5145 Eberhardt Robert 2011.de - en PDF

T ECHNICAL U NIVERSITY G RAZ
DI SSERTAT ION
I INSTITUTE FOR H OCHSPANNUNGSTECHNIK

AND S YSTEMMANAGEMENT
e LECTRICAL e ROPERTIES AND
G ASUNGSVERHALTEN OF BIOLOGICAL AND SYNTHETIC e STAR
IN H OCHSPANNUNGS-
I SOLATIONSSYSTEMEN UNDER K ÄLTEEINFLUSS
dissertation
for Earning a Doctor of Technical Sciences
from
Dipl. Ing. Robert Eberhardt
1. Assessor: O.Univ.-Prof. Dipl.-Ing. Dr. techn. Hc Michael Muhr

2. Assessor: Prof. Dr.-Ing. Ernst Gockenbach, Hannover
Institute of High Voltage Engineering and System Management

Graz University of Technology
Graz in September 2011

thanksgiving
Hereby I would like all the people who have supported me during the four years that lasted my work around
the dissertation, thank.
My supervisor Michael Muhr, coaches and coach who allowed work only and my Zweitbegutachter Ernst
Gockenbach for his suggestions. Likewise, Frank Uhlig for assistance in chemistry-oriented questions.
Furthermore, all my colleagues at the Institute of High Voltage Engineering and System Management at the
Technical University of Graz for the good cooperation and the further development process of many mutual
learning, in particular Bettina Wieser for their patience with me.
In addition, my colleagues and friends from Siemens Transformers Austria Weiz, Robert Schwarz, Georg
Pukel, Fritz Baumann and the head of R & D Martin Stössl for the great help.
And of course my parents for good basis, my family and friends, but especially my wife Andrea for always
open ear and the tolerance which is demanded of their fellow human beings whether of scientific work
frequently.
Graz, in September 2011
Dissertation Robert EBERHARDT iii

STATUTORY DECLARATION
I declare under penalty of perjury that I have written this work independently, others not used as the sources / resources given
and the sources used literally and content taken from locations have been identified as such.
Graz, 07.09.2011 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,
(Signature)
STATUTORY DECLARATION
I declare did I have authored this thesis unabhängig, did I have not used other than the declared sources / resources and did I
have Explicitly marked all material Which has been quoted Either literally or by content from the sources used.
September 7th, 2011 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,
(Signature)
Dissertation Robert EBERHARDT iv

Short version:
This thesis deals with a comparative study of
Breakdown behavior and gas production of synthetic and biological esters in comparison to mineral oil, and
in connection with cellulose in inhomogeneous fields,
either at low temperatures as well as
Room temperature.
It was assumed that after strong cooling of the moisture exchange between the insulating liquid and
cellulose leads to a reduction of the electrical resistance. To investigate this, a test setup was developed
were tested with each 20 sample intervals with the 10 mm and 20 mm at -25 ° C, at -10 ° C and at room
temperature to AC breakdown with ramp-shaped voltage.
The setup was designed so that between the electrodes for the breakdown of the cellulose surface, a
leakage path was available. Before cooling the test setup, including the samples from Transformerboard
was heated to a typical transformer operating temperature (tested at + 60 ° C). Before and after the
experiments, a breakdown voltage gas-in-oil analysis as well as a determination of the breakdown voltage
(by IEC 60156) was performed and the moisture content according to Karl Fischer.
The obtained results of gas-in-oil analysis were presented both in absolute terms and in its differences from
baseline, and further analyzed with the five common evaluation schematics.
The results of the breakdown voltage studies were tested for independence and analyzed using descriptive
statistics. Finally, the degree of destruction of the cellulose was evaluated on the basis of visible puncture
marks.
From the results of the investigation findings on the electrical and chemical low temperature behavior of
Esterflüssigkeiten obtained.
Keywords:
Transformer oil, transformer paper, noxious gases, gassing, gas-in-oil analysis, synthetic esters, natural
esters, transformer, high voltage;
Dissertation Robert EBERHARDT v

Abstract:
This work deals with a comparative study of the breakdown behavior and the gas production of biological
and synthetic ester liquids Compared with mineral oil in connection with cellulose in inhomogeneous fields
at low Temperatures and room temperature.
It was Assumed did strongly When cooled, the moisture exchange between the insulating liquid and
cellulose at strong cooling would lower the dielectric strength. To investigate this, a test setup which
developed and breakdown tests were Implemented with 20 samples at a gap distance of 10 mm and 20
mm. The tests were Conducted at -25 ° C, -10 ° C and room temperature using ramp-shaped AC voltage.
The setup designed so what did a creepage path between what the available Electrodes Allowing on the
cellulose surface. Before cooling, the test setup, Including the Transformerboard samples, which heated up
to a typical transformer operating temperature (test temperature +60 ° C).
Before and after the breakdown voltage tests, a gas-in-oil analysis, a breakdown voltage test (gemäß to IEC
60156), and a moisture content test (Karl Fischer method) were Conducted.
The Obtained results of the gas-in-oil analysis, Both in absolute values and in Their differences from the
initial values, were shown and Analyzed with five common evaluation methods.
The results of the breakdown voltage tests were checked for independence and Analyzed using descriptive
statistics. Finally, the degree of cellulose degradation which Evaluated by the visible breakdown marks.
Through the investigation knowledge gained what about the electrical and chemical behavior of cooled ester
liquids.
Key words:
Transformer oil, Transformerboard, pressboard, ester synthetic, natural ester
transformer, high voltage, gas in oil, DGA, dissolved gas analysis;
Dissertation Robert EBERHARDT vi

contents
1 Introduction ................................................. .................................................. ........ 1
1.1 Problems for an insulation system at low temperatures ........... 7
1.2 Objectives and organization of this work ............................................ ....... 8th
2 Properties of insulating and pressboard ............................. 10
2.1 General Temperature and gas formation mechanisms of liquids ............................................
.................................................. ........... 10
2.1.1 Temperature behavior ................................................. .......................... 10
2.1.2 Gas formation ................................................. ......................................... 13
2.2 Petroleum ................................................. .................................................. .. 15
2.2.1 Composition and manufacture ............................................... ..... 16
2.2.2 Temperature and gas production behavior of oil ........................ 19
2.3 Synthetic esters ................................................ ..................................... 21
2.3.1 Composition and manufacture ............................................... ..... 23
2.3.2 Temperature and gas formation behavior of synthetic esters ..... 24
2.4 Natural esters ................................................ .......................................... 26
2.4.1 Composition and manufacture of soybean oil .................................. 27
2.4.2 Temperature and gas formation behavior of natural esters ......... 30
2.5 Cellulose ................................................. .................................................. .. 31
2.5.1 Production and structure of cellulose for transformers ................ 33
2.5.2 Gas formation behavior of cellulose ............................................... .... 35
2.6 The oil - cellulose - insulation ............................................ ................... 35
2.7 More gas production operations ................................................ ................... 36
2.8 Dielectric behavior ................................................. ................................ 36
2.8.1 Dielectric behavior of liquids ............................................. 36
2.8.2 Dielectric behavior of impregnated cellulose ............................. 42
2.8.3 Special, the exchange of moisture and low temperatures relevant aspects
......................................... ................................................. 43
2.9 Behavior of the fluids at low temperatures ................................. 44
3 Task ................................................. ........................................... 46
Dissertation Robert EBERHARDT vii

3.1 Current state of research ................................................ ..................... 47
3.2 Experimental design and considerations for cooling ............................. 48
3.3 Selection of fluids ............................................... ........................... 50
3.4 Experimental Design ................................................. ....................................... 51
3.5 Procedure ................................................. .................................................. ...... 51
3.6 Evaluation ................................................. ............................................... 53
4 Studies of alternative liquids at low temperatures .. 54
4.1 Experimental setup ................................................. ........................................ 54
4.2 Dielectric studies of the cooled oil-cellulose insulation 55
4.3 DGA - Dissolved Gas Analysis - gas-in-oil analysis ................................. 57
4.3.1 The sampling ................................................ .......................... 58
4.3.2 The extraction of the dissolved gases by means Toepler pump ................... 59
4.3.3 The gas analysis by gas chromatograph ........................................ 60
4.3.4 Evaluation and interpretation ............................................... ............. 62
4.4 Other chemical and electrical tests on the liquids 68
4.4.1 Moisture in Oil - Coulometric Karl Fischer titration .............................. 69
4.4.2 Breakdown voltage according to IEC 60156 .............................................. 72
4.5 Evaluation methods ................................................. .............................. 73
4.5.1 Regression ................................................. ......................................... 73
4.5.2 Descriptive statistics ................................................ ............................. 73
4.5.3 Sighting of the punch traces of the cellulose .............................. 74
5 Results ................................................. .................................................. .... 75
5.1 Breakdown voltage tests on oil-paper insulation system ........ 75
5.1.1 Studies of independence and distribution function ........... 76
5.1.2 Results of descriptive statistics .............................................. .... 79
5.2 Gas-in-oil analysis ........................................... ........................................... 81
5.2.1 Interpretation Results of generally recognized schemes .............. 82
5.2.2 Gas formation in the experiments in absolute values (ppm) ..................... 84
5.2.3 Gas formation in the experiments relative (in% of baseline) .... 87
5.3 Oil characteristics ................................................. .............................................. 90
5.4 Sighting the breakdown lanes on the cellulose ..................................... 92
Dissertation Robert EBERHARDT viii

6 Discussion ................................................. .................................................. .... 95
6.1 Considerations for independence, sample number and concentration of gas .. 95
6.2 By impact behavior at low temperatures .......................................... 96
6.2.1 Discussion of breakdown voltages ............................................ 96
6.2.2 Evaluation of breakdown lanes on the cellulose ......................... 97
6.2.3 Oil characteristics - breakdown voltage according to IEC 60156, and water content
.......................................... .................................................. ........ 98
6.3 Gassing ................................................. ..................................... 99
6.3.1 Gas formation ................................................. ......................................... 99
6.3.2 Evaluation schemes ................................................. ..................... 100
6.4 Referring to the current state of research ................................ 102
7 Summary ................................................. .................................................. ..... 104
7.1 Dielectric behavior ................................................. .............................. 104
7.2 Gassing ................................................. ................................... 105
7.2.1 Usability of the evaluation schemes 105 ......................................
7.3 Considerations for further investigations .................................. 106
8th Impact on the practice .............................................. ......................... 107
8.1 Cold start ................................................. .................................................. . 107
8.2 Gas-in-oil analysis ........................................... ......................................... 108
8.2.1 Gas production ................................................. .................................. 108
8.2.2 Evaluation schemes ................................................. ..................... 108
9 Summary ................................................. ....................................... 110
9.1 Dielectric behavior ................................................. ............................ 110
9.2 Gassing ................................................. ................................... 111
10 Bibliography ................................................. .................................. 113
11 Attachment ................................................. .................................................. .... 120
Samples impregnation ................................................. ......................................... 120
Dissertation Robert EBERHARDT ix

introduction
1 Introduction
The global energy situation shows that the supply of large metropolitan areas remains an important task,
whose demands grow both in quality and in quantity. It is estimated that by 2030 nearly two thirds of the
world's population will live in cities.
A particular challenge for the establishment and development of the serving infrastructure provide the
rapidly proliferating so-called megacities represent Was there 1959 world only two cities with more than 10
million inhabitants (United Nations definition of "Mega City"), namely New York. and Tokyo, as it was in
2004 already 22 cities in which nearly 10% of the world's urban population lived.
Two thirds of the makers of the world cities see over the next five to ten years investment needs in the
energy supply. Environmental consequences of course, play an important role in the investment measures.
[1]
Illustration 1: Global energy production, expected growth by 2030 [2]
Dissertation Robert EBERHARDT 1

introduction
Added to the decades comes lasting upward trend in energy consumption. According to the World Energy
Report the IEA (International Energy Agency) will global energy consumption from 2006 to 2030, even
taking into account the expected increase in efficiency to 75% larger (see Figure 1) [2].
The majority of this consumption trend, will be as described above, take place in cities, which is their energy
consumption will increase most will be geographically the "emerging markets" of the emerging third world
countries. The European area is too, but not so serious affected (see Figure 2).
Figure 2: Monthly production of electric energy in TWh of some European countries [3]
In the supply of such agglomerations plays the quality of
The transmission network after the generation undisputed one of the major roles. It is necessary to build
more powerful transformers and switchgear even smaller space and still populated mainly closer. Especially
the power transformers as a link between the transmission network (high and extra high voltage level) and
the distribution (Mittelbis high voltage level) here represent important components.

introduction
On one hand, they represent large investments with life cycles of up to 50 years and on the other hand they
are at particularly fail critical positions in the transmission chain.
With few exceptions, almost always these are transformers with a mixed insulation soaked with a highly
viscous liquid solid. Wherein the solids (mainly cellulose) takes over the mechanically load-bearing
properties, and in addition to the electrical insulation also holding the liquid, the object of the cooling
medium. More precise details on this in Chap. represented 3.1 and 3.4. While there are also versions with
transformer pure solid insulation (cast resin) insulation and gas (mostly SF 6 - Sulfur hexafluoride), but they
are used only in special cases and are not part of this work.
Many decades has been used to isolate oil. It is deeply researched and all the properties are well known. In
addition to the many advantages it also has the serious disadvantages of high fire load and the long
biodegradability.
For these reasons, the aim is to replace the mineral oils in the long run by alternative insulating fluids. For
this example, natural or synthetic Esterflüssigkeiten on offer.
Although there are other alternative insulation fluids, for example silicone oil, or fluoropolymers, with good
electrical and thermal properties [17], but the cost of these liquids are partially around the tens to hundreds
of times higher
and thus come in the practice For
Power transformers out of the question.
Esterflüssigkeiten not have the disadvantages of the mineral oil, their fire load is much lower, its focal point
is much higher and they are considered from the standpoint of environmental impact, much less critical [4].
For comparison, mineral oil has a calorific value of 46 MJ / kg [5], natural Esterflüssigkeiten 34 MJ / kg
(soybean oil) [6] and synthetic esters 31 MJ / kg [5]. The results for mineral oil at a power transformer 40
with a t amount of oil stored energy of 1840 TJ (only caused by the oil, other combustible materials such as
cellulose, were not taken into account).

introduction
In a container filled with synthetic ester transformer while it is only about a quarter less (total around 1,240
TJ), but it is the much higher focus involve. This is for mineral oil at about 150 ° C [7] and for synthetic and
natural ester between 300 ° C and 340 ° C [5], [8].
result from reduced fire load for the operators of the plants following secondary benefits [9]:
• In the panel no firewalls are necessary
• The cost of fire liability and insurance are lower
• The requirements for the fire extinguishing system for the control panel in the substation can be
optimized
• The distance between the transformer and adjacent installations and / or buildings is less critical
• Environmental impact assessment of construction projects can be passed easily through reduced
health hazard and fire load
The resulting from a technical perspective benefits of Esterflüssigkeiten to mineral oils are listed below:
• The much higher moisture absorption capacity of several hundred mg / kg (ppm) without any effect
on the dielectric properties [5]
• Aging tests with esters have shown compared with mineral oil that this positive impact on the aging
behavior of pressboard. The Depolymerisationswert of aged in esters Board is substantially higher
than that of cellulose in the same treated mineral oil [10]
Last but not least an increased environmental awareness of the population also makes the concerns of the
degradability of the insulating liquid in the case of a leak-related
Exit necessary.
Due to lack of scientific research and practical results of the use of alternative insulating fluids is still
restricted. Also research to improve maintenance rules for these insulation materials, their dissolved gases
are still concerning necessary.

introduction
In this work the properties of alternative insulating fluids are treated in comparison with conventional mineral
oil.
Applications of alternative insulating fluids
The property of good fire resistance and excellent degradation characteristics make these liquids handy for
the population-level use in urban areas and other areas with contamination problems. In order to
may reduce the risk of injury and
Damage from secondary loss events, such as combustion or poisoning is minimized are not produced
directly by the action of voltage.
Esterflüssigkeiten are in the medium voltage range up to 40 kV for many years in wide use. The observable
behavior in this area is satisfactory and many transformer manufacturers have Estereinheiten in the medium
voltage range in the standard program.
In large transformer range for voltages above 40 kV, this breakthrough is still pending. This is not least to
the lack of scientific studies
due. The financial expenditure For one
Large transformer is many times higher than in a distribution transformer, therefore still reach into the field
producers and users currently primarily on the mineral oil-filled units back.
This limitation of the possible applications is based, as already mentioned, to insufficient scientific
consideration of the properties of natural and synthetic esters.
Problem "cold start" - alternative insulating liquids under cold exposure
In Esterflüssigkeiten it comes from cold influence in a dramatic increase in viscosity. This problem is an
issue of fuels in the winter for a long time. For example, the required consisting of esters biodiesel
for his
Usability in winter a solution. for fuels
is This object is achieved by addition of additives to
Simply get at improving the flow properties and pour point reduction. In transformer oils, this is very difficult,
however, because the addition of

introduction
Additive lowers the important property of electrical resistance and the liquid thus making it unusable as a
high-voltage insulation. In the
Insulating Envirotemp FR3 by Cooper Power Systems, for example, attached to the flow property
improvement by the manufacturer 1% additive. Larger amounts would not be used from the viewpoint of
electrical resistance. Since the insulating fluids must also fulfill the function as a coolant in the transformer,
are not only the dielectric properties but also physical properties such as viscosity, decisive for the suitability
by. Natural Esterflüssigkeiten have due
their molecular structure
(Long-chain fatty acids) already at room temperature a higher viscosity than mineral oil, this is still within an
acceptable range. Considering further that a transformer
average in operation
has temperatures of 50 to 60 ° C and the Esterflüssigkeiten at these temperatures have sufficient tendency
to flow, thus provides this condition estergefüllter units from the viewpoint of the viscosity is not a problem.
However, the temperature dependence of the viscosity has an effect with respect to the necessary carrying
out a cold start,
in geographical regions with low
Outside temperatures negatively. makes the resulting reduction of the cooling properties
perhaps heating of the estergefüllten
Transformers before commissioning necessary.
The electrical behavior at low temperatures, however, is not yet sufficiently researched area in oil-paper
insulation systems with natural and synthetic esters. The extent to which there is a reduction of the electrical
resistance thereby to be scientifically studied in the present work.
Especially the behavior of water present in the liquid water could help to degrade the insulation of an
oil-paper insulation system. The maximum amount of moisture that can be dissolved in the esters decreases
as the temperature (see Figure 3). There is the possibility that it comes in Esterflüssigkeiten to an increased
concentration of water on the cellulose surface.

