due to the long diffusion time, while the fraction that resides in
the thinner structures (windings barriers and spacers) will change dynamically with temperature and
move into the oil at higher temperatures and back again when the temperature drops.
Figure 6-1: shows that water content in mineral oil changes linearly with relative moisture, while the
relationship is more complicated for cellulose. Particularly at low relative moistures, it is difficult to
measure and accuracy is low.
Figure 6-1: Total water content vs. relative moisture in paper (left) [85] and mineral oil (right) [86]
By combining the curves from Figure 6-1:, equilibrium curves for water in an impregnated system like
those shown in Figure 6-2 can be established. These are the curves normally used for transformer
insulation assessment by measuring the concentration of water in the oil by using Karl Fisher titration,
and then estimating the concentration in the cellulose. To do so, the transformer temperature at the
55
time of sampling must be known. In practice, the average of the top and bottom transformer oil
temperatures is used and it is assumed that all cellulose is at this temperature. In reality, the oil will
have the same water concentration due to oil circulation. Water content in the cellulose is
temperature- and therefore location-dependent. A possible exception is for compact coolers with a
mid-tank oil outlet, where the lower tank may end up with more stagnant oil.
Figure 6-2: Equilibrium curves for water in new impregnated insulation with Nynas Nytro 10X and Munksjø
paper
One complicating factor is that water solubility in oil may vary. In particular, during the oil ageing
process, polar and acidic compounds are produced, allowing water content in the oil to rise. Figure 6-3
shows the maximum water concentration the oil can absorb at a given temperature before free water
forms. The formula KW = Ae-E/T can often be used to describe how water solubility changes with
temperature. KW is water solubility, A and E are constants and T is the absolute temperature. When oil
ages, acidity increases and the oil can dissolve more water. This seems to be governed by the content
of water soluble acids TANLMA, in which TAN refers to “Total acid number” and LMA means “Low
molecular weight acids.”
Figure 6-3: Moisture saturation limit vs. temperature for mineral oil with varying acid number content.The NV
values correspond to the total acid number and acid number reduction due to water rinsing: TANTOTAL/TANLMA [87].
56
Increases in the oil’s water solubility can change the equilibrium curves. This is because aged oil will
carry more water at a certain relative humidity than new oil.
In principle, relative moisture can be measured to avoid this difficulty. Relative moisture sensors exist
on the market. There is still some discussion about their sensitivity, accuracy and stability. These
sensors are based on water intake into a thin substrate, causing changes to its capacitance. This is
because water has a very high permittivity (around 80 at room temperature) compared to other
relevant detector materials, with a permittivity of around 3. Such sensors always have a built-in
temperature sensor for reference purposes. Oil temperatures vary in the transformer while the
absolute moisture concentration is uniform for a loaded transformer, due to oil circulation. Figure 6-1:
for mineral oil (above) shows that for a given absolute water content, the relative moisture will depend
on the temperature.
When relative moisture sensors are used, the water solubility in the specific oil must be known in order
to calculate water content at a given temperature and then, knowing how solubility changes with
temperature, determine the relative moisture content at the winding temperature. Water in cellulose
can then be calculated by using known relationships for cellulose, as shown in Figure 6-1: for cellulose
(above).
6.1 Two-temperature rig for partitioning studies

Lundgaard et al. [48, 88] investigated the temperature-dependent equilibrium distribution of moisture
and other ageing indicators using an in-house test rig shown in Figure 6-4. In this test rig, oil circulates
between two cellulose-containing chambers (Kraft paper and pressboard), which can be kept at
independently set temperatures. The chambers are denoted chambers 1 and 2, with respective
temperatures T1 and T2. Upon reaching equilibrium, contaminant concentration is presumed to be the
same throughout the circulating oil. Oil can easily be extracted from the rig for contaminant
measurement, and three solid-state relative humidity sensors (Vaisala) measure both temperature and
“water activity” aw (believed to be equivalent to relative humidity). Two temperature controllers are
used to keep the system at the chosen temperatures.
Figure 6-4: Two-temperature rig
The rig is built with one large, dominant chamber (chamber 1) filled with oil and cellulose at a chosen
contamination level. The temperature of this chamber is set to T1. A small chamber (chamber 2) is
also filled with cellulose and set at an independent temperature T2, above or below T1. The oil is
circulated from chamber 1 to chamber 2 and back to chamber 1. There are 20 times more cellulose in
chamber 1 than in chamber 2. Therefore, the amount of contamination in chamber 2 has only a very
small influence on the circulating contaminant level and the contaminant level in the cellulose in
chamber 1, so the cellulose in chamber 1 serves to a reasonable degree as an “infinite” contaminant
buffer.
Lundgaard et al. prepared four different systems using this rig:
1. New paper in oil contaminated with a mixture of formic and acetic acid [79, 88]
2. Service-aged pressboard in service-aged oil from a transformer in Suldal, Norway [48, 79]
3. Laboratory-aged mineral oil with upgraded paper and pressboard [48]
4. Laboratory-aged synthetic ester (Midel 7131) with upgraded paper and pressboard [48]
57
𝐶𝑀20°𝐶
𝐶𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑓𝑎𝑐𝑡𝑜𝑟 = Equation 6-1
𝐶𝑀𝑇𝑠
The correction factor is defined as the concentration of the chemical marker compound (CM) at the
reference temperature (20°C), divided by the concentration at the specific temperature (Ts).
6.2 Water partitioning in a model system and service-aged
materials
System 1 in Figure 6-5 shows the moisture content in cellulose against the moisture content in oil
plotted in log-log scale for the system 1 results obtained for aged materials and results published by
ABB for clean new materials. [79]. Water content for three different materials are plotted for four
different T2 temperatures with varying water content in the circulating oil caused by variations in T1.
Most of the points for new materials are above the clean, new system lines, while most of the points
for service-aged crepe paper are below. They are more variable for service-aged pressboard.
10 10
Moisture in cellulose [%]

1 1
Moisture compared to clean, new system Moisture compared to clean, new system
(ABB curves), for T2 = 40 oC. (ABB curves), for T2 = 60 oC.
Top to bottom: 40, 60, 80 and 100 oC. Top to bottom: 40, 60, 80 and 100 oC
New Kraft paper New Kraft paper

Service-aged pressboard Service-aged pressboard
Service-aged creped paper Service-aged creped paper
0.1 0.1
10 100 10 100
Moisture in oil [ppm] Moisture in oil [ppm]
10 10
1 1
Moisture compared to
Moisture compared to clean, new system ABB curves, for T2 = 100 oC
(ABB curves), for T2 = 80 oC. Top to bottom:
Top to bottom: 40, 60, 80 and 100 oC 40, 60, 80 and 100 oC
New Kraft paper New Kraft paper

Service-aged pressboard Service-aged pressboard
Service-aged creped paper Service-aged creped paper
0.1 0.1
10 100 10 100
Moisture in oil [ppm] Moisture in oil [ppm]
Figure 6-5: Water partitioning for aged systems at four different temperatures (40, 60, 80 and 100˚C).
On one hand, the results provide no support for the hypothesis that there is a need to develop specific
partitioning curves for aged materials. On the other hand, they show that the accuracy expected when
deriving water in cellulose from equilibrium charts and values of water in oil is no better than
approximately 0.5%.
In another experiment [48], a laboratory-aged system with mineral oil and upgraded paper was
included and compared to a service-aged material system collected from a transformer in Suldal,
Norway. Correction factors as a function of water temperature were derived and compared with the
factors published by Jalbert et al. [47] (see Figure 6-6). It was observed that the quantity of these
58
markers in oil is clearly temperature-dependent. The results obtained are in line with what had
previously been published [47, 79].
Figure 6-6: Water correction factor for a mineral oil system comparison using [76] and [56].
6.3 Acid partitioning