introduction
Figure 3: Water absorption behavior of Esterflüssigkeiten compared to mineral oil [56]
1.1 Field problems for an insulation system at deep
temperatures
result for the user of oil-paper insulation system in connection with low temperatures without solidification of
the liquid always possible problems as the need for so-called cold start there. This is about the connection
of the transformer to the grid, possibly at full load, even though the transformer temperature and thus the
temperature of the insulating reached the surrounding temperature, which can be in cold or winter readily
down to -30 ° C or less , This means that the insulation is exposed to in the cold state of the full electrical
and thermal stress. The insulating liquid has a higher viscosity at low temperatures, the cooling channels
must therefore be designed on the lower flowability, thus possible hot spots,
low ambient temperatures, rapid heating than the total transformer can be cooled and cause no
damage. From the viewpoint of the electric load, in particular the humidity in the period in which the
insulation system is cooled or has just reached the lowest temperature, but the moisture equilibrium
between liquid and cellulose has not yet set is critical. During this period, the relative humidity in the

introduction
Oil increases, as it takes some time until the water diffused into the cellulose to be bound there
[11], [14]. It is therefore clear that at low
Temperatures, the insulating liquid can not be considered separately from the cellulose. This assumption
should be studied scientifically for the first time in the present work.
Primarily the following points should be considered:
• As a short-term cooling effect on low temperatures on the breakdown behavior of an oil-paper
insulation system?
• What are the different amounts of gas produced during these carbon copies and versions of the
various liquids used?
To perform this until now pending investigations, it was necessary both to develop an experimental
arrangement in which a heating and cooling possibility existed and secondly to create a pilot program with
which the above points can be examined for the harmful gas and dielectric behavior. Furthermore, this
arrangement had to include in the breakdown scenario as also provide a creepage distance on the cellulose
border as a way for the rollover available in both liquid and cellulose.
1.2 Objectives and structure of the present work
The aim of this study was to expand the range of possible applications of synthetic and natural esters,
by scientific
Investigations were carried out both with esters and mineral oil for comparison. For this, a testing apparatus
and test procedure were developed, which should provide more analysis options (see section 3.5 and 4.1).
On the one hand the suitability under actual conditions of the transformer fluids was associated with
pressboard in the cold of interest. For this, the breakdown behavior at room temperature and after rapid
cooling and should
Dissertation Robert EBERHARDT 8th

introduction
Influence of associated oil-paper moisture dynamics are investigated. On the other hand, the possibility was
envisaged to check the fluids used in these experiments to their gassing by the gas coefficients were
determined before and after the penetration tests by gas in oil analysis.
The results of the gas studies should be evaluated with various conventional mineral oil-assessment
schemes to determine at which gases would occur similarities, differences or even falsification of
diagnostics at Esterflüssigkeiten, such as the concealment or pretense of cellulose error by CO or CO 2
Production in the ester (see Section 2.2.2, 2.3.2 and 2.6.3).
Structural work
Chapter 2 describes the properties of the fluids and pressboard samples used. It shows the assumptions
and their underlying facts about the materials.
In Chapter 3, the task is explained in detail. the reasons for the creation of the experimental design and the
test procedure and the selection of fluids and the evaluation are outlined.
Chapter 4 contains a detailed description of the studies conducted with the liquids and the cellulose at low
temperatures. Chapter 5 contains the results of the studies listed. In chapter 6, the results are discussed in
Chapter 5, and compared with the provisions made in Chapters 2 and 3 assumptions.

Properties of insulating and pressboard
2 Properties of insulating and pressboard
In this chapter of insulating fluids and material properties and descriptions used in the tests the
Transformerboard used are discussed. Initially, the relevant, fundamental physical and shown in particular
the electrical properties of liquids for comparison.
Table 1: Basic properties of the liquids used for comparison [40], [19], [5], [8]:
property unit provision mineral oil synthetic esters natural ester
Breakdown voltage kV IEC 60156 70 55 50
Loss factor tan δ IEC 60247 <10.10- 4 10-30.10- 4 10-30.10- 4
permittivity ε IEC 60247 2.2 3.3 3.2
pour Point °C ISO 3016-40 - 50 - 15 to - 25
Flash point °C ISO 2592 135 - 145 257 310-325
focus °C ISO 2719 150 - 175 310 354-360
Viscosity (kin. At 40 ° C) mm 2 / s ISO 3104 20 30 33 - 45
density ρ ( 20 ° C) kg / m 3 ISO 3675 900 960 920
2.1 General Temperature and gas formation mechanisms of
liquids
2.1.1 Thermal behavior
It arises with the increasing viscosity with decreasing temperature, the problem of declining flowability. Thus
the cooling properties of the insulating liquid due to falling velocity decrease dramatically. In the case of
continuous operation, especially under load, no consideration has to be made to this fact, since the
insulating liquid is already sufficiently heated by the occurring heat loss of the transformer.

Critical is only the case of switching on after a long break in which the insulating medium is allowed to cool
to the low ambient temperature. The extreme case is reached when the temperature falls below the pour
point of the liquid. After that, the insulating medium can no longer flow due to solidification. The energy
removal from the waste heat producing elements of the transformer is now limited to the capacity of the fluid
through its heat capacity. If this exhausted, no more heat is added and the temperature of the paper
insulation can be up to critical levels increase. The temperature behavior of the electrical resistance of the
liquid used in itself is already partially explored and it has been shown
In conjunction with cellulose other hand, new areas of research, the electrical strength arise concerning,
regarding the moisture balance of the two substances. Especially in the lowering of the temperature of an
oil-cellulose insulation system it comes to the release of water in the liquid, which now then seeks to move
by diffusion randomly in all directions to the nearest surface and to attach there.
Is this a cellulose surface, the water diffuses into the material to be stored there as a paper moisture until
equilibrium (see Figure 5) is reached. Since, however, continue to decrease the already low diffusion
coefficient in the liquid [41] (or in the impregnated with the liquids cellulose) with decreasing temperature it
may be assumed that there, at a becoming free of water, only a deposition and an increase in concentration
arrives at the paper surface, which decreases only gradually by a further transport of water molecules into
the interior of the cellulose. Well, it turns from a user perspective the question
to what extent this in the case of
Transformer disconnection of a Estereinheit may result at low ambient temperatures to a reduction of the
electrical resistance of a tangentially-loaded in the worst case cellulose surface.

The gas formation behavior of fluids can theoretically predict only inaccurate, it must be determined
empirically. From the ingredients and previous studies only rough estimates can be made. Since all fluids
are composed of hydrocarbons, in essence, the products of decomposition must be composed of the same
constituents. therefore may contain carbon monoxide and carbon dioxide are expected (with the alkenes
and alkynes) and free hydrogen and cellulose decomposition products as well as gases in the esters of the
alkanes of the low hydrocarbons methane, ethane, propane and butane. Although an increased rise of
ethyne and ethene can be expected due to the short-term high temperatures in the arc (see section 2.2.2,
2.3.2 and 2.4.2), the large number of different
ingredients difficult However, here as well as in the
Breakdown voltage, the possibility of modeling.
Among other things, two essential properties of insulating fluids greatly change with temperature: the
viscosity and water absorption capacity (see Figure 3 and Figure 4). The increase in viscosity with
decreasing temperature to a hand, as described above, to a reduction of cooling due to the lower flowability.
On the other hand, it also leads to a reduction of the diffusion coefficient, and thus a delay in the material
transport, for example water, in the liquid. Since the humidity tends with changes in temperature to an
exchange between cellulose and insulating liquid is cooled at a cooling from such transportation, even when
the liquid is not saturated with moisture, can be assumed. The obstruction of molecular motion on the
cellulose surface and on the other hand within the cellulose, as mentioned above,
to a superficial
lead concentration increase.
At the same time the water absorption capacity of liquids decreases with temperature. This means that even
when not wet saturated liquids, an increased release of water molecules in the insulating medium, which in
turn tend to be deposited at the nearest surface.

Figure 4: Representation of the temperature dependence of the viscosity of various insulating fluids [29]
Figure 5: Representation of the moisture balance between oil and cellulose [58]
2.1.2 gas formation
Since the oil-board insulation on the one hand from polymers of different hydrocarbons beinhaltendem
insulating and on the other hand leg-holding of polymers of different carbohydrates cellulose, are cleaved by
the action of various energies fragments or components thereof. As liquids include bonds with other
energies, the cellulose, the gassing is treated separately here.

In the present study the gases listed in Table 2 were examined [47]
Table 2: Names and chemical symbols of the analyzed in this work gases:
Surname symbol
nitrogen N2
oxygen O2
hydrogen H2
Carbon monoxide CO
carbon dioxide CO 2
methane CH 4
Ethan C2 H6
Ethene (ethylene) C2 H4
Ethyne (acetylene) C2 H2
propane C 3 H 8th
propene C3 H6
Bond types and energies
Various types of bonding of the atoms in the molecules (one carbon-hydrogen bonds, single, double and
triple carbon-carbon bonds) require different high energies to be split. The binding energy is expressed in kJ
/ mol. So with this specified power 6.022 · 10²³ individual bonds can be split. Table 3 shows the values of
energy, occurring in mineral oil and ester bonds together. The information can be given to the values only in
areas due to external influences.

Table 3: Energies occurring in mineral oil and esters bonds [57]:
binding Energy in kJ / mol
CH 400-415
CC 345-355
C=C 610-630
C≡C 835
CO 355-380
C=O 724-757
OH 460-464
2.2 mineral oil
Mineral oils are the insulating fluids used in practice by far the most common. They are basically suitable for
almost every Isolierzweck and accordingly frequently in transformers,
in oil-impregnated cables,
Capacitors, transformers and bushings used. However, the main application lies with the transformers,
which is why they are also called "transformer oil" [28].
When mixed dielectric in combination with cellulose Mineral oil is a decades-proven in continuous use,
electric high-strength high-voltage insulator [20]. Since the properties are well known through the years of
use of the mineral oil, it was used as a reference for the investigations carried out. It was the sort Nytro 4000
X the manufacturer NYNAS used. It was prepared by a vacuum and heat treatment for drying and
degassing and by filtering.
Here briefly the manufacturer of the most important characteristics are summarized again: The breakdown
voltage according to IEC 60156 is specified at an electrode spacing of 2.5 mm with> 70 kV and the loss
factor (IEC 60247) with <5 × 10 Third the focal point
is indicated by at least 135 ° C. The
permittivity ε r is 2.2 at 25 ° C and the volume resistance is in accordance with IEC 60247 400 GΩm.

2.2.1 composition and preparation
Mineral oil consists, apart from impurities such as sulfur or the like, basically from four different hydrocarbon
groups: paraffins, naphthenes, aromatics and olefins (see Figure 6). Paraffins (or alkanes) are
double-bond-free chain molecules, wherein
them if they
are called have branches, "iso-paraffins". The linear types of these molecules are also known as waxes.
When cold its free flow is impaired, so they are not suitable for insulating fluids for applications at low
temperatures. Furthermore, they have the lowest thermal stability and only low water and solid solvency and
thus contribute to siltation.
Figure 6: Representation of the molecular structures of hydrocarbons in mineral oil [29]
Second major component is called the naphthenes, and cyclo-paraffins or cyclo-alkanes. This is to cyclic
hydrocarbons without double bonds. They have much better low temperature properties and better fuel
solvency.

Aromatics, however, are ring-shaped molecules with double bonds, they have a ring of six carbon atoms
with alternating double and single bonds as a characteristic feature.
Monocyclic aromatics in themselves have useful properties, especially in terms of gas-solving ability and
oxidatioinsstabilisierende effect, but the aging resistance of these molecules is very limited. They are
increasingly used in capacitors where their gas-solving ability is used, but not in transformers.
Polycyclic aromatics are often harmful (carcinogenic) and are under electrical stress negative effects,
especially in surge they put the electrical resistance decreased and they have in turbo charging propensity.
Therefore, these aromatics are already
in the
, As far as possible the production process of the insulating liquid, withdrawn. The fourth part of the olefins
are mentioned. Basically, they are components of the group of the paraffins, but they have double bonds
and are therefore partially unsaturated. This makes them chemically vulnerable and susceptible to aging
and oxidation. Modern insulating oils contain only very small amounts of olefins.
The actual content of these components varies depending on the composition of the crude oil and type of
refining process (see Figure 7). Depending on the constituent group the bulk of
by weight, the liquids are
variously referred to [30], [20].
• 42-50% paraffin content: naphthenic oils
• 50-56% paraffin content: Between oils
• 56-65% paraffin content: paraffinic oils

Figure 7: The content of different hydrocarbons, after refining, [30]
2.2.1.1 manufacturing
On his way from crude oil are ready to use insulating oil passes through oil, roughly speaking, a five-step
process. First bitumen is deposited to a maximum of 350 ° C by fractional distillation and separation
performed according to the different boiling points.
Thereafter, it is deposited by cooling to -30 ° C or pour point reducing by the addition of additives, the wax
may be contained. As a third step (by extraction with a solvent, for example SO 2) the proportion of undesired
polycyclic aromatic compounds (PAH's) is reduced.
As the penultimate step of producing the so-called hydrotreating by the addition of hydrogen under high
pressure, a "finishing" further undesirable, but not removable play is performed. Thus they are converted
into "desirable" substances. For example, polar compounds are converted through this process step in
non-polar and therefore represent from electrical point of view no longer a problem. [30]
a "finishing" process, in which the oil is still processed and any additives are added is done Finally. As
additives antioxidants and passivators are used. Inhibitors such as 2,6-di-tertiarybutyl-phenol-para-cresol
(DBPC) may be used to determine the aging resistance

to increase by blocking reactive radicals passivators serve the copper (and thus the cellulose) in the
transformer by, as the name implies, to protect against passivation example corrosive sulfur [31] [20].
The treatment (see Figure 8) has a cleaning of the mineral oil of particles of water and dissolved gases to
the destination. This is done on the one hand by a coarse filtration with a pore size of about 100 microns
and a fine filtering of 2-10 micron pore size. For drying and degassing the oil is heated to about 60 ° C and
distributed in a thin vacuum process liquid onto a large surface on which dissolved gases and water vapor
are withdrawn. According to this manufacturing and treatment process, the oil is operational and can be
filled. [28]
Figure 8: Schematic representation of the oil preparation process with degassing and dehumidification under vacuum [28]
2.2.2 Temperature and gas production behavior of oil
temperature behavior
For petroleum in the literature a Brennunkt of 150 - 175 ° C specified. As stated in the introduction, it comes
through this low value to massive problems in fire protection.
For applications at low temperatures there is no objection because of the, compared to the natural
Esterflüssigkeiten, very low pour points. New

Mineral oil at room temperature can absorb ppm water (according to [56]) is about 40 to 50 and this value
decreases with temperature. At -20 ° C, the half thereof, that is 20 to 25 ppm of water are added may only.
Accordingly, therefore, at a cooling little water is free.
Mineral oil due to the low absolute humidity values of the smallest drop of the electrical resistance can be
expected. The transformer Practice has shown that there is at cold start in regions with low ambient
temperatures to no problems.
In order to achieve changes here, it is very likely to be necessary with a much higher relative humidity
values, as usual in practice, (ie over 90%) to work and even then it can not be assumed that a safe impact.
Attempts were therefore made for the investigations carried out here, mineral oil with rather high for the
transformer practice moisture values (5 to 14 ppm, see Table 20 ABOVE) to use a worst-case scenario to
simulate the reference here.
Gas formation behavior
Mineral oils consist of groups of CH 3-, CH 2 and CH. These groups are connected by CC bonds. By more or
less strong, mainly thermal energy of such groups or fragments are cleaved thereof. These fragments can
be: CH 3, CH 2, However, CH, C, or H. They are extremely fickle and recombine immediately to gas molecules
such as HH (hydrogen, H 2) CH 3 H (methane, CH 4) CH 3 CH 3 ( Ethan, C 2 H 6) CH 2 = CH 2
(Ethylene / ethylene, C 2 H 4) or CH≡CH (ethyne / acetylene, C 2 H 2). More rarely, hydrocarbon gases with C 3 and
C 4 Groups or even longer-chain hydrocarbons (for example X-wax) is formed.
The gases dissolve in oil or collect as a free gas (Buchholz relay) can be made using DGA (dissolved gas
analysis or gas-in-oil analysis) can be determined in the quality and quantity (see also Section 4.3).
The higher to cleaving the bond energies of the fragments and are to be recombined, the higher the
required, supplied from the outside