The acids present in the following two systems are quite different.
 A system with new paper in oil contaminated with a mixture of formic and acetic acid
 A service-aged system with a mixture of carboxylic acids with both water-soluble low-
molecular-weight acids and non-soluble high-molecular-weight acids
It was shown earlier that little of the fatty acids is dissolved in paper [80, 89]. The increase seen with
temperature will be partitioning.
Figure 6-7: Variation in acidity with temperature for a model system (left) and a service-aged system (right)
Attempts to measure the quantity of acids in the paper showed no correlation with temperature [90].
For the model system, cellulose acidity was measured at roughly 2–4 mg KOH/g for paper and 1–2
mg KOH/g for pressboard, which was low compared to the "theoretical" content of 7.79 mg KOH/g for
cellulose. For the aged system, the content of water-extracted acids measured in the cellulose was in
the 1–1.7 mg KOH/g range. It should be mentioned here that in addition to partitioning, other chemical
reactions are also taking place which can affect the concentration measured [90].
59
6.4 Partitioning of furanic derivatives and alcohols

It is expected that water, furanics and alcohols all have a temperature-dependent equilibrium between
those of cellulose and oil. There are well-established and standardized methods for measuring furanic
compounds in mineral oils.
Figure 6-8 shows the content of these substances obtained from partitioning studies conducted with
service-aged materials. As expected, the concentration in the oil increases with temperature.
6 10
Furans and alcohols in oil
2FAL
5MHF
Furan or alcohol content [ppm weight]

Furan or alcohol content [ppm weight]
2FOL
5MEF
4 Methanol 1
Ethanol
Furans and alcohols in oil

2 0.1
2FAL
5MHF
2FOL
5MEF
Methanol
0.01 Ethanol
0
40 60 80 100 40 60 80 100
Temperature T1 [oC] Temperature T1 [oC]
Figure 6-8: Furanic derivatives and alcohols in oil vs. large chamber temperature. Linear plot (left) and lin-
log (right).
Based on these curves, correction factors are calculated to normalize the results to 20°C. The factors
are calculated by fitting the measured concentrations to an exponential correlation to temperatures.
Table 6-1 shows the ageing-marker correction factors calculated from the experiments, together with
the factors for water suggested in IEC 60422 standard [91]. It should be noted that unlike water, the
correction factors suggested for alcohols and 2-FAL should be validated in control tests. According to
the literature, only two labs have performed this type of testing [47, 48]. In Figure 6-9, a good
comparison of the CfM for CH3OH is obtained based on the two sets of data and data obtained with
aged mineral oil and TUK paper. However, the results obtained for 2-FAL show different trends
between the two sets of experiments, including the data obtained with aged mineral oil and TUK
paper. More experiments will be needed to validate the real trend for 2-FAL.
Figure 6-9: CfM Equilibrium curves obtained for various chemical markers [44, 56].
In 2007, Jalbert et al. [40] showed the dependence of methanol (CH3OH) in naphthenic oil on the
number of chain scissions and an equivalent relationship for 2-FAL. Later, they reported that oil
conditions had some effect on marker trends [92]. As seen in Figure 6-10a, methanol detection in oil is
virtually linear with NS, regardless of breathing systems and oxidative inhibiting conditions. A linear
relationship was also observed with 2-FAL (Figure 6-10b), except for the uninhibited oil sample aged
under air. In the latter case, probably due to an increase in oil acidity, a very high 2-FAL concentration
60
(200 ±30 ppm) in oil was measured with a relatively low number of chain scissions (NS=0.6),
corresponding to a DPv of about 730. Such behavior suggests that aged oil has an impact on the
partition of 2-FAL between the paper and the oil. Therefore, the absolute value of the 2-FAL
concentration cannot provide a fully accurate picture of paper ageing in a specific transformer oil.
However, the use of methanol appears to be a potential ageing indicator for assessing paper
insulation condition regardless of insulating oil conditions.
Figure 6-10: Dependence of chemical indicator concentrations in oil,a) CH3OH and b) 2-FAL, with the number of
chain scissions of an ordinary Kraft cellulose specimen under different ageing conditions.
6.5 Partitioning in synthetic ester

The correction factors as a function of temperature for water and methanol in synthetic ester (Midel
7131) and cellulose systems are shown in Figure 6-11 [48]. For mineral oil, it is clear that the quantity
of these ageing markers in oil, as in water, is temperature-dependent. Methanol content seems to be
more temperature-dependent than water content. Moreover, it is interesting to note that in regard to
furanic derivatives, contrary to what was observed for the mineral oil investigated, no clear
temperature dependence was observed. In Table 6-1, the correction factors for the various
compounds are listed at different temperatures.
61
Figure 6-11: Methanol and water correction factors for a synthetic ester and cellulose system [48]
Table 6-1: Correction Factors for Water and Ageing Markers in Mineral Oil or Synthetic Ester
20°C 30°C 40°C 50°C 60°C 70°C 80°C 90°C 100°C

Mineral oil + thermally upgraded paper + low-density pressboard
H2O 1.05 0,70 0.47 0.31 0.21 0.14 0.09 0.06 0.04
CH3OH 1.01 0.75 0.56 0.42 0.32 0.24 0.18 0.13 0.1
2-FAL 1.07 0.98 0.91 0.84 0.77 0.71 0.66 0.61 0.56
2-FOL 0.99 0.78 0.61 0.48 0.38 0.30 0.23 0.18 0.15
Synthetic ester liquid + thermally upgraded paper + low-density pressboard
H2O 1 0.84 0.71 0.60 0.50 0.43 0.36 0.30 0.26
CH3OH 0.99 0.63 0.41 0.26 0.17 0.11 0.07 0.05 0.03
Perrier et al. [93, 94] have shown that there is a large difference between transformers filled with
mineral oil and ester liquid (Figure 6-12 and 6-13). Mineral oil has a low affinity for water. However, its
water solubility increases markedly with temperature. Other liquids such as esters are more miscible
with water than mineral oil and show greater solubility at higher temperatures. They can absorb up to
ten times more water than mineral oil, and for this reason the partitioning curves are different for liquid
and cellulose. At lower temperatures (e.g., <100°C), water content in cellulose is little affected, even
though water concentration is higher in an ester. At elevated temperatures this may change: the
quantity of water that can be absorbed by the liquid depends on the temperature and type of liquid.
Usually there is a relationship such as mineral oil < silicone oil < natural esters < synthetic esters,
where mineral oil is able to absorb the least water, and synthetic esters, the most. Graphs similar to
Figure 6-1 have been produced for natural esters, as shown in Figures 6-12 and 6-13. The two graphs
show that for the same water content in paper, synthetic esters have higher water content than
mineral oil.
62
Figure 6-12: Perrier-Lukic equilibrium curves for paper and pressboard in mineral oil [93, 94]
Figure 6-13: Perrier-Lukic equilibrium curves for paper and pressboard in natural esters [93, 94]
63
64
7. Field Experience
This section provides brief examples of transformer case studies where marker measurements are
available.
7.1 Case Studies

The following case studies were submitted with data on some or all of the following parameters: the
degree of polymerization, furanic derivatives, carbon oxides and alcohols (methanol and ethanol) in
the oil.
Case #1
Table 7-1: Transformer Parameters
Voltage Rating Design Year of Cooling Cellulose mass Oil mass

(kV) (MVA) manufacture (t) (t)
110/10 25 GSU Shell 1963 ONAF 7 17
This unit, the characteristics of which are shown in Table 7-1, had been gassing with elevated levels of
hydrogen and methane and was showing indications of partial discharge activity (see Figure 7-1).
Partial discharges were measured online using HV bushing capacitive test taps.
Figure 7-1: Partial discharge measurements using bushing test taps, PD levels of 0.95nC and 1.35nC
The oil analysis shown in Table 7-2 indicated that cellulose degradation had taken place, but that oil
had been regenerated and the furanic compounds appear to have been removed by this process.
Therefore, the 2-FAL value was low.
Table 7-2: Oil Analysis
2-FAL ppm CH3OH ppb @ 35°C CH3CH2OH ppb @ 35°C