Heat energy to separate them. Therefore, one can from the measured gases infer the type of error.
Hydrogen is present at lowest energy, and even at partial discharges without arcing. Ethene is formed prior
to ethane and methane at temperatures around 500 ° C. Ethyne, however, briefly requires higher
temperatures (800 to 1200 ° C) and rapid cooling in order to collect as a stable recombination product. It is
therefore a clear indicator of an arc, which reaches in its ion channel temperatures of several thousand ° C,
while it is surrounded by oil with normal temperature which cools the area of the channel after the
breakdown of the arc quickly. CO and CO 2 be formed by oxidation, however,
is the formation of significant quantities only in larger
Aging periods possible. [47]
The basic structure of esters is different compared to only insofar that a number of additional CO and OH
groups are attached from the fatty acids in the molecules and can also be cleaved by the action of thermal
energy.
This leads to the supposition that esters as insulating liquids in one hand
similar Spin-Off and recombination the
held hydrocarbons and thus similar gases are produced, but could on the other hand at
pure oil errors increased
Kohlenstoffoxidverbindungen occur. This would according to current DGAAuswertemethoden (described
[60] in) are, however, interpreted as a paper error. So it could come to pretense or concealment of cellulose
degradation.
2.3 Synthetic esters
Synthetic esters are artificially produced Esterflüssigkeiten. Esters form a group of substances of organic
compounds that arise when an oxygen acid reacts with an alcohol, with elimination of water. (See Figure 10)
The physical properties of the ester produced can be

change greatly by the choice of starting materials. For example, short-chain Carbonsäureester are still very
soluble in water, whereas all esters having more than four carbon atoms already completely hydrophobic
behavior [12], [53].
From the perspective of electrical engineer offer Carbonsäureester characteristics that qualify them as
insulating oils. The electrical resistance and dielectric characteristics are very good, the thermal conductivity
is high, the pour point is low and they are readily and completely biodegradable. The high flash and fire
points and the good degradability provide the greatest benefits over petroleum is [29]. In the tests carried
out here was Midel 7131 the company M & I used. It is a pentaerythritol Tetracarbonsäureester. He was
treated by a vacuum and heat treatment for drying and degassing and by filtering.
Here briefly the manufacturer of the most important characteristics are summarized again: The breakdown
voltage (IEC 60156) is indicated with> 75 kV at an electrode spacing of 2.5 mm and the loss factor (IEC
60247) with <8 × 10 Third The flash point is given as 260 ° C. The dielectric constant ε r is 3.2 at 25 ° C and the
volume resistance (in accordance with IEC 60247) is for DC> 30 GΩm [5].
Figure 9: The structural formula of pentaerythritol Tetracarbonfettsäureesters Midel 7131 by M & I with the basic four-fold
structure and the acid radicals (R 'to R' '' ') [12]

2.3.1 composition and preparation
From an electrical and environmental point of view has the Pentaerythrittetracarbonsäureester, licensed
from BASF in 1982 and has since been produced by M & I as Midel 7131, already proven in a variety of
distribution transformers [4], [54].
The ester consists of pentaerythritols (polyhydric alcohols), which are esterified with carboxylic acids sixth,
seventh or eighth value [29]. The structural formula is shown in Figure. 9 The preparation of an ester (see
Figure 10 and Figure 11) is carried out by adding an alcohol to a carboxylic acid as an equilibrium reaction
with elimination of water. If one removes the water so the equilibrium shifts in favor of the ester [55]. For use
as insulating highest possible purity is essential. Therefore it is necessary that the starting materials already
contain a minimum of contaminants, as these otherwise accumulate and in the esterification so that the
molecules undesirable characteristics, such as higher conductivity or a polar appearance,
After the manufacture of a preparation with filtering and degassing or drying under vacuum is necessary
prior to filling also in the synthetic esters.
Figure 10: Reaction equation of Estersynthese the example of rapeseed oil [52]

Figure 11: Reactor for the production of Carbonsäureestern [55]
2.3.2 Temperature and gas formation behavior of synthetic esters
Both, in comparison with the mineral oil, high fire point of 310 ° C as well as the low pour point of -50 ° C
gives the synthetic ester basically good properties as insulating liquid. A disadvantage is the comparatively
high viscosity (see Figure 4) corresponding to the medium at low temperatures, due to the poor flowability,
only gives limited cooling properties. The penetration behavior of the pure liquid is from -25 ° C to +25 ° C
only slightly dependent on the temperature but rather on the moisture concentration [22]. However, it is
likely that under the Miteinbezug of cellulose in the test arrangement, the temperature drops very much a

Reduction of the breakdown voltage will occur. This is attributable to the fact that when lowering the
temperature, moisture is discharged out of the liquid into the cellulose. During cooling forms at the board
surface a significantly higher moisture concentration as the water only needs some time due to the low
diffusion constant [41] in order to penetrate further into the interior of the cellulose and distribute evenly
there. However, it remains to be considered that the saturation moisture content of the natural ester at
-25 ° C must still be accepted at more than 1000 ppm [52] and it is only probable, but not certain whether
the liquid actually gives off water at a cooling to a temperature at 10% relative humidity enough to have a
measurable effect on achieve.
From the structural formulas of the synthetic ester (Figure 9) it can be seen that this differs from the mineral
oil by a plurality of points. Mineral oil has only small amounts of bound oxygen, as opposed to arrive at the
ester in each molecule CO several compounds.
Basically, the formation of gas thus behavior is similar to that of mineral oil, and the esters of fatty acids, the
chains are cleaved by external energy effects and there are fragments recombine immediately to stable
gases (see 2.2.2). However, the fatty acid chains in Estermolekül are much more homogeneous and partly
longer than in mineral oil. that a chain in many, very unstable CH fragments is blown up by an arc, which is
then to stable rapidly the means in practice, C 2 H = C 2 connect H (ethene) and CH≡HC (ethyne).
Unlike petroleum, the hydrocarbon chains are associated to triglyceride molecules. An energy action from
outside so not only has the ability to cleave different hydrocarbon fragments, but also CO and CO 2
to create. For it must be the whole
Hydrocarbon group, individually or as a whole chain, and thereafter, the C = O or OC = O fragment are
separated. The binding energy of a CH bond is only slightly stronger than the CO bond. Thus it is with the
same amount of energy is needed
to one of a hydrocarbon chain

cleave hydrogen atom, also possible to separate an entire fatty acid chain of a Estermolekül. The possibility
of acid formation and subsequently offers to the synthetic esters, the potential for cellulose degradation (see
also Section 2.4.2).
2.4 Natural ester
In this work soybean oil was used as a natural ester. It was cleaned by the manufacturer, degassed and
combined with color and antioxidants. Below those found in the literature search results, the soy oil are
concerning summarized.
Vegetable oils are mainly composed Trigliceridmolekülen with three esterified fatty acids (see Figure 12).
Which fatty acids which are dependent on the particular plant. These differ in the chain length and degree of
saturation.
Are occupied by hydrogen in the chain all the valence electrons and there is no double bond between two
carbon molecules, one speaks of saturated fatty acids. These are very resistant to oxidation, but occur
rarely in the plant, they increase the viscosity and reduce the pour point. Substances with a high proportion
of saturated fatty acids are solid at room temperature (fats). Depending on how many double bonds occur,
they are called single, double or polyunsaturated. With the number of double bonds, oxidation stability, pour
point and viscosity decrease. In an insulating oil should use as few polyunsaturated fats occur as possible to
ensure a positive aging behavior. On the one hand, the electrical resistance decreases,
As a compromise between viscosity and rapid aging can therefore seeks a high proportion of single or
double unsaturated fatty acids to obtain vegetable oils [51], [19].

2.4.1 composition and preparation of soy oil
Soybean oil (Oleum Sojae) is obtained by pressing or extraction from Glycine max (L.) Merr. (Fabaceae)
won. The origin of the soybean plant is located in Southeast Asia, it has already been v in southern China to
the 1500th . Domesticated Chr. The plant grows best in subtropical climates at temperatures between 25 °
C and 32 ° C and it is already being cultivated industrially in the US today. In the 2003/04 soybean with an
estimated 201 million tons accounted for over 58% of Weltölsaatproduktion [33] had.
The main components of soy oil are linoleic acid (over 50%), oleic acid (over 20%) and palmitic acid (about
10%). Other components are α-linolenic acid, stearic acid, arachidic acid and vaccenic acid. Because it is
made of a whole natural product, the compositions can vary. Also of interest is the triglyceride composition
composed mainly of LLL and OLL (20%) and PLL, LLLN, OOL, and POL (approx 10%), where O for oleic
acid, L of linoleic acid, Ln for linolenic acid and P for palmitic acid is [33].
Figure 12: Construction of a triglyceride molecule, here in the OLLn configuration (oleic acid, linoleic acid, linolenic acid), also
other combinations are possible [52]
The extraction of oil begins with the selection of seeds. By breeding and biotechnological processes, it is
possible to influence the composition of the oil both in the fatty acid structure and in the
Triglyceridkonfiguration so that as little subsequent change is necessary.

After the now following cultivation and harvest the fruits are stored and compressed (see Figure 13). Then
there is the case of fruit with lower oil content
to extract in order to reduce the oil content of the grist to less than 2% (such as soy bean)
absolutely necessary, the cake (solid press residue). This ensures a sufficient income and an economic oil
extraction are possible [51].
Figure 13: Recovering crude vegetable oils using the example of rapeseed oil [51]

Thereafter, a refining takes place. In this process, unwanted
Impurities removed (see Figure 14). Examples of these are metals, free fatty acids, soap residues and
residues of pesticides [51].
Figure 14: Block diagram showing the refining of vegetable oil, [51]
In order to use such pre-treated vegetable oil for electrical insulation, it still requires a fat modification. This
is necessary because it is grown, fluctuating in the compositions of natural products and not all ingredients
are conducive to the purpose of electrical insulation and aging stability. In the modification processes,
however, is mostly about changing the individual triglyceride molecules, removal of unwanted ingredients
already took place in the previous steps. There are mainly the modification process of the fractionation,
transesterification and curing the insert (see Figure 15) [51]. When fractionating triglycerides of different
melting points are separated from each other. In this case, the pour point of the oil is reduced,
In the transesterification, the redistribution of the fatty acids on the glycerol and thus a further change in the
physical properties by the addition of a catalyst. The composition of the individual fatty acids remains

untouched. Thus, it is possible to approach a statistical distribution of the fatty acids on the molecules, and
thus a more homogeneous liquid. During curing, however, comes very well to a chemical change in the fatty
acids themselves, more specifically on the number of double bonds present. This increases, as mentioned
above, the oxidation stability, but also increases the pour point and viscosity. It is important to find a
compromise in which as many polyunsaturated fatty acids are cured as possible without reducing the
number of components monounsaturated strong. Finally additives such as dyes, pour point depressants,
oxidation inhibitors or passivators are still attached after a
last
Processing (filtering, dehumidification, degassing) the insulating oil may be used.
Figure 15: The most important methods for fat modification: fractionation, transesterification, curing [51]
2.4.2 Temperature and gas formation behavior of natural esters
A flash point of about 280 ° C makes soybean oil to a very useful insulating the view of the fire load. The
solidification point was determined in tests with -21 ° C. Thus these esters could not be used for the tests
with -25 ° C, however, the use at -10 ° C was not a problem. In itself same applies to the humidity and
temperature behavior of the natural ester such as the synthetic esters. However, there is a difference in the

higher viscosity, it has an even lower diffusion time constant result. Therefore, the assumption is valid for
the natural ester that the transients go slower and
in the 180-minute duration of the
even less can come to reaching a balance through impact tests incl. preparation. Rather must be assumed
that a "quasi-steady-state" because of the slowness of diffusion, as in this test period expected no
significant amounts of water that may be missing on the surface of the paper,
can be stored in the cellulose. since the
Moisture saturation level according to [52] is only a few 100 ppm during natural esters, are measurable
effects of a rapid cooling here most likely.
The gas formation behavior of the natural ester is the ester of the synthetic or mineral oil of the similar (see
section 2.2.2 and 2.3.2). So there is exposure to energy and the ability to generate HC subgroups and in the
structural formula (see Figure 12) are also evident opportunities for carbon fragment formation.
Further still several ways the production of acids, such as formic acid offer (see Figure 16). Acids are, unlike
the dissolved inert gases, however, a problem. They affect seriously compromises the cellulose aging and
contribute to the reduction of the DP value.
Figure 16: Representation of the structural formula of methanoic acid (formic acid)
2.5 cellulose
As in the real transformer, a mold is always used by cellulose, the insulating liquid to be tested can not be
tested separately, if practical results are required. The cellulose met in the transformer

on the one hand as a supporting element constructional properties, for example as coil support and
stabilizing member. In the case of a short circuit, the cellulose is exposed to heavy mechanical loads.
However, it has to other other important properties. Has impregnated cellulose to a higher electric strength
than the insulating liquid alone. The oil-impregnated cellulose fibers provide through their many trapped oil
volumes are a variety of barriers that prevent the fiber bridge punches and interrupt streamer. It only comes
to high-current partial discharges and not to complete breakdowns.
Therefore board barriers to support the insulation in heavily polluted areas such as the winding head, the
high-voltage side discharges and the scattering gap between upper and lower voltage side essential (see
Figure 18) [28], [34].
Figure 17: ABOVE: Photos of 3mm thick strips being used from Transformerboard. BELOW: The structural formula of cellulose
[34]

2.5.1 Production and structure of cellulose for transformers
In the transformer two types of cellulose products are generally used in the insulation, the paper and the
pressboard (or pressboard or block span). While paper is used only for conductor insulation without
mechanical stresses, are the pressing board to also supporting and stabilizing functions.
Basically, pressboard is a thick insulating highest quality. Both fiber products are made of the same basic
ingredient, from unbleached sulphate cellulose, consisting of long-chain Kohlehydratmakromolekülen that
are cross-linked by intra- and intermolecular hydrogen bonds.
As a raw material wood comes from very slow and tight-grown trees are used. Engringige spruce and pine,
slowly grown in cold climates, such as Scandinavia or Canada that meet these conditions and in order to
ensure that even high mechanical loads is securely held state [34].
The most important component is mainly the α-cellulose. Is composed of chain-like polymerized β-cellulose
and combines a plurality of these "parts" to a fiber-macromolecule [see Figure 17]. The average actual
number of βZelluloseeinheiten in the fiber is determined by the DP-value (degree of polymerization) is
specified and in unprocessed wood up to 15 000. In the processing to paper and pressboard, this is reduced
to a new value, about 2000, which
yourself during the transformer operation mainly by
The influence of moisture continuously reduced. Is a value of 200 obtained, it means a significant loss of
mechanical strength and the end of the life of the unit.
Another important part of the paper and the pressing chip is the hemicellulose. It consists of
macromolecules from carbohydrates, which have a degree of polymerization less than 200th Takes them
from a limited amount (<10%) as it carries by facilitating the formation of hydrogen bonds significantly to
increase the strength. However, if the proportion of hemicellulose above this limit,
thus reducing the mechanical strength of the
Total material again.

The actual load of the final product depends solely on the intermolecular hydrogen bonds between adjacent
fibers. These bridges are the actual vulnerabilities and break when overloaded, the fibers themselves do not
stop because its load limit is much higher than that of intermolecular bridges [34].
The production process consists of the essential steps of the fiber separation, purification, capable of
forming, drying and pressing. At the start of processing, it is necessary to separate the fibers so thoroughly
but gently as possible from each other without too much to add to the degree of polymerization. This also
applies to all other production steps. After separation in the cleaning are further constituents of the wood,
such as lignin, separated from the fibers and washed out. After that, all fibers are as good as possible from
low DP value.
Now, the important process of layering begins. Paper consists of many individual layers (about 30 per mm
thickness of the pressboard). The thinner the layers, the higher the quality of the paper or of the press
boards. These sheets are then dried and pressed in several stages. This leads to bridging between the
macromolecules and the actual structure of the board is formed. Pressboard is fabricated to 5 mm
thickness. For thicker elements several layers pressboard are non-aqueous polyester resin adhered to the
so-called block clamp [34].
Figure 18: Construction of the insulation of a power transformer [20]

2.5.2 gas formation behavior of cellulose
The process of gas formation in the cellulose is similar to that in the liquids, it is also here by the action of
thermal energy for the removal of building blocks of the polymer chains. The binding energies of the CO
bond between the anhydroglucose rings is much less than the C-C bonds of the oil or the rings themselves
(see Table 3).
So the splits found at much lower temperatures instead (from about 105 ° C). The long chain
macromolecules are broken into shorter parts on the one hand and the DP value decreases, on the other
hand the gases while CO and CO 2 [ 47].
2.6 The oil - cellulose - insulation
The interaction of oil and paper affects many electrical and chemical processes. As already described under
2.4.1, the electrical resistance of a mixed dielectric oil and board is higher than that of the insulating liquid
alone. Basically, an oil-cellulose insulation of a combination of an electrically insulating liquid (mineral oil,
silicone oils or Esterflüssigkeiten) with various fibrous products (pressboard or pressboard and paper).
Wherein the mechanically loadable pressboard is used to meet onerous both mechanically supporting
objects, as well as electrically insulating functions. The (soft) paper, however, is only used for insulation
purposes (conductor insulation) [28] [20].
Apart from the well-known electrical insulating oil-cellulose insulation system has another important task that
removal of heat through the heat losses.
On the one hand it is important to dissipate the heat generated at the core conductors and constant
operation of the unit to the operating permanently in the
to keep the permissible range.
On the other hand, the thermal capacity of the insulation and the cooling medium oil must also be capable of
short notice greater amounts of heat (as they occur, for example in case of overload) to receive and carry
away without damage

[28], [20]. Here comes the above mentioned problems of higher viscosity or even the possibility of
solidification of Esterflüssigkeiten at low temperatures to fruition. It may be necessary for the practical use of
a Estereinheit to heat the volume of oil before switching to lower already when switching the liquid viscosity
to values that does not impede the required for cooling circulation.
2.7 Additional gas production operations
The analyzed gases may also be reasons other than the above-mentioned result (see section 2.2.2, 2.3.2
and 2.4.2): Other thermal effects (hot spots in the transformer) may produce hydrogen. Chemical reactions
on the inner wall of the transformer housing, for example, with various protective coatings, or coatings which
produce various gases, have been observed in practice. Even with rust procedures and under the action of
sunlight or by superheated gases core sheets can be produced [47].
All of these non-arc-based gas sources in this work due to the very short possible exposure time (max. 72
hours), the non-existence be excluded from unknown protective coatings, the lack of daylight and avoiding
unknown materials with very high probability to be.
2.8 Dielectric behavior
2.8.1 Dielectric behavior of the fluids
For discharges and breakdowns in liquid dielectrics there is no comprehensive theory of physics because
they contain a variety of materials with different physical properties. These properties are by
changes in the Composition, different
Manufacturing conditions, impurities, and by aging processes very

subject to large variations and deviations. Impurities must therefore be removed as far as possible from the
liquids before use, as these are the weakest point (fiber bridge through). [28] There are
different theoretical approaches, the breakthrough in a
insulating to describe. For various electrical
Stress times the insulating medium are different approaches available. Each of them describes the area
sufficient, however, no comprehensive theory for the movable amorphous structure of a liquid is, as already
mentioned, present, since both the mean free paths of gases as well as the completely ordered structures of
crystals are not given [29] , (- veiled gas breakdown microbubbles) and solid-state theory (Theory of the
electron impact), therefore, the mathematical models from the theory of gases, use is made. Furthermore,
the models of the Suspensionsteilchentheorie come (polarization effects of fibers and particles direct the
discharge at the bridge fiber breakdown, a)
and percolation theory (Training of
Preferential directions in the liquid) to support [29]. In Figure 19 the fields of application of the individual
models are illustrated.
Figure 19: Illustrating the various models of the punch in fluids

2.8.1.1 Theory of microbubbles (gas Theoretical model)
With surge voltage shaped stress the discharge behavior is similar in liquids the discharge behavior in
gases, leading to "Theory of
has led Mikobläschen "or the" veiled gas discharge ". A formation of electron avalanches would require the
presence of areas where the mean free path is sufficiently large that impact ionization would be possible.
This in turn would be provided if it is assumed that the liquid in areas of low density ( "oil-vapor-containing
microbubbles") are [36] [28].
Formation of microbubbles:
• Natural presence of areas of low density
• Production by accelerating charged particles or volumes and their intense electromagnetic
hydrodynamic motion
• Injected space charges accumulate on molecules and produce Coulomb repulsion expansion and
thus low density regions
• Injected charges on microscopic hills generate currents and local overheating, leading to the
formation of microbubbles
Inside this bubble, the breakdown behavior with the theory of gas blows is explained. Various operations,
such as the pressure-dependent behavior of the discharges are also also modeled.
2.8.1.2 percolation theory
Another explanation for the breakdown behavior of liquids is the percolation theory. This is based on the
assumption that discharges gradually arise from charge carriers, which is first in a disordered state and
without field, by applying a more ordered in such conditions, up to the breakdown develop (see Figure 20)
[28].