0.476 622 411
It was eventually decided to scrap the transformer. A number of paper samples were taken and the
DPv was measured on these samples. (See Figures 7-2, 7-3 and 7-4 and the results in Table 7-3.)
65
Figure 7-2: Suggested paper sample locations in a HV pancake winding
Figure 7-3: Shell form transformer
Figure 7-4: HV pancake winding
66
Table 7-3: DPv Results Taken during Teardown
Case #2 [95]
This was a 1,000-MVA 400/275-kV autotransformer with low 2-FAL and methanol, but also a low DPv.
The transformer was proactively decommissioned and scrapped after only 19 years in service
because it was believed to be at significant risk of failure from localized thermal ageing due to a
suspected manufacturing error causing oil flow restriction (Figure 7-5), even though low amounts of 2-
FAL (less than 0.5 ppm) had been measured (Table 7-4). During scrapping, the lowest measured DPv
was only 161, much lower than the DPv of 524 calculated using the highest measured 2-FAL level of
0.473 ppm and the Chendong equation. However, the CH3CH2OH concentration was higher than the
CH3OH concentration, showing cellulose overheating.
Figure 7-5: Winding hotspot at the top end of a 400-kV winding in a 1,000-MVA 400/275-kV transformer scrapped after
only 19 years in service
67
Table 7-4: Ageing Markers of Scrapped 1,000-MVA Transformer
Ageing marker Lab 1 Lab 2

2-FAL (ppm) 0.295 0.473
CH3OH (ppm) 0.132 0.097
CH3CH2OH (ppm) 0.280 0.225
CO (ppm) 642 747
CO2 (ppm) 2,490 2,576
Case #3
This was a 240-MVA 400/132 kV autotransformer with high 2-FAL, low methanol and a low DPv. The
autotransformer was decommissioned after 48 years in service. The transformer had been topped up
with poor-quality reclaimed oil in the past. It was thought that the high furanic derivative levels
measured were a result of contamination from the poor reclaimed oil rather than actual solid insulation
ageing. During scrapping, an inspection of the windings found that some of the winding insulation had
deteriorated and was of a dark-brown color, a sign of very advanced paper ageing, as shown in Figure
7-6. A DPv of 230 was estimated on the basis of the highest 2-FAL level, 5.12 ppm, Table 7-5. This
suggests that the high furanic compounds measured in three sets of oil samples, ranging from 3.86 to
5.12 ppm, are probably genuine, although some of these furanics may possibly come from the
reclaimed-oil contamination.
Prior to decommissioning, the measured methanol and ethanol contents were 0.10 mg/kg and
0.11 mg/kg, respectively (Table 7-5). The ratio of methanol/ethanol was greater than 0.5, suggesting
general heating instead of any localized hotspot involving solid insulation.
Table 7-5: Ageing Markers of Scrapped 240-MVA Transformer
Ageing marker Maximum value (ppm)

2-FAL (ppm) 5.12
CH3OH (ppm) 0.10
CH3CH2OH (ppm) 0.11
CO (ppm) 809
CO2 (ppm) 6,052
Figure 7-6: Ageing series winding conductor insulation in a 240-MVA 400/132 kV autotransformer scrapped
after 48 years of service
Case #4: [55]

These were six free-breathing core-form transformers that we scrapped (see Table 7-6). Paper
samples were collected on five units with oil in order to measure the chemical markers. As shown in
Table 7-7, the final DGA analysis indicated no particular problem and showed no obvious signs of
abnormal or accelerated solid insulation ageing. Table 7-8 shows the values obtained for CH3OH and
2-FAL in respect to the measured DPv (weighted-average DPv), based on more than 100 DPv
68
measurements on each unit. The variations in cellulose chemical markers are in line with the real DPv
measurements.
Table 7-6: Transformer Parameters
Voltage (kV) Rating (MVA) Design Year of Cooling Cellulose Oil mass
manufacture mass (t) (t)
230 45 Core 1958 ODAF ? 31
Table 7-7: DGA Data before Removing Transformers from Service
Table 7-8: Ageing Markers for the Six Transformers
69
70
8. Interpretation model using methanol