Figure 20: Modeling of the insulating modeled on the percolation theory [28]
2.8.1.3 Solids Theoretical Model
Now the theory of microbubbles raises the question of their origin. To answer this, it is helpful to apply the
theoretical modeling of the insulating liquid, along the lines of a solid.
The Streamerausbreitung after the microbubbles theory preceding events, the provision of carriers, their
transport and the formation of low density areas are on the electrochemical processes which take place
when one considers the insulating medium as a solid, explainable.
Charge carriers are partially as negative and positive ions as well as free charge carriers already
present in the liquid. Constantly running

Dissociation and recombination processes, as well as by the Schottky-effect from the metal structure exiting
higher electron provide further carrier provides [29].
The introduction of a metal electrode in an insulating liquid leads to the formation of a double layer
according to Stern, which constitutes a further development of the Helmholtz double layer. By continuously
available oxygen and its adsorption metal surfaces are covered with an oxide layer. If, on the outer side of
the electrode for the attachment of polarizable molecules and positive charge carriers, so this represents the
inner Helmholtz layer. Adjacent negative charge carriers between the positive ions are adsorbed, this
represents the outer Helmholtz layer. These two monomolecular layers form the rigid Helmholtz double
layer. By thermal motion of the ions is adjacent to the outer layer further. In this diffuse - layer an
exponential charge curve [29] arises.
Figure 21: Bilayer by Stern [29]
When a voltage is applied, it comes at the positive electrode by field ionization to the transition of electrons
from the insulating liquid in the metal (see Figure 22). In the negative electrode, electrons are both from the

Metal and from the near-electrode liquid molecules due to field emission from [29].
Figure 22: Representation of the mechanisms of the charge carrier discharge of metal points (or surface roughness) in the
insulating liquid, UP: field ionization; BOTTOM: field emission [29], [37]
2.8.1.4 Suspensionsteilchentheorie
This model treats especially the so-called fiber bridge punch. In this work with
impregnated cellulose worked. This requires
unavoidable contamination of the liquid with microscopic cellulose fibers.
at prolonged exposure to direct and also
AC voltage, this fibrous contaminants align according to the external field and migrate into the area of
maximum field strength. Subsequently therefrom complex fiber bridges which may reduce the dielectric
strength of the insulation path enormously form (see Figure
23). Timer for this is also in a new, well-dried cellulose present, higher moisture content (0.5% water). This
creates conductive channels and

comes to education, Chapter 2.8.1.1 in the microbubble theory
Conditions for formation of lower density, such as higher current densities and local overheating described.
The thus facilitating breakdown can be represented as a local heat shock [29], [39].
Figure 23: Illustrating the formation of a fiber bridge [29]
2.8.2 Dielectric behavior of impregnated cellulose
The use of cellulose as a barrier increases the electrical strength of the insulation system,
compared to the pure oil route considerably. Out
punch mechanical point of view carries the cellulose itself is not through a higher dielectric strength but by
the structure resulting from the fiber in many microscopic barrier to electrical resistance. A breakdown
through an oil-board system may therefore, apart from the increased strength due to the formation of
barriers against fibrous bridges, such as a breakdown will be viewed through a liquid without cellulose [28].
Furthermore,
tangential field components occur which in many
high voltage engineering interfaces are a critical load. Oil cellulosic interfaces make in this regard, but an
exception: Due to the fiber structure of the board, a quasi-continuous transition from the pressboard results
in the free oil (see Figure 24).
The capillary forces prevent the known smooth surfaces wetting problems. In addition, given the very low oil
pressboard gap width increases (high electrical resistance) outwardly quasi steadily, the electric resistance
decreases steadily on the values of the free oil path. The oil into

projecting fibers act practically as microscopic barriers in the tangential direction [28].
Figure 24: A cellulosic sliding distance under tangential field stress [28]
2.8.3 Special, the moisture exchange and low temperatures
aspects relevant
, Was used in the present work on the one hand by a rapid cooling and the additional use of cellulose on the
other hand, attempts to determine the extent to which the moisture exchange between insulating paper and
affects the electric resistance. An attempt was made for the measurements possible "non-stationary"
Conditions of the moisture balance of the oil-cellulose
to reach the insulation system, it was practically worked with a temperature gradient.
The cooling was just before reaching the selected temperature (-10 ° C and -25 ° C, except in the
experimental runs at room temperature, in this case no heating or cooling was previously carried out) is
stopped, so that the desired temperature by the inertia of the system (in

Preliminary determined) has been reached. Thereafter, the setup immediately after pulling the DGA sample
(about 30 minutes) was subjected to voltage. The test procedure lasted 90 to 120 minutes.
It was thought that could not set a moisture equilibrium between the respective tested liquid and the
impregnated cellulose in this short time. however, must be cooling with the result that the saturation
humidity goes back and thus greatly increases the relative humidity and therefore an excess of water
contained released into the cellulose. Therefore, it was expected that this moisture due to very high diffusion
times [41] accumulates on the surface of the cellulose, and there, the electrical resistance, specifically
lowers in the tangential direction. The present study aims to show the extent to which this assumption for
conditions as they are called in the real transformer is correct.
2.9 behavior of fluids at low temperatures
By H. Borsi has already been shown in [22], that the electrical resistance of most conventional insulating
fluids tested by itself (without cellulose) between +25 ° C and -25 ° C and constant conditions are
substantially not dependent on temperature ,
mineral oil
Mineral oil has been proven over decades of use in transformers, placed in cold regions. The pour point is
low, at about -40 ° C and the viscosity is low compared to the Esterflüssigkeiten. At -20 ° C, this
corresponds approximately to the value of the ester at 0 ° C (see Figure 4).
The water absorption capacity decreases with temperature. At a temperature of
-20 ° C can be added for a further 20 to 25 ppm water, at room temperature for about 40 to 50 ppm. For
aged oils, these values can increase by a factor of two [56].
The penetration behavior of mineral oil at low temperatures falls for wet oils from a decrease in temperature
below 10 ° C and remains constant from 0 ° C. For

dry oil, at moisture levels below 5 ppm, the breakdown voltage with decreasing temperature does not
change [22].
synthetic esters
In Verteiltransformatorenbau there are already many years of experience for synthetic esters. With a pour
point of -50 ° C this liquid almost ideal for more powerful and more intense cooling transformer classes,
except for the high viscosity (at -20 ° C a multiple of mineral oil). The high water absorption capacity of more
than 1000 ppm at -25 ° C is generally not necessarily a disadvantage.
The problem of the transport of this water could be because at lower temperatures which are lowered still
further from the outset low diffusion coefficient of the ester [41]. Therefore, a Involving the ever-present in
practice cellulose can potentially lead to new outcrops due to the tendency of the moisture exchange.
Without cellulose no temperature dependence of the breakdown voltage was observed for the synthetic
esters, even when the humidity was increased to up to 1000 ppm. It could only a fundamental dependence
of the electrical resistance of the synthetic ester of its moisture content, but not shown on the temperature
[22].
natural ester
The use of non-heated vegetable oils as cooling and insulating media in power transformers is by its
relatively high altitude pour point of
- 15 to -25 ° C clearly limited. The solidification point of the ester used herein was determined in preliminary
experiments with -21 ° C.
Basically same applies to the humidity and temperature behavior of the natural ester such as the synthetic
esters. One difference is the higher viscosity, it has an even lower diffusion time constant result. Therefore,
it may be assumed for vegetable oils that the transients go even slower. The maximum moisture absorption
capacity of natural esters is at -20 ° C a few hundred ppm [56].

task
3 Exercises
The aim of this work was to study of the characteristics of natural and synthetic Esterflüssigkeiten at
low temperatures and their
perform gassing to obtain in this way science-based analyzes for various applications.
In particular, attention to the electric resistance of the liquid in combination with cellulose was so set as
oil-board insulation system. When presenting the framework for the establishment of a test and a test
program the real conditions served in a transformer in order to gain insight about the practical and actual
use of liquids. It was also important to consider the following:
• Use of recycled liquids or new oil
• Use of recycled cellulose
• Cooling at room temperature but not with real operating as a start value (ambient temperature typ.
+60 ° C) to achieve a real possible moisture gradient in the liquid
• Cellulose samples must be during the game in temperature of the test liquid to allow moisture
exchange
However, one important premise of practice had to be bypassed, it became a cellulose surface with a
tangential field stress as they may not occur in the real transformer,
in the test arrangement realized (see
Figure 25 and Figure 26). This was to investigate the hypothesis that the humidity after rapid cooling leads
to a strong reduction of the electrical resistance of a cellulose surface, necessary.
The ratios in real units are exclusively non-critical from the viewpoint of the electric field strength because
they have lower Inhomogenitätsgrade and the tangential surfaces are burdened with substantially lower field
strengths. Should therefore conclusions for practice are drawn from the results of this work, it means that
these investigations will be accepted as a "worst case"

task
allowed because there will never be in real transformer to such poor conditions.
3.1 Current state of research
The behavior of Esterflüssigkeiten at low temperatures already moved shortly after the launch of Midel 7131
the company M & I in the interest of research. Borsi studied in [22], the dependence of the water solvent
power and the dependence of the breakdown voltage of the liquids with different water contents on the
temperature, among other things, this synthetic ester without cellulose. He showed that the water dissolving
power had a strong temperature dependence of the electrical resistance
however
was much more dependent on the moisture content than the temperature. Kahn et al. investigated in [61]
and [62] the gassing behavior of synthetic and natural Esterflüssigkeiten in terms of temperature error (using
cellulose) and punches (without cellulose). Your results of studies for electrical faults showed that, apart
from an increased CO production and a more moderate Ethinproduktion at
esters, no significant
Changes in the harmful gas compositions and concentrations had surrendered between the fluids. It was
found by you that the total gas production in the esters was lower than in the used oil.
Of Höhlein-Atanasova and Frotscher has been shown in [64] through a heat aging study of different esters
in the headspace vessels that CO and CO 2 are generated in the esters even with thermal errors.
Furthermore, it was found that the CO concentration rises in esters at a thermal aging before the, typical of
petroleum gases. In [63] the Duval Triangle around some variants was, among other things, for
Esterflüssigkeiten
(Not mineral oils'), extended. The investigations
simulated breakdown error revealed that a change of the limiting value between heavy and light discharges
of the ethene / ethyne-ratio of 0.29 to 0.33 is useful.

task
3.2 experimental design and considerations for cooling
As experimental set a new sample form has been developed which includes both the oil-paper insulation
system as also represents an inhomogeneous field distribution and creepage distance as the breakdown
possibility is (see Figure 27). This arrangement consists of a circular plate electrode connected to ground
potential, and a copper strap from standard flat conductor material [15] to which the high voltage potential is
applied.
Therebetween a cellulose strip [16] is used standing, with their
Longitudinal edge touches both electrodes. The amount of this cellulose strip thus provides the electrode
gap. were chosen 10 mm and 20 mm, in order not to exceed the withstand voltage of the test vessel, which
is 150 kV. The plate electrode is connected to ground potential had a diameter of 120 mm and had a
edge radius from 10 mm. The copper bracket would have the
Cross-sectional dimensions of 1.6 mm thickness and 13 mm width with an edge radius of 0.5 mm and had a
radius of 60 mm curved (see Figure 26).
Figure 25: LEFT: The samples form U-strap flat conductor under oil; RIGHT: sketch of the entire test vessel (all dimensions in mm)
with an inserted sample and another sample (perpendicular in the retaining ring)

task
Figure 26: Drawings of the sample mold used with plate, the cellulosic strips in the two different widths (10 mm and 20 mm) and
the copper strap individually and in the installed position (all dimensions in mm)
Figure 27: Field simulation of the samples used form pad of the copper conductor

task
3.3 Selection of liquids
Basically, mineral oil, and each one of natural and synthetic esters should be used. It should be a practical
work, the results should also have regard to actually run or at least in the near future be operated units
relevance.
It was important that they are oils that were available as insulating fluids already on the market and further
already at least in the
Medium voltage level have been used. This included new or novel insulating liquids, which were still in the
research stage, out. The fluid Midel eN M & I did not get on the short list because of the legal problems of
the company.
BEC fluid ELANTAS was not used, since this liquid could not be used in large transformers, and this is an important aspect for the application of
gas-in-oil analysis. This is only used for monitoring in large transformers. Since BEC fluid has as PentaerythritTetrafettsäureester the same
basis as the Midel much easier available for the TU Graz 7131 from M & I, the results obtained can be transferred with high probability on the
liquid BEC fluid. When mineral oil was the sort Nynas Nytro 4000X, an inhibited naphthenic mineral insulating oil, selected. The main reason for
this liquid was the great availability, since this liquid has already been used in many other studies at the Institute of High Voltage Engineering at
the Technical University Graz. Most mineral oils on the market from various manufacturers (eg Shell, Technol, Nynas, etc.) are, for that matter
strikethrough and gassing, equivalent and therefore could be decided upon availability. As synthetic ester Midel came 7131 by M & I used. This
is a Tetracarbonsäureester, which is used for several decades in many Verteiltransformatorenbau to 50 kV and should be used soon in large
transformers up to 220 kV. There are also studies on the suitability of this liquid in step switches [12]. etc.), which relates to the strikethrough
and gassing, equivalent, and therefore could be decided according to availability. As synthetic ester Midel came 7131 by M & I used. This is a
Tetracarbonsäureester, which is used for several decades in many Verteiltransformatorenbau to 50 kV and should be used soon in large
transformers up to 220 kV. There are also studies on the suitability of this liquid in step switches [12]. etc.), which relates to the strikethrough
and gassing, equivalent, and therefore could be decided according to availability. As synthetic ester Midel came 7131 by M & I used. This is a
Tetracarbonsäureester, which is used for several decades in many Verteiltransformatorenbau to 50 kV and should be used soon in large
transformers up to 220 kV. There are also studies on the suitability of this liquid in step switches [12]. which is used for several decades in many
Verteiltransformatorenbau to 50 kV and should be used soon in large transformers up to 220 kV. There are also studies on the suitability of this
liquid in step switches [12]. which is used for several decades in many Verteiltransformatorenbau to 50 kV and should be used soon in large
transformers up to 220 kV. There are also studies on the suitability of this liquid in step switches [12].

task
The choice of natural ester liquid fell on the Envirotemp FR3 of the manufacturer Cooper Power Systems.
For the natural ester pour point was (the temperature at which the ester is still just liquid) a very important
criterion.
Since it would probably not be possible to carry out the test series at a temperature of -25 ° C with a natural
ester, but should at least the rows
-10 ° C to be completed. therefore were
conducted preliminary tests, the cooling on, even with the liquid BIOTEMP ABB. It was found, however, that
these already solidified at -4 ° C and therefore was not useful for the planned low-temperature experiments.
3.4 Design of Experiments
To obtain scientifically relevant results, had to be considered in the design of experiments already several
points. Limiting factors were the expected high variability of the results due to the stochastic properties of
the breakdown mechanisms in the oil-ZelluloseIsoliersystem and the limited number of independent
punches in the 17 liter test vessel.
By the resulting necessity to examine as many samples to be tested, the number of limited distances to two
(10 mm and 20 mm spacing) was. In addition, all experiments were performed in duplicate in order to
achieve a statistical method against different treatments. This meant twice 10 measured values for each
distance, each liquid and each temperature.
3.5 sequence
were used as reference tests with treated fresh oil at room temperature. For the low temperature tests were
assumed by the operating case of a transformer. Since transformers are dimensioned such that the
operating temperature of 60 ° C

task
above the ambient temperature, it was also used for the planning of low-temperature experiments. The test
vessel, including filling and impregnated samples was therefore heated to these operating temperature
before cooling of 36 hours. So that the operating situation of the transformer was simulated. For the tests at
-10 ° C corresponded to the assumed
Operating heated 50 ° C and was stirred at -25 ° C to 35 ° C. After the lapse of 36 hours warm-up began
with the slowdown in the institute's extreme air space. A "worst case" scenario to obtain,
began following AC breakdown tests
immediately after the reaching of the planned temperature while still above the samples removed for the
DGA and the breakdown voltage measurement according to IEC 60156 as well as the moisture in oil
according to Karl Fischer (see section 4.3) were made.
Now, the actual breakdown voltage tests were conducted with the
Experimental design performed. The determination of the breakdown voltage based on DIN 53481 with
upramping voltage, starting from zero volts to the punch, wherein the slew rate is selected according to the
standard so that the breakdown occurred at a time of 10 to 20 seconds after switching on. This should
ensure that the amount of energy supplied for all three liquids were as comparable as possible to achieve
the same type of possible stress. For a comparable basis should be created for the DGAUntersuchungen
that due to the different partial discharge behavior of fluids [13], for example, using 1-minute withstand
voltage tests, would not have been possible.
Immediately after completion of electrical studies further oil samples were taken for the above tests to
determine what was the difference between the measured values compared to the state before the electrical
stress.

task
3.6 evaluation
The scientific evaluation of the various results was performed using several statistical methods. A distinction
was drawn between the evaluation of the electrical and the evaluation of the chemical results. The results of
the moisture in oil Karl Fischer and the breakdown voltage in accordance with IEC 60156 served on hedging
the oil quality.
When evaluating the results of the electrical tests, the individual measurements using scatter plot were first
with linear regression on your
Checked out independence. After a place now graphical determination of the distribution in the Probability
the usability of the data could be confirmed and there were calculated the statistical parameters such as
mean and standard deviation.
From these results, the availability of audited alternative insulating fluids could on the one hand in
low temperatures and on the other hand
Correctness of the assumption that the resultant by the temperature change of surface moisture degrading
the electrical resistance, are checked. For the evaluation of the data obtained by the gas-in-oil analysis
basically existing evaluation schemes have been used (see also section
4.2):
• IEC 60599
• IEEE / TDGC
• after Doernenburg
• after Rogers
• after Duval
• Scheme for MSS / VDE
Furthermore, the amount of gas differences between the measurement before and after the measurement
were formed and absolutely examined the differences in ppm and percentage between the liquids on
abnormalities out. The results were discussed then and it could be concluded to be on which gases in
alternative insulating fluids for the failure of discharges of weak energy board involvement special attention.

Studies of alternative liquids at low temperatures
4 Investigations into alternative fluids at low temperatures
4.1 Experimental setup
mounted on a dense and mobile platform metal cylindrical tube of Duranglas® was a test vessel as used.
Furthermore, the arrangement was provided with shield electrodes, in order to increase the electrical
resistance of the vessel. An image and a scale drawing is shown in Figure 25 and Figure 28th In the tube,
the test arrangement was (see Section 3.2), consisting of a disk-shaped ground electrode with a laterally
mounted sample holder (the guaranteed the vertical stand of the paper sample) and the bow-shaped high
voltage electrode is made of copper.
Furthermore, a sample holding ring was installed, in which were kept still to be tested paper samples during
temperature cycling up to their examination. For taking samples and for emptying the vessel, an outlet was
fitted with a ball valve at the bottom of the metal platform.
Figure 28: LEFT: Photo of the test vessel used with inserted sample without oil and other samples; RIGHT: top view of the filled
vessel with the sample in the retaining ring, without the head electrode, copper clamp and the sample in the support block

4.2 Dielectric tests on the cooled oil ZelluloseIsoliersystem
The test set described in Section 4.2 was filled after cleaning with alcohol and acetone, with the liquid to be
examined and the previously impregnated samples were mounted on the sample holding ring. At the same
time, the oil sample for determining the breakdown voltage according to IEC 60156, and the moisture
content was removed by Karl Fischer. After that, the temperature cycle of heating and cooling took place
optional.
The warm-up was in the heating furnace (42 kW power), in which the test vessel was then placed together
with the sample is performed (see Figure 29). There, the setup was 36 h to either 50 ° C (-10 ° C for the
tests) or
+ 35 ° C (for the -25 ° C experiments) heated.
After this simulated operation, the installation took place in the institute's extreme air space. carried out the
test samples immediately after installation of tests at room temperature. For this, the vessel over a 2
kΩDämpfungswiderstand to two cascaded 100 kV modular transformers has been connected (made by
measuring transformers, maximum output voltage: 200 kV, 50 Hz). The contacted in parallel with the voltage
measurement specimen consisted of a divider of the company Isofarad (ratio 1: 2000, 100 nF) and a
multimeter by Voltcraft (VC 5070).
Figure 29: Preparation of the test vessel in Greater furnace for heating to the simulated operating temperature

Figure 30: LEFT: Contacted experimental setup in extreme climatic chamber (preliminary); RIGHT: Photo of strong bubbling
(preliminary test, -1 ° C, synthetic esters)
For the tests the cooled liquids tension was initiated in extreme climate chamber via a 150 kV ceiling duct
(see Figure 30 left). Immediately before the penetration tests, a DGA sample was taken via the discharge
valve of the test vessel.
After completion of the sampling was started with the breakdown experiments. For this purpose, the U-bar
electrode, the test voltage was always secured alternately a 10 mm and a 20 mm sample of paper in the
support block, centrally and perpendicularly mounted thereto, and after a rest period of about a minute
applied. This was a ramp-shaped increased until breakdown. The slew rate is chosen so that it came s in a
time of 10 to 20 after the switching to the breakdown of the insulation resistance of the specimen. This
procedure was based on the standard DIN 53,481th After testing a DGA sample was pulled back. Since,
according to findings obtained from preliminary experiments, could be assumed that a change in gas
concentrations take place only in the upper third

would (see Figure 30 on the right) and to avoid contamination and blistering the DGA vessel could only be
connected to the lower outlet, two-thirds of the vessel volume have been discharged through the DGA
vessel and then closed, the valves in order to draw a sample ( see also Chapter
4.3.1).
4.3 DGA - Dissolved Gas Analysis - gas-in-oil analysis
The analysis of the dissolved gases in the insulating liquid is an excellent way to determine insulation of a
power transformer of the state of the oil-paper. It offers several major advantages.
Firstly, the removal and examination without limitation operation under tension, respectively, is possible
under full load.
On the other hand, it provides insight into the condition of the paper insulation without a cellulose sample
must be taken (and would thus the insulation may be destroyed). It offers good explanatory power than any
in the last operating period errors that have occurred. However, a disadvantage of the integral evaluation
character, it is impossible to establish whether many small or a few large errors are the cause of the change
in the composition of the dissolved gases.
There are basically typical major faults, such as partial discharges, punches,
Paper destruction and thermal error due to the
diagnose different concentration increases in major measured gases.
The analyzed gases are generally low-hydrocarbons and carbon oxides. Typically, hydrogen (H 2) Methane
(CH 4) Ethane (C 2 H 6) Ethene (C 2 H 4, and ethylene), ethyne (C 2 H 2, and acetylene), propane (C 3 H 8th) and propene
(C 3 H 6 and propylene), carbon monoxide (CO, carbon monoxide) and carbon dioxide (CO 2, and carbon
dioxide) was determined.
In the gas chromatograph, the amounts of the gases are determined and then calculates the concentrations
by means of the sample volume. these are determined, the above errors with greater or lesser security can
be named [45] based on various evaluation schemes.

The analysis of the gases dissolved in oil is divided into four key areas:
• sampling
• Extraction of the dissolved gases by means of pump Toepler
• gas analysis
• evaluation
The following briefly discuss each of these sections.
4.3.1 Sampling
The removal of the sample is a very accurate and conscientious operation to carry out, as here made
mistakes, such as an air lock in the sample vessel, can cause severe measurement inaccuracies. It is
therefore always in the same way to proceed:
• Connection of the sample vessel (see Figure 31) at the test vessel. This was done with DN 16/12
Kleinflanschbauteilen and silicone tube with 10 mm internal diameter. In this case, the vessel was
fixed vertically by means of a laboratory stand so that all the bubbles could rise to the top and were
purged from the vessel.
Figure 31: Sample vessel for the "gas-in-oil" - analysis. The arrangement of a container between two taps allows completely
bubble-free filling of the insulating liquid to be examined. The volume of the vessels was 150, 200 and 300 ml [46]

• Bleed and flush the sample vessel. This is done standing upright sample vessel, wherein the inlet
tube is at the bottom. In order to
ensures that all air bubbles under
The aid of the buoyancy force and the flow, able to move upward and be rinsed. Here is flushed
with at least one liter of liquid, the posterior sample even with approximately two thirds of
Prüfgefäßinhaltes (about 13 liters).
• Drawing the sample. First, during the passage of the insulating liquid of the valve at the outlet and
then the valve is closed at the inlet. Thus, the sample is sealed in the interior of the vessel and can
be connected to the Toepler pump.
4.3.2 Extraction of the dissolved gases by means of pump Toepler
The Toepler pump (see Figure 32) is a vacuum extraction device, the pistons are made of liquid mercury.
This is due to the fact that gases in mercury is difficult to solve the only method that can be extracted with
sufficient accuracy from a sample of the gases.
The Toepler pump draws with several strokes of the piston mercury the dissolved gas from the sample and
stores it in a glass of volume is charged with which by opening a valve of the gas chromatograph (see
Figure 34).

Figure 32: Photo of Toepler pump, which is used in the oil laboratory the composite-Umwelttechnik GmbH in St. Andrä /
Carinthia and was also used for the analyzes of this study [46]
4.3.3 The gas analysis by gas chromatograph
A gas chromatograph (see Figure 33) analyzes a gaseous sample with respect to the information contained
in their gases, both qualitative and quantitative,
by separating the components from each other, and determines the quantities of the individual
substances.
Basically, a gas chromatograph of the following structure (see Figure 34): A source of the carrier gas (argon,
helium or nitrogen), the input possibility for the gas sample, a capillary metal tube of defined length and a
defined diameter (the so-called "separation column", in the dividing the sample into the components takes
place) and at the separation column

connected detector indicative of the leakage of a constituent of the sample. For this, a flame photometer or
an ionization detector is mostly used.
Hydrogen (H 2) about 5 ppm

Methane (CH 4) about 1 ppm
Acetylene (C 2 H 2) about 1 to 2 ppm
Ethylene (C 2 H 4) about 1 ppm
Ethane (C 2 H 6) about 1 ppm
Carbon monoxide (CO) and carbon
dioxide (CO 2) about 25 ppm
Oxygen (O 2) and nitrogen (N 2)
about 50 ppm
Figure 33: LEFT: image of the of the composite gas chromatograph-Umwelttechnik in Sankt Andrae / Carinthia [46]; RIGHT:
Detection limits of the detected gases [45]
Figure 34: Schematic structure of a gas chromatograph [28]
The analysis of the nature of the different gases present in the sample is done by separation of the gas
mixture by a carrier gas that carries the various components through the separation column, wherein
different substances are moved at different speeds. For this, a sample of the gas mixture to be examined in
the

introduced carrier gas stream prior to the separation column and moved by this gas flow through the
column. Whenever a portion of the sample (after the separation in the column consisting only of a material)
arrives at the end of the separation column, this is reported by the detector. The passage time through the
column is characteristic of the nature of the substance and the amplitude of the eruption of the detector
meets statement about the quantity of the substance contained. For this, in turn, an accurate calibration gas
mixtures of known composition is essential [28].
4.3.4 Analysis and Interpretation
Due to the fact that the nature of the resulting cracked gases from the power density at the fault location and
the insulating materials involved depends, can be by the knowledge of the type and amount of gases
produced a statement on the presence and type of a fault meet. It could be determined so-called key and
accompanying gases from previous experience, the references to the error supply (see Table 4) [28]. but it
is crucial not only the absolute values of these gases, the ratios of the gases each provide important
information to diagnose the error. There were developed several evaluation procedure, different gas ratios
to assess use [45].
For the work performed in this evaluation of the data obtained by the gas-in-oil analysis, the evaluation
schemes described below have been used. Furthermore, the amount of gas differences between the
measurement before and after the measurement (absolute were
in ppm and percentage to the
Output value relative) is formed.

Table 4: Key and associated gases in error detection in transformers [28]:
4.3.4.1 IEC 60599
We distinguish the following six types of errors:
• PD partial discharges
• D1 discharges low energy
• D2 discharges high energy
• T1 increases in temperature below 300 ° C
• T2 increases in temperature between 300 ° C and 700 ° C
• T3 temperature rises above 700 ° C
The characterization results from the gas ratios ethyne / ethene, methane / hydrogen, ethene / ethane and
carbon dioxide / carbon monoxide. The exact interpretation of the coefficients are given in Table 4 below.
Furthermore, a CO indicated 2 / CO ratio <3 or> 10 indicates that the cellulose has been damaged [45].

Table 5: DGA error characterization in accordance with IEC 60599 [47]:
HC2 CH HC4
Error type 2 HC 2 HC
2 4
H 24 2 6
PD - <0.1 <0.2
D1 >1 0,1 - 0,5 >1
D2 0.6 to 2.5 0.1 to 1 >2
T1 - >1 <1
T2 <0.1 >1 1-4
T3 <0.2 >1 >4
4.3.4.2 IEEE standard
This method compares two, as far as possible spaced measurements together. (Total Daily Combustile gas
- TDCG) using the time between measurements, a daily rate of combustible gases from the current values
calculated.
For this rate, there is now - above a threshold value - four different portions of the error classification, of C1
(satisfactory operation) to C4 (safe failure in a short time), see Table 6. In addition, various gas ratios are
used and either Dörnenburg or Rogers evaluated [50].
Table 6: Error codes and criteria in accordance with IEEE standard [45]:
status
H2 CH 4 C2 H2 C2 H4 C2 H6 CO CO 2 TDCG
C1 100 120 35 50 65 350 2500 720

101-700 121-400 51-100 66-100 351-570 2500 - 721 -
C2 36 - 50
4000 1920
701 - 401 - 101-200 101-150 571 - 4001 - 1921 -
C3 51-80
1800 1000 1400 10000 4630
C4 More More More More More More More More
status error
C1 no mistake
C2 Normal operation, errors can occur
C3 High probability of error
C4 Secure error probability

4.3.4.3 MSS / VDE
The Müller-Schliesing-Soldner process evaluated when crossing an absolute amount of fault gases five
quotient with a five-digit code as total earnings, see Table 7. It also evaluates the relevant thermal fault
gases propane and propene [45].
Table 7: MSS ratio test [45]:
HC2 CH 2 HC4 HC4 CO 2

Error type 2 HC 2 HC 2 HC
2 6
H 4 2 6 3 6 CO
quotient areas
<0.3 0 0 0 0 1
0.3 to 1.0 1 0 0 1 1
1,0 - 3,0 1 1 1 2 1
3.0 to 10.0 2 2 1 3 0
> 10.0 2 3 1 3 2
diagnosis Reference sequences
normal aging 0 0 0 0 0
Discharge with great energy 2 1 2 2.3 1
Discharge with less energy 2 2 1 2.3 1
Not
TE high energy density 1 3 0 0
indicative
Not
TE low energy density 0 3 0 0
indicative
örtl. heating to 300 ° C 0 0 0 1 2
. Örtl warming 300 - 1000 ° C 0 0 1 2 2
Warming örtl.> 1000 ° C 1 0 1 2.3 2
örtl. warming and discharge 1 1 1 2 2
örtl. warming and TE 0 3 1 2 2

4.3.4.4 Dörnenburg
This evaluation method is as a result of one of three fault indications of: temperature damage, partial
discharge, arcing. The procedure to a meticulous evaluation scheme (see Figure 35), first threshold values
for the gases to be checked and if these are exceeded, four Dörnenburg ratios are reviewed. A
disadvantage is that only a single error indication is possible, and mixed forms are not detected [45].
No mistake
N N
gas sample
H 2 CH 4 C2 H6 Not suitable gas
Y Y Ratio test OK N
C2 H2C2 H4 CO concentrations
> 2L1 > L1 recheck
Y
R1 =R1
CH= CH
4 4 = C=2CH2 4H 4
R2 R2
H2 C 2 H 44
Y Y Y Partial discharge of
R1 R3 R4
R 3 3= =CC22HH2 2 2 6H 6 low energy
CH 44 R R 4R4
= C= 2CH <0.1 <0.3 > 0.4
C2 H5
Error not recognizable
N N N
N N N retest discharges, arcing
fault can not be seen

R1 R2 Y
R3 Y
R4 Y
retesting thermal fault
0.1 to 1 > 0.75 > 0.3 <0.4
N
N N N
R1 YY R2 Y
R3 Y R4 Y
>1 <0.75 <0.3 > 0.4
Figure 35: Flowchart of Dörnenburg-DGA assessment [45]
4.3.4.5 Duval
The method according to Duval was originally developed for the analysis of gases from the Buchholz relay
and had to be modified for use in the DGA evaluation. It evaluates the three gases methane, ethylene and
acetylene according to their percentage allocation, the sum of the three gases is 100%. Evaluation is carried
out graphically on the so-called "Duval Triangle", see Figure 36 [45].

Figure 36: Duval'sches triangle [45].
4.3.4.6 Rogers
The assessment by Rogers is merely regarded as an additional tool and not as an independent method for
error detection. It is used for more accurate fault isolation, and uses four different gas ratios (see Table 8).
The limits are purely empirically determined and will be subject to fluctuations in the future [45].