The challenge of any indirect correlation is the accuracy of the interpretation model. The model needs
to account for all transformer parameters, including design, oil-to-paper ratio, etc. In a recent
publication [56], Jalbert et al. propose an interpretation model based on a transformer post-mortem
analysis. In their study, they analyzed the DPv of 20 core-type power transformers. For each
transformer, over one hundred DPv tests were performed. They show that for one manufacturer, the
paper-to-board ratio is practically constant for transformers with different voltage levels built in the last
15 years (see Figure 8-1a). This means that methanol partition between the paper and board is a
constant for a given temperature. They also show that winding paper weight is relatively proportional
to oil weight, regardless of transformer design and size (see Figure 8-1b). Since the concentration
measured depends on the oil-to-paper ratio and appears to increase proportionally, this behavior
indicates that cellulose degradation levels can be determined using the oil-soluble marker for all
transformer designs.
0,20 1400
Paper/oil Standard
0,18 Standard
Paperless
a) 1200
Paperless
b)
0,16
Board/oil
0,14 Standard 1000
Paper weight (kg)

Paperless
0,12
800
Ratio
0,10
600
0,08
0,06 400
0,04
200
0,02
0,00 0
0 10 20 30 40 50 0 20000 40000 60000 80000 100000 120000
Number of apparatus Oil weight (kg)

Figure 8-1: a) Solid-insulation ratios for various core-type transformers; b) Paper weight vs. oil weight for
various core-type transformer [56].
Thus, the authors transpose a kinetic equation of cellulose depolymerization (see Section 4) to a
kinetic equation of methanol formation.
DP0
 1 =Ja(1– e k a t ) + Jckct Equation 8-1
DPt
where DP0 is the initial DPv found in a transformer after drying (about 900), DPt is the DPv at time t,
and the coefficients Ja and Jc are the number of CH3OH molecules produced by chain scissions in the
amorphous and crystalline phases respectively, with their corresponding formation rates k a and kc.
Finally, weighted average (mean) number of scissions (NS) is plotted against the CH 3OH
concentration corrected to 20°C and a regression curve is obtained (Figure 8-2).
3,5

Weight average mean NS (DP0/DPt-1)
3,0

2,5


2,0 

1,5 



1,0 

 
0,5 ONAN


 

0,0 R
0 200 400 600 800 1000 1200 1400 1600 1800

CH3OH (ppb) at 20°C
Figure 8-2: Methanol prediction model for core-type transformers [56].
71
This curve gives the following interpretation model:
 1  1.5542(1 - e - 0.0054CH 3 OH ) + 0.00101[CH 3OH]

DP0
Equation 8-2
DPt
Or:
DP0
DPt 
- 0.0054CH 3 OH Equation 8-3
1.5542(1 - e ) + 0.00101[CH 3OH]  1
where [CH3OH] is the concentration of methanol in ppb, corrected to 20°C. This model has a good
correlation with r2=0.94103. Using this model, the authors developed threshold values based on the
stipulations for 2-FAL [96]. These threshold values are reported in Table 8-1.
Table 8-1: Methanol Threshold Level and Its Condition [56]
[CH3OH]1 Mean calculated Paper condition

(ppb) DPv
0-50 1,000-700 Healthy
51-200 700-450 Moderate deterioration
201-1,440 450-250 Extensive deterioration
>1,440 <250 End-of-life criteria
1 Corrected to 20°C using an equation published in reference [47].
However, more data are needed in order to validate or improve this model.
72
9. Summary and outlook