Table 8: Error Codes Rogers [45]:

Code of circumstances
Characteristic gas
Limits and 10 times limits
ratios C2 H2 CH 4 C2 H4
C2 H4 H2 C2 H6
C2 H2 1 ppm 10 ppm C 2 H 4
1 ppm 10 ppm CH 4
1 ppm 10 ppm H 2
<0.1 0112 1022 0012
50ppm 5ppm C 2 H 6 1ppm
0.1 to 1
10ppm
1-3
>3
No. characteristic errors typical examples
0 No mistake 0 0 0 normal aging

Discharges in gas-filled spaces as a result of inadequate
0 but
impregnation, supersaturation, cavitation or by large
1 partial discharges low not 1 0
energy density moisture
significantly
2 higher partial discharge 1 1 0 As above, but leads to perforation of

energy density resistant insulations
3 Low-energy 12 0 1 2 employed in the oil by sparking potential

discharges - Differences of bad contacts
Discharges performance breakthroughs arc
breakdowns between turns or coils or between
4 High-energy 1 0 2
discharges
Coils to earth. Destructive switch currents
5 Thermal
low temperature
Error <150 ° C 0 0 1 General overheating of the insulated conductors
6 Thermal
bottomerrors
temperature range between 0 2 0
150 ° C - 300 ° C Local overheating of the core by the concentration of the
river. Increasing hot-spot temperatures; Variation of small
hot spots in the core, short circuit connections in the
7 Thermal
mediumerrors
temperature range between 0 2 1 core, overheating of the copper by eddy currents, poor
300 ° C - 700 ° C contact to the core and tank circuit currents.
high temperatures>
8 Thermal Error 700 ° C 0 2 2
4.4 Further chemical and electrical tests on the liquids
The investigations are divided into a chemical and an electrical part. Chemically before and after each test,
both DGA

Study (see Section 4.3) as well as a determination of the oil humidity using the coulometric Karl-Fischer
method and electrical point of view of a measurement of the breakdown voltage according to IEC performed
60,156th The moisture in oil, and the breakdown voltage were determined in the institute's own oil
laboratory, DGAAnalysen were from the St. composite Umwelttechnik GmbH Andrä / Carinthia performed.
4.4.1 Moisture in Oil - Coulometric Karl Fischer titration
The coulometric Karl-Fischer titration determined by an electrochemical method the absolute water content
of an input liquid sample. In order to obtain the proportional humidity value, an accurate weight
measurement of the sample is necessary. The meter itself consists of two parts, the control unit and the
actual titration, in which the sample is introduced by a diaphragm (see Figure 37). This method of moisture
determination of liquids and solids has been known since 1935 and is used by default in all oil laboratory. It
allows detecting water to 1 ug, that is, weight of sample of one gram can be up to 1 ppm (mg / kg) can be
accurately measured. A prerequisite for this is a sufficient accuracy of the scale used,

Figure 37: Ölfeuchtemeßgerät Karl Fischer
The moisture content of mineral oil is between 1 and 30 ppm. In order to determine such small amounts of
water exactly a conscientious handling of samples and a detailed work is essential.
In the Esterflüssigkeiten the moisture content is significantly higher, more specifically to 800 ppm, in this
work 200ppm limit was determined both in the natural and the synthetic ester ester as.
The Moisture determination by coulometric Karl Fischer method based on a two-step electrochemical
reaction. forming in the first step
Sulfur dioxide with methanol, an ester (alkyl sulfite) provided with a nitrogen base (RN) is neutralized (see
Figure 38). In the second step, this ester is oxidized with iodine and water to alkyl sulfate. The case
consumed water equivalent of the detected moisture in oil.
CH 3 OH + SO 2 + R 3 N → R 3 NH + + CH 3 OSO -2
R 3 NH + + CH 3 OSO -2 + I 2 + H 2 O + 2 R 3 N → 3 R 3 NH + + CH 3 OSO -3 + 2 I -
CH 3 OH + SO 2 + I 2 + H 2 O + 3 R 3 N → 3 R 3 NH + + CH 3 OSO -3 + 2 I -
2I - + 2e → I 2
Figure 38 When Karl-Fischer titration running reactions [43]

The electrochemical proportion of this process is the production of iodine from iodide. This iodine is
generated by means of the generator electrode in the titration cell. The amount of required iodine
stoichiometrically corresponds exactly to the amount of water binding and is calculated by simply
Aufintegrieren of the iodine-generating current.
Once all the water that was introduced with the sample in the titration cell, has reacted with the iodine and
the ester is carried out overproduction (iodine), which in turn is detected by the sensor electrode using
amperometric measurement method. This marked the end of the process is determined and the result is
clear. The goal of the titration process, so it is just detectable to produce more iodine than is necessary for
water absorption.
Due to the sensitivity of the amperometric measuring method, however, the excess of iodine detectable is
only a negligible fraction of the measured value. In practice, the loop is forced through a small, continuously
penetrating in the cell quantity of water to continuously produce a little iodine to compensate for this
quantity. This so-called drift moves to be constant, since it represents the actual stop condition for water
determination of a sample in the range of less than 10 g / min and needs. It is titrated in practice until the
continuous titration has fallen to the value of the drift [44].
Process flow of moisture analysis:
• Prior to sample introduction, the cell must be in a steady state with constant drift
• The sample is introduced into the cell and the titration procedure is started by pressing a button
• Now the cell iodine produced and this is combined with water until all of the water of the introduced
sample is used up and there is an overproduction of iodine
• This overproduction is detected and stopped the process.
• The current required to iodine production was integrated out and thus determines the charge
required

• via Faraday's law the amount of iodine and thus the mass of the bound water is calculated from the
charge
• After entering the sample weight, the relative proportion of water in ppm (mg / kg) is displayed
To eliminate possible outliers and measurement uncertainties, the moisture content is determined three
times and averaged afterwards. Obvious outliers are removed from the test series.
4.4.2 breakdown voltage according to IEC 60156
Accompanying each main trial before and after the test, the breakdown voltage after IEC was measured
60,156th For this, a DTA breakdown voltage meter Baur was with a standardized test vessel used (see
Figure 39).
For measurement, a sample volume of 500 ml is required. As the electrode cap-shaped electrodes are
standard (R = 30 mm, d = 2.5 mm) is used. The voltage (AC, 50 Hz) is zero volts beginning, s increased at a
ramp rate of 2 kV / until breakdown. This test is carried out six times and then averaged. Between two
punches, the oil is 5 minutes with a magnetic stirrer, mixed [49].
Figure 39: Test vessel according to IEC 60156 with electrodes and stirring bar [45]

4.5 Evaluation Methods
4.5.1 regression
To check in a simple manner the independence and freedom tendency of the two test series each made, an
analysis was performed using linear regression for all measurements.
Using the method of least squares (the normal distances of the straight to the individual measuring points
are as small as possible), a straight line fitted to the test series that approximates the course as possible.
This is, with its equation y = kx + d completely determined. Scatters a very large number of measurement
points distributed normally exactly so, d represents the mean value and the slope is k = 0th
In practice, however, a slope k ≠ 0 is always given. Come on the slopes of the individual measurement
series positive and negative signs in approximately equal number of times before and the values of the
slopes are comparable, so independence can be assumed. If the individual readings but interdependent
(Such as a continuous improvement or
Deterioration during the measurement), the slopes of all the series of measurements was always the same
sign [42] have.
4.5.2 Descriptive Statistics
Descriptive statistics is used to clear illustration or for the convenience of description of empirically
determined data by displaying special characteristics in graphs and tables. [42]. For the data obtained in this
work, the arithmetic mean and standard deviation were used.

Arithmetic mean
The arithmetic mean is called an estimate of the expected value, and sample mean or average. It is
calculated [42] as follows:
standard deviation
The standard deviation is a measure of the scattering of the measured values around the average value. It
has the same dimension as the sample and corresponds to the mean deviation from the mean [42] and
having the formula
calculated.
4.5.3 reviewing the punch marks on cellulose
The evaluation of the visible part optical punch marks on the samples was performed by sighting. In Table 9,
the categories used to which the samples were assigned cited.
Table 9: Categories the breakdown traces of paper samples:
visible trace category abbreviation

No visible optical tracks Oil shock K0
Discoloration of the sample, no or very small penetration depth
Paper Punch K1
Dielectric channel clearly visible, partially furrows Paper Punch K2

Results
5 results
5.1 breakdown voltage tests on oil-paper
insulation
Here are the results of the investigations of the electrical resistance are listed. Starting with the measured
values (see Table 10 to Table 12), followed by the investigations of the results to dependence and
distribution (see Chapter
5.1.1) to the results of descriptive statistics (see Section 5.1.2)
Table 10: The measured values of the individual samples for the breakdown studies with mineral oil:
Temp range number 1 2 3 4 5 6 7 8th 9 10
°C kV kV kV kV kV kV kV kV kV kV
1 55 55 65 60 50 55 60 55 55 40
10 mm
2 55 60 65 60 50 60 55 50 60 55
20
1 70 75 80 75 70 85 75 75 65 65
20 mm
2 75 65 80 75 80 70 70 85 75 85
1 65 55 45 65 60 65 60 65 70 75
10 mm
mineral oil
2 65 65 65 60 60 65 55 65 65 60
- 10
1 100 85 85 85 90 100 95 85 90 85
20 mm
2 85 85 80 80 75 95 85 90 90 85
1 50 55 55 55 55 50 55 65 50 50
10 mm
2 65 50 50 55 55 50 60 55 55 55
- 25
1 70 70 55 75 65 75 75 75 75 70
20 mm
2 70 70 75 70 65 75 65 70 75 65

Results
Table 11: The measured values of the individual samples for the breakdown studies with synthetic esters:
Temp. Range number 1 2 3 4 5 6 7 8th 9 10
1 80 80 75 60 70 80 75 65 75 65
10 mm
2 75 70 75 65 65 75 70 80 75 65
20
1 95 90 130 105 110 120 110 120 95 110
20 mm
2 90 105100110 95 95 100 100 95 90
1 70 80 95 80 90 90 85 75 80 70
10 mm
synthetic esters
2 60 80 75 75 70 95 75 80 60 70
- 10
1 90 95 90 90 95 90 90 95 95 95
20 mm
2 115,120 80 100 100 95 85 95 100 100
1 75 75 75 70 80 70 65 65 75 80
10 mm
2 75 45 70 70 80 70 65 70 70 65
- 25
1 100 95 105 105 110 105 110 105 105 80
20 mm
2 100115 95 110 95 85 105115100115
Table 12: The measured values of the individual samples for the breakdown studies with natural ester:
Range Temp. number 1 2 3 4 5 6 7 8th 9 10
1 60 70 60 60 75 75 80 70 70 70
10 mm
2 75 70 75 75 75 65 65 65 60 60
20
1 110100100 90 110110 95 115 80 95
20 mm
2 105100105105 90 80 90 80 100 95
natural ester
1 70 80 70 80 70 80 75 75 70 80
10 mm
2 80 80 80 85 85 90 70 75 80 75
- 10
1 85 80 85 85 90 90 85 95 90 95
20 mm
2 90 95 90 105 95 105110105 90 90
5.1.1 Studies of independence and distribution function
To determine the independence of a regression analysis of the test series was performed by Excel. The
results are shown in Table 13 below.

Results
Table 13: The calculated values for the slopes of the regression line k of the test series carried out with mineral oil, synthetic
esters and natural ester (the smaller the values for k are, the less tendency have the measured values):
regression mineral oil Regression synthetic esters

temperature /
k 1 k row number 2 Temperature / k 1 k row Row 2
distance distance
20 ° C 10mm -1.09 -0.48 20 ° C 10mm -1.00 0.00

20 ° C 20mm -0.75 0.96 20 ° C 20mm 0.87 -0.66
- 10 ° C 10mm 1.72 -0.33 - 10 ° C 10mm -0.50 0.00
- 10 ° C 20mm -0.36 0.72 - 10 ° C 20mm 0.39 -1.50
- 25 ° C 10mm 0.06 -0.12 - 25 ° C 10mm -0.18 0.33
- 25 ° C 20mm 0.87 -0.24 - 25 ° C 20mm - 0.6 0.63
Regression natural ester

temperature /
k 1 k row Row 2
distance
20 ° C 10mm 1.21 -1.78

20 ° C 20mm 1.12 -1.63
- 10 ° C 10mm 0.24 -0.66
- 10 ° C 20mm 1.27 0.39
In Figure 40, the probability networks of the investigations are presented. These were calculated for normal
distribution and for the Weibull distribution (both with 95% confidence interval).

Results
Probability networks of corresponding tests

Weibull - 95% CI
Mineral oil 20 ° C 10mm Mineral oil 20 ° C 20mm Mineral oil -10 ° C 10mm Mineral oil -10 ° C 20mm
90
50
10
30 45 60 50 70 90 40 60 80 60 80 100
Mineral oil -25 ° C 10mm Mineral oil -25 ° C 20mm Synt. Ester 20 ° C 10mm Synt. Ester 20 ° C 20mm
1 50 10
90
percent
30 45 60 60 72 84 60 75 90 60 90 120
Synt. Ester -10 ° C 10mm Synt. Ester -10 ° C 20mm Synt. Ester -25 ° C 10mm Synt. Esters -25 ° C 20mm
90
50
10
50 75 100 60 90 120 40 60 80 80 100 120
Nat. Ester 20 ° C 10mm Nat. Ester 20 ° C 20mm Nat. Ester -10 ° C 10mm Nat. Ester -10 ° C 20mm
1 50 10
90
40 60 80 60 90 120 60 75 90 50 75 100
Probability networks of corresponding tests

Normal distribution - 95% CI
Mineral oil 20 ° C 10mm Mineral oil 20 ° C 20mm Mineral oil -10 ° C 10mm Mineral oil -10 ° C 20mm
99
90
50
10 1
45 60 7550 75 100
40 60 80 70 90 110
Mineral oil -25 ° C 10mm Mineral oil -25 ° C 20mm Synt. Ester 20 ° C 10mm Synt. Ester 20 ° C 20mm
percent
99 90 50 10 145 55 65 70 60 80 60 75 90 60 90 120
Synt. Ester -10 ° C 10mm Synt. Ester -10 ° C 20mm Synt. Ester -25 ° C 10mm Synt. Esters -25 ° C 20mm
99
90
50
10 1
50 75 100 80 100 120 50 75 100 80 100 120
Nat. Ester 20 ° C 10mm Nat. Ester 20 ° C 20mm Nat. Ester -10 ° C 10mm Nat. Ester -10 ° C 20mm
99
90
50
10
60 75 90 100 80 120 60 80 100 80 100 120
Figure 40: The calculated from the results of experiments probability networks ABOVE: for Weibull distribution; BELOW: for
normal distribution;

Results
histograms mineral oil histograms mineral oil

Weibull normal distribution
Mineral oil 20 ° C 10mm Mineral oil 20 ° C 20mm Mineral oil -10 ° C 10mm Mineral oil 20 ° C 10mm Mineral oil 20 ° C 20mm Mineral oil -10 ° C 10mm
10.0 10.0
6 6
6 7.5 6 7.5
4 4 5.0 4
4 5.0
2 2 2.5 2 2 2.5
60 56 52 48 44 40 8 80 75 70 65 60 55 8 85 80 75 70 65 60 8
0 0 0.0 64 60 56 52 48 44 40 8
0 0 0.0
frequency
frequency
64 85 70 65 60 55 50 45 75 68 90 70 65 60 55 50 45 75
Mineral oil -10 ° C 20mm Mineral oil -25 ° C 10mm Mineral oil -25 ° C 20mm Mineral oil -10 ° C 20mm Mineral oil -25 ° C 10mm Mineral oil -25 ° C 20mm
10.0 10.0
7.5 6 7.5 6
6 6
5.0 4 5.0 4
4 4
2 2.5 2 2.5 2
2
70 65 60 55 8
90 84 78 72 66 8 96 90 84 78 8 75 70 65 60 55 8
0 0.0 0 0 0.0 0
96 60 56 52 48 44 40 64 75 102 60 56 52 48 44 64 80
Histograms synthetic esters Histograms synthetic esters

Synt. Ester 20 ° C 10mm Synt. Ester 20 ° C 20mm Synt. Ester -10 ° C 10mm Synt. Ester 20 ° C 10mm Synt. Ester 20 ° C 20mm Synt. Ester -10 ° C 10mm
8th
4.8 4.8 4.8 4.8
6 6
3.6 3.6 3.6 3.6
4
2.4 2.4 4
2.4 2.4
2 1.2 1.2 2 1.2 1.2
0 0.0 0.0 80 75 70 65 60 8
0 0.0 0.0
80
frequency
55
frequency
50
90
90
80
60
120 110 100 90 80 130

0
85 90 80 70 60 100
60
0
13
10
65
70
0
70
70
80
11
Synt. Ester -10 ° C 20mm Synt. Ester -25 ° C 10mm Synt. Esters -25 ° C 20mm
75
Synt. Ester -10 ° C 20mm Synt. Ester -25 ° C 10mm Synt. Esters -25 ° C 20mm
0
12
8th 8th
6.0 6.0
6 6 4.5 6 6 4.5
4 4 3.0 4 4 3.0
2 2 1.5
2 2 1.5
70 60 50 8
110 100 90 80 8
0 0 0.0
70
90
0.0
50
0 0
80
95
55
80
0
5
90
120 80 110 100 90 80 120

0
60
12
11
10
0
80
65
10
5
45
10
85
70
0
11
0
75
11
Histograms natural ester Histograms natural ester

Nat. Ester 20 ° C 10mm Nat. Ester 20 ° C 20mm Nat. Ester 20 ° C 10mm Nat. Ester 20 ° C 20mm
6.0 6.0
4.5 3 4.5 3
3.0 2 3.0 2
1.5 1 1.5 1
100 90 80 70 4 110 100 90 80 4
0.0 0 0.0 0
frequency
frequency
75 70 65 60 55 50 80 110 75 70 65 60 55 80 120
Nat. Ester -10 ° C 10mm Nat. Ester -10 ° C 20mm Nat. Ester -10 ° C 10mm Nat. Ester -10 ° C 20mm
6 6 6 6
4 4 4 4
2 2 2 2
100 90 80 70 8
85 80 75 70 65 60 8 85 80 75 70 65 8
0 0 0 0 105 100 95 90 85 80 75 8
90 110 90 110
Figure 41: The histograms to the obtained experimental data, for each liquid to both adapted Weibull as well as with customized
normal distribution. ABOVE: for mineral oil; CENTER: the synthetic ester; BELOW: for the natural ester
5.1.2 Results of descriptive statistics
In chart 1, the mean values of the breakdown voltages and associated standard deviations of the
experiments are summarized. The values may be found in Table 14. The calculation of the breakdown
voltages

Results
relied values of the individual samples are listed in Table 10 to Table 12 below.
Dielectric tests
120
110
100
90
Breakdown voltage in kV
80
70
60
50
40
20 ° C -10 ° C 10mm 10mm 10mm -25 ° C 20 ° C -10 ° C 20mm 20mm 20mm -25 ° C
Mineral oil Synthetic ester Natural ester
Figure 1: The means and standard deviations of the experiments performed with the three liquids
Table 14: Means and standard deviations of the punch studies in tabular form:
T emperatur and Abstan d

20 ° C - 10 ° C - 25 ° C 20 ° C - 10 ° C - 25 ° C
10mm 10mm 20mm 20mm
liquid 10mm 20mm
mineral oil 56.0 62.5 54.5 74.8 87.5 70.3

synthetic
MW kV 72.0 77.8 70.5 103.3 95.8 102.8
ester
natural ester 68.8 77.5 0.0 97.8 92.8 0.0
mineral oil 5.8 6.2 4.6 6.4 6.4 5.3
STDDEV synthetic
6.2 9.9 7.8 11.2 9.1 9.4
in kV ester
natural ester 6.5 5.7 0.0 10.4 8.0 0.0

Results
5.2 Gas-in-oil analysis
Table 15 shows the basic values of all samples analyzed are shown. In the following subsections, the
interpretation and evaluation by various conventional methods (Doernenburg, Rogers, IEC, MSS, Duval and
IEEE, see Section 4.3.4) are shown.
Table 15: Results of the gas-in-oil analysis, listing of the amounts of all analyzed gases, V = before the breakdown test, then N =;
TGG = total gas content:
Gaskonzentr a tion M ineral ö l in p pm

V / N TGG Temp. ID. O 2 N2 H 2 CO CO 2 CH 4 C 2 H 2 C 2 H 4 C 2 H 6 C 3 H 6 C 3 H 8th
V 7.8% 23350 53360 21.1 8.1 291 3.9 12.7 4.4 0.7 13.7 2.3
1
N 7.7% 23360 52140 155 18.2 302 28 256 55.9 4.9 27.6 5
20 ° C
V 7.8% 23410 53390 42.9 8.4 271 4.5 22.1 6.3 0.6 2.8 0.4
2
N 7.3% 21570 50110 151 14.7 274 29.5 278 58.9 5 21.6 2
V 8.9% 26300 61200 66.7 15.6 386 3 2.9 2.6 0.3 1.7 0.4
1
N 8.9% 26350 60460 98.4 18.2 376 18.5 192 39.5 3.5 18.3 1.6
- 10 ° C
V 9.2% 27450 63120 50.1 10.4 443 2.9 2.4 2 0.2 1.1 0.2
2
N 9.3% 28030 62050 68.7 14.9 479 11.6 104 22.7 2.1 10.4 1
V 8.7% 25450 60270 54.7 13.7 372 3.6 3.4 2.7 0.3 2 0.3
1
N 8.1% 24950 54850 34.7 13 361 5.5 32.5 8.5 0.8 4.8 0.6
- 25 ° C
V 8.1% 24180 55370 14 10.1 377 2.4 2 1.8 0.2 1.4 0.3
2
N 8.5% 25430 57340 56 12.5 396 6.5 46.8 11.5 1 5.9 0.5
Gask oncentration s ynthetischer Este r in ppm

V 7.4% 20560 52190 14 13 454 2.4 1.7 2.4 0.4 1.6 0.4
1
N 7.4% 20210 52950 61.2 34 507 6.5 141 17.1 1.3 4.3 0.8
20 ° C
V 7.6% 21900 53060 83.7 27.9 553 5.2 79 11.4 1 3.7 0.7
2
N 7.7% 21710 53970 75.8 45.9 593 9.2 201 25 1.9 6.3 1.1
V 8.4% 24230 58200 28.3 18.8 658 2.8 1.1 1.6 0.3 0.7 0.1
1
N 8.6% 24690 58700 11.9 17.2 745 3.3 15.5 2.6 0.4 1.1 0.4
- 10 ° C
V 8.6% 24620 59400 24.9 23.3 771 4.3 11.7 3.1 0.6 1.3 0.4
2
N 8.6% 25050 59310 23.5 28.6 725 4.9 45.5 6.4 0.8 1.9 0.5
V 8.5% 24370 58550 14.2 14.6 832 3.3 0.7 1.4 0.4 1 0.3
1
N 8.3% 24180 57820 12.6 15.8 632 3.2 38.1 2.7 0.4 1.1 0.3
- 25 ° C
V 7.7% 22160 52710 52.2 6 620 3.1 8.1 2.8 0.5 1.5 0.5
2
N 7.5% 21580 52310 19.5 9.8 482 3.7 62.6 5.6 0.6 1.8 0.4

Results
ga skonzentratio n natural ester in ppm

V 6.2% 830 55730 35 9.4 586 2.7 1.2 0.7 3.3 0.6 0.6
1
N 6.2% 250 57940 110 56.1 559 10.7 261 30.1 6.3 5.5 1.1
20 ° C
V 6% 4850 52490 33.2 9.8 522 3.5 13.1 2 2.9 0.5 0.4
2
N 6.3% 4510 55260 95.5 35.2 589 9 208 23.5 4 3.3 0.8
V 7% 9360 58490 37.6 9.7 653 2.8 0.5 0.5 1.9 0.4 0.4
1
N 7.4% 10330 60860 54.8 13.6 708 5.6 54.7 8.2 2.4 1.7 0.7
- 10 ° C
V 7.6% 14650 59300 10.9 13.3 476 2.9 3.4 1.6 1.3 0.3 0.2
2
N 7.3% 14240 57850 39.2 14.4 393 5.7 57 9.1 1.6 1.5 0.4
Table 16: Mean values (from all measurements at all temperatures of the respective liquid) and standard deviations of the
differences of the gas penetration tests in% of
Output value and absolutely in ppm:
Mittelwe rte and Standa r dabweichunge n the Diff e narrow

kind liquid size H2 CO CO 2 CH 4 C2 H2 C 2 H 4 C 2 H 6 C 3 H 6 C 3 H 8th
MW 52.4 4.2 8.0 13.2 144.0 29.5 2.5 11.0 1.1
mineral oil
STDDEV 57.7 3.7 18.0 9.9 99.3 20.5 1.7 6.5 0.9
MW - 2.1 8.0 -34.0 1.6 66.9 6.1 0.4 1.1 0.2
ppm syn. ester
STDDEV 26.9 9.3 115.1 1.9 51.3 6.3 0.4 1.2 0.2
MW 45.7 19.3 3.0 4.8 140.6 16.5 1.2 2.6 0.4
nat. ester
STDDEV 27.4 21.3 70.9 2.5 103.6 10.8 1.2 1.7 0.1
MW 205.8 46.4 2.1 369.0 2,820.6 868.9 652.8 509.4 230.7
mineral oil
STDDEV 247.8 46.9 4.4 229.2 2,166.4 438.0 337.4 373.0 154.2
MW 31.7 52.0 -3.4
3.4 49.3 2,660.4 182.3 66.9 62.1 77.0
% syn. ester
STDDEV 151.8 61.2 16.8 65.4 3,331.6 211.6 83.0 56.9 117.2
MW 176.8 201.1 - 0.2 162.5 8,888.6 1,820.9 44.6 525.4 89.6
nat. ester
STDDEV 92.3 226.5 13.7 93.4 9,572.5 1,645.6 31.6 217.5 12.5
5.2.1 Interpretation results of generally recognized schemes
The results of gas-in-oil analysis were evaluated with the six schemes according Doernenburg, Rogers, IEC,
MSS, Duval and IEEE, and the results are summarized in Table 17th The abbreviations are explained at the
bottom of the table group.

Results
Table 17: Results of the interpretations of the gas-in-oil analysis according to various schemes, such as: Abbreviations:
20 ° C 20 ° C - 10 ° C - 10 ° C - 25 ° C - 25 ° C
mineral oil
1 2 1 2 1 2
Doernenburg LNÜ LNÜ FNE LNÜ LNÜ FNE
Rogers FNE FNE FNE FNE FNE FNE
IEC D1 / ZT D1 / ZT D1 / ZT D1 / ZT D1 / ZT D1 / ZT
MSS FNE FNE D1 FNE FNE FNE
Duval D1 D1 D1 D1 LNÜ D1
IEEE / TDGC C1 C1 C1 C1 C1 C1
20 ° C 20 ° C - 10 ° C - 10 ° C - 25 ° C - 25 ° C
synthetic
ester 1 2 1 2 1 2
Doernenburg FNE FNE LNÜ FNE FNE FNE
Rogers FNE FNE FNE FNE FNE FNE
IEC D1 / ZT / ST D1 / ZT / ST D1 / ZT D1 / D1 ZT / ZT / ST D1 / ZT / ST
MSS D1 D1 FNE D1 FNE D1

Duval D1 D1 LNÜ D1 D1 D1
IEEE / TDGC C1 C1 C1 C1 C1 C1
20 ° C 20 ° C - 10 ° C - 10 ° C
natural
ester 1 2 1 2
Doernenburg FNE FNE FNE FNE
Rogers FNE FNE FNE FNE
IEC OX / ST ZT / OX / ST D1 / ZT / OX D1 / ZT / OX
MSS FNE FNE D1 D1

Duval D1 D1 D1 D1
IEEE / TDGC C1 C1 C1 C1

Results
D1 Low energy discharges
D2 high energy discharges
T1 Temperature error below 300 ° C
T2 Temperature error between 300 and 700 ° C T3
Temperature error over 700 ° C
LNÜ Limit not exceeded
FNE not recognized error
C1 No mistake
C2 Normal operation, errors can occur C3
High probability of error
C4 Secure error probability
ZT Cellulose decomposition thermally
ST Poss. Contamination by step switch OX
oil oxidation
5.2.2 gas formation in the experiments in absolute values (ppm)
The most important criterion of the investigations of the gases produced the differences in the measured
gases were here in Chapters 5.2.2 and 5.2.3 and calculated according to the breakdown investigations.
Some of these differences are so high and different that double standards had to be used for different
gases.
In diagram 2 the average values and
Standard deviations of the calculated differences of the measured gases shown in ppm and in Chart 3 to 5,
the diagram values of the differences of the individual experiments for comparison.

Results
Means and standard deviations of the differences Acetylene - C 2 H 2

absolute
Mineral oil
synth. Ester Nat.
ester 250
100
200
80
Difference in ppm
150
Difference in ppm
60
100
40
0 50
C2H2
0 20
- 50
H2 CO CO2 CH4 C2H4 C2H6 C3H6 C3H8
- 20
- 100
- 40 - 150
Diagram 2: The differences of the measured gases before and after the breakthrough experiments in absolute values (mean and
standard deviation, unit: ppm). LINKS: all measured
Noxious gases other than acetylene; Right: The measured values of ethyne, shown for the outstanding amounts in a different
scale,
Gas differences petroleum absolutely
300
20 ° C 1
250
20 ° C 2
Difference in ppm
- 10 ° C for 1
200
- 10 ° C 2
- 25 ° C 1
150
- 25 ° C 2
100
0 50
H2 CO CO2 CH4 C2H2 C2H4 C2H6 C3H6 C3H8
- 50
Chart 3: Gas differences of the individual experiments in absolute values (in ppm) for mineral oil

Results
Gas differences synthetic esters absolutely
150
100 20 ° C 1
20 ° C 2
Difference in ppm
0 50 - 10 ° C for 1
- 10 ° C 2
- 50
- 25 ° C 1
- 25 ° C 2
- 100
- 150
- 200
Chart 4: The gas differences of the individual experiments in absolute values (in ppm) for the synthetic ester
Gas differences absolutely natural ester
300
250
20 ° C 1
200
Difference in ppm
20 ° C 2
150 - 10 ° C for 1
- 10 ° C 2
100
0 50
- 50
- 100
Chart 5: Gas differences of the individual experiments in absolute values (in ppm) for the natural ester

Results
Table 18: The calculated differences in the gas concentrations before and after the breakthrough experiments in absolute values
(in ppm or mg / kg; TGG = total gas content):
G asdifferenzen mineral oil in ppm
Temp. No. TGG O2 N2 H2 CO CO2 CH4 C2H2 C2H4 C2H6 C3H6 C3H8
10 -1220 133.9 10.1 11 24.1 243.3 51.5 4.2 13.9 2.7

20 ° C 1 -0.1
2 -0.5 -1840 -3280 108.1 6.3 3 25.0 255.9 52.6 4.4 18.8 1.6
0 50 -740
740 31.7 2.6 -10 15.5 189.1 36.9 3.2 16.6 1.2
- 10 ° C 1
2 0.1 580 -1070 18.6 4.5 36 8.7 101.6 20.7 1.9 9.3 0.8
0.5 2.8 0.3

-25
25 ° C 1 -0.6 -500 -5420 -20.0 -0.7 -11 1.9 29.1 5.8
2 0.4 1250 1970 42.0 2.4 19 4.1 44.8 9.7 0.8 4.5 0.2
gas d ifferen z en syntheti s cher e art in ppm
Temp. No. TGG O2 N2 H2 CO CO2 CH4, C2H2, C2H4 C2H6 C3H6 C3H8
0 -350
350 760 47.2 21.0 53 4.1 139.3 14.7 0.9 2.7 0.4
20 ° C 1
2 0.1 -190 910 -7.9 18.0 40 4.0 122.0 13.6 0.9 2.6 0.4
1.0 0.1 0.4 0.3

-10 ° C 1 0.2 460 500 -16.4 -1.6 87 0.5 14.4
2 0 430 -90 -1.4 5.3 -46 0.6 33.8 3.3 0.2 0.6 0.1
-0.2
0.2 -190 -730 -1.6 1.2 -200 -0.1 37.4 1.3 0.0 0.1 0.0
- 25 ° C 1
2 -0.2
0.2 -580 -400 -32.7 3.8 -138 0.6 54.5 2.8 0.1 0.3 - 0.1
GASD iffere n zen natural E s ter in p pm
3.0 4.9 0.5

20 ° C 1 0.0 -580 2210 75.0 46.7 -27 8.0 260 29.4
2 0.3 -340 2770 62.3 25.4 67 5.5 195 21.5 1.1 2.8 0.4
54 7.7 0.5 1.3 0.3

-10
10 ° C 1 0.4 970 2370 17.2 3.9 55 2.8
2 -0.3
0.3 -410 -1450 28.3 1.1 -83 2.8 54 7.5 0.3 1.2 0.2
5.2.3 gas formation in the experiments relatively (in% of the initial value)
The gas production was also shown as a percentage, relative to baseline. Thereby resulting in the
Esterflüssigkeiten for ethyne (and sometimes for ethene) so high differences from the other gases that they
had to be displayed in separate standards in order to achieve a clear representation. In diagram 6, the
averages and standard deviations of the calculated

Results
Difference of the measured gases shown in% and in diagram 7 to Chart 9, the values of the differences of
the individual experiments for comparison.
Means and standard deviations of the differences Acetylene - C 2 H 2

in% of the initial value
2000
1800 Mineral oil
synth. Ester Nat.

1600
ester
1400 9000
Difference in% of the initial value

Difference in% of the initial value
1200
7000
1000
800 5000
600
3000
400
200 1000
0 C2H2
- 1000
Diagram 6: The differences of the measured gases before and after the breakthrough experiments in relative values (mean and
standard deviation, as shown in% of the initial value). LINKS: all measured noxious gases other than acetylene; Right: The
measured values of ethyne, shown for the outstanding amounts in a different scale,
Gas oil differentials in% of baseline ethyne C 2 H 2
7000
1500 6000
1300
5000
1100 20 ° C 1
20 ° C 2
4000
900
- 10 ° C for 1
Difference in% from baseline
- 10 ° C 2
700 3000
- 25 ° C 1
500 - 25 ° C 2
2000
300
1000
100
H2 CO CO2 CH4 C2H4 C2H6 C3H6 C3H8 0

- 100
C2H2
Diagram 7: The relative gas differences of the individual experiments (in% of the initial value) for mineral oil; LINKS: all measured
noxious gases other than acetylene; Right: The measured values of ethyne, shown for the outstanding amounts in a different
scale,

Results
Gas differences synthetic esters in% of ethyne C 2 H 2

output value
700 9000
600 8000
7000
500
20 ° C 1
6000
400 20 ° C 2
5000

- 10 ° C for 1
300
- 10 ° C 2
4000
200 - 25 ° C 1
3000
- 25 ° C 2
100
2000
0 1000
- 100 0
C2H2
Chart 8: The relative gas differences of the individual experiments (in% of the initial value) for synthetic ester. LINKS: Results for
all gases except acetylene; RIGHT: ethyne represented due to the high values on a different scale
Gas natural ester differences in% of ethyne C 2 H 2 ethene C 2 H 4

output value
25000 4500
900
4000
800
20000
3500
Difference in% from baseline difference in%
700
3000
600
15000
20 ° C 1 2500
500
20 ° C 2
400 2000
- 10 ° C for 1 10000
300 - 10 ° C 2 1500
from baseline
200 1000
5000
100
500
0
0 0
H2 CO CO2 CH4 C2H6 C3H6 C3H8
- 100 C2H2 C2H4
Diagram 9: The relative gas differences of the individual experiments (in% of the initial value) for natural esters. LINKS: Results
for all gases except acetylene and ethylene; Center and right: ethene and ethyne, shown in a different scale because of the high
values

Results
Table 19: The calculated differences in gas concentrations before and after the penetration tests as a percentage of the initial
value:
G asdifferenzen mineral oil in % of A usgangswertes
-1.3 0.0 -2.3 634.6 124.7 4 618 1916 1170 600 101 117
20 ° C 1
2 -6.4
6.4 -7.9 -6.1 252.0 75.0 1 556 1158 835 733 671 400
- 3517 6521 1419 1067 976 300