9.1 Summary
This technical on new chemical markers shows that methanol is ready to be used by the utilities as a
complementary tool for assessing the residual life of transformer cellulose insulation. The direct link
between cellulose bond scission and methanol generation gives methanol a great advantage over
other markers. Moreover, this marker is sensitive to the ageing of both conventional and thermally
upgraded Kraft papers, unlike furanic derivatives, which are more sensitive to the ageing of
conventional Kraft papers. One of the major advances in this technical brochure is the importance of
taking account of transformer design, and especially the oil/paper ratio. Indeed, the interpretation of
any marker is directly linked to the quantity of materials involved. Round-robin tests on alcohol
measurements among different laboratories showed that this analytical technique is robust and
provides acceptable results. Moreover, correction factors must be used with partition phenomena,
especially oil temperature, in order to normalize the concentrations to 20°C. This is essential in
tracking real cellulose ageing. A first interpretation model for core-type transformers is also presented
at the end of this review. However, it requires further validation and improvement by the scientific
community.
9.2 Outlook
To improve ageing diagnosis, various aspects must be addressed in the future:
 Quantification of the effects of oxygen, moisture and acidity on the oil-cellulose equilibrium
 Development of interpretation models for shell transformers and other types of equipment
insulated with oil and paper
 Meticulous exploration of the influence of the use of ester liquids in order to understand the
interaction between this type of liquid and alcohol markers
The challenge posed by the use of these markers consists in differentiating between ageing of the
cellulose windings as a whole and ageing of only a small portion that is subject to a hotspot. This
aspect may be addressed by using ethanol once a better interpretation of this marker is available. At
this time, only a ratio of CH3CH2OH/CH3OH>1 indicates a possible hotspot involving paper, but the
area affected is currently unknown [94].
73
74
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78
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779 - CIGRE - Field Experience With Transformer Solid Insulation Ageing Markers

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A2/D1

Field experience with transformer

J. JALBERT, Convenor and

* Task Force Leader

2. Transformer design aspects ................................................................................... 15

3. Transformer materials ............................................................................................. 21

4. State-of-the-art ageing markers .............................................................................. 27

5. Round robin on alcohol measurements ................................................................. 49

6. Influence of different factors on ageing marker measurement ............................ 55

7. Field Experience ...................................................................................................... 65

8. Interpretation model using methanol ..................................................................... 71

9. Summary and Outlook............................................................................................. 73

10. References ............................................................................................................... 75

Figures and Illustrations

Figure 7-3: Shell form transformer ......................................................................................................................... 66

Equation 4-13 ........................................................................................................................................................ 40

2. Transformer design aspects

2.1 Design information

Group Rating Comment

2.2 Main design concepts

Figure 2-1: Principles of core-form transformers, from [3]

Figure 2-2: Principles of shell-form transformers, from [3]

2.3 Main active materials

2.4 Design aspects influencing the amount of active materials

2.5 Loading and operation

2.6 Design aspects influencing the generation of ageing markers

2.7 Correlation between ageing markers and design types

 Core and  Shell forms

 Core and  Shell forms

Figure 2-4: Total cellulose weight in kilograms as a function of rating

 Core and  Shell forms

● Core and  Shell forms.

Solid insulation1 Thermal class2 Composition Material description

Kraft paper Laminated wood

Cap sectors with snouts Laminated pressboard

Figure 3-1: Illustration of cellulosic insulation for transformers

3.2 Main insulating liquids

Liquid insulation Thermal class1 Materials description and

3.3 Cellulosic insulation ageing factors

The main degradation mechanisms are the following:

Figure 3-2: Simplified degradation mechanism for transformer paper-oil insulation

Figure 3-3: Degradation of insulating paper as a function of temperature

Cellulose is a polymeric chain of anhydrous-ß-glucose joined by glycosidic bonds. The degree of

Figure 3-4: Chemical structure of cellulose molecules

4. State-of-the-art ageing markers

Degradation by-products Standard method of determination Type

4.1 CO and CO2 Gases

4.2 Furanic compounds

Figure 4-1: Chemical structure of furanic compounds [20]

Compound Observed cause

Weight 2-FAL 5-HMF 2-FOL 5-MEF 2-ACF

Figure 4-2: Mechanism proposed for the generation of 2-FAL[24]

4.2.3 Stability of furanic derivatives

Figure 4-3: Stability of furanic derivatives at 110°C [19]

4.2.4 Partitioning of furanic derivatives

4.2.5 Correlation between 2-FAL and DPv

Figure 4-5: 2-FAL measurements obtained from 12 countries [20]

4.3 Methanol and Ethanol

Identification of methanol and ethanol as chemical indicators related to paper

Components of Kraft Model compound studied CH3OH CH3CH2OH

4.3.2 Stability of methanol and ethanol in oil

4.3.4 Laboratory ageing experiments

4.4 Kinetic studies on relating paper ageing to the production of