-10
10 ° C 1 0.0 0.2 -1.2 47.5 16.7
2 1.1 2.1 -1.7 37.1 43.3 8th 300 4233 1035 950 845 400
-6.9
6.9 -2.0 -9.0 -36.6 -5.1 -3 53 856 215 167 140 100
- 25 ° C 1
2 4.9 5.2 3.6 300.0 23.8 5 171 2240 539 400 321 67
ga sdiff e refine synthetic E s ter in % the output value
. No. TGG O2 N2 H2 CO CO2 CH4 Temp C2H2 C2H4 C2H6 C3H6 C3H8
613 225 169 100

20 ° C 1 0.0 -1.7 1.5 337 162 12 171 8194
2 1.3 -0.9 1.7 - 9 65 7 77 154 119 90 70 57
13 18 1309 63 33 57 300
-10 ° C 1 2.4 1.9 0.9 -58 -9
2 0.0 1.7 -0.2 -6 23 -6 14 289 106 33 46 25
-2.4 -0.8 -1.2 -11 8 - 24 -3 5343 93 0 10 0

- 25 ° C 1
2 -2.6 -2.6 -0.8 -63 63 - 22 19 673 100 20 20 - 20
G asdiff e Conference e n natural c H he Est e r in% of the off G angsw ertes
91 817 83
20 ° C 1 0.0 -69.9 4.0 214 497 -4.6 296 21 650 4200
2 5.0 -7.0
7.0 5.3 188 259 12.8 157 1488 1075 38 560 100
26 325 75
-10
10 ° C 1 5.7 10.4 4.1 46 40 8.4 100 10840 1540
2 - 3.9 -2.8 -2.4 260 8 - 17.4 97 1576 469 23 400 100
5.3 Oil characteristics
There were in all studies, both before and after, the breakdown voltage and the absolute water content
measured. The results are listed in Table 20th

Results
Table 20: Oil characteristics of the individual series of measurements; ABOVE: mineral oil; CENTER: synthetic esters; BELOW: natural
ester:
mineral oil
before after that
Moisture penetration moisture penetration ppm

kV ppm kV
10mm 11 84 11 71
20 ° CI
20mm 11 84 11 71
10mm 5 89 5 83
20 ° C II
20mm 10 86 11 74
10mm 11 87 11 84
- 10 ° CI
20mm 11 87 11 84
10mm 14 94 15 82
- 10 ° C II
20mm 14 94 15 82
10mm 8th 88 9 94
- 25 ° CI
20mm 11 74 17 62
10mm 8th 88 9 94
- 25 ° C II
20mm 13 82 13 75
synth. Ester
before after that
kV ppm kV
10mm 67 67 133 61
20 ° CI
20mm 72 65 129 51
10mm 58 61 96 55
20 ° C II
20mm 58 61 96 55
10mm 68 75 204 76
- 10 ° CI
20mm 68 75 204 76
10mm 128 80 253 79
- 10 ° C II
20mm 128 80 253 79
10mm 72 77 199 62
- 25 ° CI
20mm 72 77 199 62
10mm 71 69 240 66
- 25 ° C II
20mm 71 69 240 66
nat. ester before

after that
kV ppm kV
10mm 83 79 92 56
20 ° CI
20mm 83 79 92 56
10mm 25 71 38 61
20 ° C II
20mm 25 71 38 61
10mm 82 67 139 64
- 10 ° CI
20mm 82 67 139 64
10mm 30 63 82 61
- 10 ° C II
20mm 30 63 82 61

Results
5.4 sighting marks on the breakdown of the cellulose
Figure 42 to Figure 47 the images made after the investigations breakdown investigations are inserted.
Regular the side views of the samples are shown, in special cases, where it was a breakdown in the central
board without external tracks, the samples were photographed in a top view (narrow side) to make the
existing channel visible. For a better comparability, the optical images were arranged so that test series are
grouped with the same temperature.
Figure 42: Photos of the tested at room temperature board strips with 10 mm distance; LEFT: mineral oil; CENTER: synthetic
esters; RIGHT: natural ester
Figure 43: Photos of the tested at room temperature board strips with 20 mm distance; TOP LEFT: mineral oil; TOP RIGHT:
synthetic esters; BELOW: natural ester

Results
Figure 44: Photos of the tested at -10 ° C board strips with 10 mm distance; LEFT: mineral oil; CENTER: synthetic esters;
RIGHT: natural ester
Figure 45: Photos of the tested at -10 ° C board strips with 20 mm distance; TOP LEFT: mineral oil; TOP RIGHT: synthetic
esters; BELOW: natural ester
Figure 46: Photos of the tested at -25 ° C board strips with 10 mm distance; LEFT: mineral oil; RIGHT: synthetic esters

Results
Figure 47: Photos of the tested at -25 ° C board strips with 20 mm distance; LEFT: mineral oil; RIGHT: synthetic esters
In Table 21 the results of Durchschlagspurensichtungen are summarized. If the totals were significantly
higher than average, a color coding was performed.
Table 21: Results of sightings of punch marks on the samples (K0 = oil shock, K1 = slight traces on the board, K2 = strong traces
on the board):
Liquid temperature distance category

°C mm K0 K1 K2
10 6 9 4
20
20 1 0 19
10 9 5 6
mineral oil
- 10
20 11 2 7
10 4 12 4
- 25
20 6 3 11
10 6 6 8th
20
20 3 7 10
10 11 6 3
synthetic esters
- 10
20 18 0 2
10 6 7 5
- 25
20 10 5 5
10 3 5 12
20
20 1 2 17
ester
natural
10 7 4 9
- 10
20 9 2 9

discussion
6 discussion
The following chapter which discusses in Chapter 5 tables and in diagrams displayed results. First, a
fundamental discussion of the suitability and availability of the procedure and the measurement results in
Section 6.1. After that
become the considerations to the results the
Dielectric investigations dealt with discussion of the breakdown values, the evaluation of the breakdown
tracks and the data of the oil characteristics in chapter 6.2. The results of studies of the individual gas
liquids, together with the results of the evaluation schemes are discussed in Section 6.3.
6.1 Considerations for independence, number of samples and
gas concentration
From the results of the regression (see Table 13 in section 5.1.1) is apparent that has changed in the period
of studies on the electric strength of the samples and not the moisture ratio between the respective fluid and
the cellulose was not changed.
In itself this proof of independence is indeed beneficial to the usability of the breakdown data for evaluation
with descriptive statistics, on the other hand, this number of samples produced in part only small amounts of
gas. In a real transformer whether, in comparison with the arc, large amount of oil, however, can also be
expected no major concentrations. So clearer results that gas concentrations would regard, requires a lot
more punches per test would be necessary.
Greater concentrations were indeed easier to detect, but the results of penetration tests would with
likely
Depending from one another and would thus not be used for the evaluation. Furthermore you away with it
on the required in this study practicality.

discussion
6.2 breakdown behavior at low temperatures
in the the next chapter become the results the perforating
stress studies discussed. In this case, starting with the memoir of the voltage values followed by a
discussion of the results of the evaluation of the optical breakdown lanes and finally a summary of the
results of measurements of the oil characteristics.
6.2.1 Discussion of breakdown voltages
In table 10 to table 12 are the Results the
Breakdown voltage tests listed in Diagram 1 and they are graphically represented with mean and standard
deviation. None of the liquids comprises in combination with cellulose and cooling to -10 ° C and 25 ° C, a
significant deterioration in the electrical resistance as compared to the values at room temperature.
Making it possible to provide no clear evidence to suggest that there is a moisture-related deterioration of
the breakdown behavior after cooling. In alternative insulating fluids with usual water content so do not need
the transformer practice failures are due calculated by moisture deposits on creepage distances. It is seen
in diagram 1 that the Esterflüssigkeiten provide constant higher penetration values as the mineral oil. This
can be explained by the fact that, as mentioned in Section 2.2.2, with mineral oil, from the standpoint of the
transformer practice yet realistic, but relatively high (5 to 14 ppm, see Table 20), wherein 10 ppm in the
generally regarded as the upper limit for trouble-free operation.
In the 10 mm samples at all liquids the same behavior of the values can be observed: At room temperature
and -25 ° C, the average values hardly differ and at -10 ° C, the breakdown voltage is increased by 8 to
10%. Since these values, however, move in the standard deviation, no importance is attached to them
statistically.

discussion
6.2.2 Analysis of the breakdown lanes on the cellulose
In Figure 42 to Figure 47 and Table 21, the results of the optical penetration evaluation are shown. The
contrasting significantly from the average results are highlighted.
It is remarkable that at room temperature at all three liquids substantially heaped strong traces of the
cellulose are visible as in the experiments with lower temperatures. Only mineral shows trends for cellulose
breakdown even at -25 ° C. This means that on the basis of cellulose destruction the theory that at the
cellulose surface deposited moisture reduces the electrical resistance, can not be confirmed.
Since the electrical resistance total not deteriorate significantly, it can be assumed that too little water has
been dispensed. The constant across all temperatures breakdown voltage values are an indication.
Furthermore, it can be seen in Table 21 that, apart from the measuring series of the synthetic ester at -10 °
C, and a series of measurements with mineral oil at the same temperature, no significant increase in oil
punches takes place with decreasing temperature. Why the copies of the synthetic ester had such strong
cellulose trends at -10 ° C (Table 20 center) can also be based on the oil moisture content or the breakdown
voltage does not explain this range of values of the other tests.
Based on the photos of the cellulose samples can be seen that it in Esterflüssigkeiten both the natural and
the synthetic esters, tendencies toward central breakdown through the cellulose sample
in the
Contrary to the punch on the cellulose surface or by the oil was. All samples in which this was the case,
were placed in photographing of Figure 44 to Figure 47 (the front side), respectively.
It is striking that in the experiments not a single sample was penetrated centrally with mineral oil, on
Esterflüssigkeiten this case occurred very comfortable on. One possible reason for this could be that the
samples of Esterflüssigkeiten require longer impregnation due to their higher viscosity and the strips were
simply still not impregnated at its center. This can, however, apart from those in preliminary experiences
with sufficient

discussion
Exclude impregnation time for another reason. This is because the cooled samples before testing for 24
hours at 50 ° C or 35 ° C were heated. At these temperatures, the viscosity is lower again and still no
difference in the incidence of the central punches between heated and unheated samples was observed.
Due to the high diffusion coefficient, it was not possible that during the period of cooling (about 9 hours) was
a water accumulation inside the cellulose strip. This situation provides opportunities for further experiments.
He
is how the studies made here show not
temperature-dependent and occurs at two distances (10 and 20 mm) equally on.
6.2.3 oil characteristics - breakdown voltage according to IEC 60156, and water content
In the oil characteristics can be seen in Table 20 that both Esterflüssigkeiten verfeuchtet were much
stronger after the breakthrough experiments as the mineral oil. The samples were taken in each case before
the warm-up phase or immediately after the examination of the cellulose samples.
Now the increased moisture is indeed in the heated samples by the objective of the oil-cellulose insulation
moisture equilibrium (see section 2.1) declare not
However, the increased moisture content of the samples of the tests at
Room temperature, which were so NOT heated.
On one hand, oil humidity increased by the absorption of humidity by the liquid, on the other hand, water is
also generated by the decomposition of the cellulose by the arc. To what extent this can result in
oil-cellulose insulation with Esterflüssigkeiten problems in the transformer operation, needs to be further
investigated.

discussion
6.3 gassing
Reference to the diagrams 2 to 9, the results of gas-in-oil analysis are shown. The graphs 2 to 5 show the
absolute values and the graphs 6 to 9 the values in percent, relative to the starting value. It is clearly visible
that can be broadly recognize the basic patterns of most gases, but differences in concentration between
the liquids are clear. Basically consistently lower gas concentrations were measured as in the liquids at
room temperature in the cooled liquid.
6.3.1 gas formation
In sum, it can be said that the total gas production in the synthetic ester was lowest.
Most striking, the expected strong ethyne and ethene production is in the Esterflüssigkeiten. When natural
ester after the tests sixth for the synthetic esters with ethyne to factor 80 and ethene to factor was a
Ethinzunahme by a factor of 200 and a ethene production by a factor of 40, based on the initial value,
measurable, In comparison, the values of ethyne took in mineral oil than a factor of 60 and ethene by a
factor of 14 to. This is justified by the fact that, in the released Estermolekülen (synthetic such as natural)
long chain hydrocarbons of at discharge, energy can be broken up into many individual homogeneous CH
fragments immediately thereafter again to stable HC≡CH (ie ethyne) recombine molecules. The sharp
increase of ethene is similar.
differing length and
there are different branches, respectively ring formation. When the synthetic ester ethene and
Ethinproduktion soft not so much on the values of mineral oil. One can therefore assume that in contrast to
natural esters in synthetic ester chains are split into larger fragments, or recombine to form larger stable end
products.

discussion
A carbon dioxide production could be detected in all fluids in very small and widely varying concentrations.
Mineral oil, the values of concentration differences from -10 to 36 ppm were, the synthetic ester from -200 to
87 ppm, and the natural esters -83 to 67 ppm. Six of the seven negative values
occurred in the experiments with deep
Temperatures, only one of them at room temperature. The decrease of the measured values of this gas is
expected to reach the poor solubility of CO 2 due in oil. In the tests, was probably not only not solved the few
gas newly produced and delivered via bubble formation, but also the already dissolved CO 2 excreted by the
vibrations from the liquids over the surface to the ambient air.
The measured values for carbon monoxide can clearer conclusions: In the case of mineral oil only values of
up to 10 ppm were produced, the synthetic esters to 21 ppm, and the natural esters even up to 46 ppm. So
the vegetable oil produced almost five times as much carbon monoxide as mineral oil. Because it is
considered as a key gas for the cellulose degradation, this increased production is observed. However, a
direct result of corruption by too high CO value came not on The MMC Energy, but the absolute
concentration was too low, at less than 100 ppm in all experiments.
As with the other fluids substantially less CO is formed as the natural esters, it can be assumed that this
carbon monoxide is produced from the thermal digestions of the triglyceride molecules and not from the
cellulose. The fact that the mineral oil,
in about the same amount
Cellulose degradation by the arc took place as in the esters (see Table
21), a lower carbon monoxide level was detected, confirmed this statement.
6.3.2 evaluation schemes
The Results shown in Table 17 used six
Evaluation schemes show that these methods detect the fault only partially. The methods according
Doernenburg, Rogers and IEEE / TDGC beat at

discussion
any attempt at, not even mineral oil. This means that the produced gas concentrations for these methods
were too low in general. The method according to Duval realized in 14 of 16 cases the error "discharges low
energy" correctly. The two cases not detected indicate "not exceeded Limit" and the result occurred in the
experiments with mineral oil (-25 ° C) and the synthetic ester
to (-10 ° C), and therefore does not have to
consider, liquid specific problems of this method out. The method according to MSS has seen only one of
six possible "hits" in mineral oil, four out of six samples for were properly assessed and the natural ester two
of four in synthetic ester. At a lower error rate and a large volume of oil that is why there is a risk that carbon
copies with little energy to remain anonymous, said recognition chance is higher in esters than in mineral oil
here.
were the IEC method can indicate multiple errors, reported "discharges low energy", "oil oxidation", "cellulose
decomposition thermal" and "contamination by step switch". The error "discharges low energy" was correctly
identified in all tests with mineral oil and synthetic esters. When natural ester he could only be detected in the
tests at -10 ° C rather than those at room temperature.
However, the error "contamination by step switch" was found in the Esterflüssigkeiten in six out of ten cases
incorrectly. In the experiments with petroleum this was not once the case. This means that there is at
Interpretation of discharge errors in Esterflüssigkeiten using traditional methods to a false
detection of oil contamination from the tap changer oil compartment comes.
Another wrong diagnosed error is the oil oxidation. This misjudgment of the IEC method appeared
exclusively in the natural ester, to be precise in four out of four attempts. was especially striking that the
criterion for oil oxidation (O 2 / N 2 < 0.3) already (in the new state of the natural ester both degassed and not
degassed) was not reached. Such differences in the concentrations are possible due to the different relative
gas solubilities between mineral oil and esters.

discussion
These abnormalities are important to consider when using natural esters in conjunction with an evaluation
by IEC scheme. The error "cellulose decomposition thermal" was shown in all tests with mineral oil and
synthetic esters. Only one of the experiments with natural ester at room temperature, this error was not
reported. This comes as an interesting fallacy, as can be seen from Table 20 that especially the synthetic
ester showed and least cellulose participation in the carbon copies of the natural esters had a significantly
high cellulose destruction in the room temperature tests.
6.4 Referring to the current state of research
As stated in [22] of Borsi for the liquids alone, the breakdown behavior of a dry oil-cellulose insulation
system with tangential loaded paper surface varies with temperature only marginal. However, higher
moisture levels than in Borsi described (up to 15 ppm) is not yet led to a reduction in the breakdown voltage.
It is suspected that the electric resistance decreases also with further increasing humidity. To prove this,
however, further studies with higher water contents are necessary.
The Kahn et al. in [61] and [62] published for room temperature results are only partly comparable with the
results obtained in this work results. The produced gas quantities of Esterflüssigkeiten were not clearly
lower compared with mineral oil. Also, in the investigations carried out here, especially
for the natural esters, In contrast to [61], significantly higher
Ethinmengen measured than with mineral oil.
in the present study because no aging studies were performed can be no direct reference is made to the
publication of Höhlein-Atanasova and Frotscher [64]. Nevertheless, a slight increase on the average CO
production falls on the natural ester. Thermal decomposition of the liquid
in the
Arc is present, of course. However, this increase was in

discussion
Contrast found in [64] the synthetic esters. This result is not clear due to the cooling.
The changes made in [63] on Duval Triangle were regarding the borders between light and heavy discharge
phenomena for the results of this work is irrelevant. For the simulated here error light discharges and the
Duval Triangle for mineral transformer oils yielded clear results.

summary
7 Summary
The results of the studies showed no statistically significant deterioration in the electrical resistance with
decreasing temperature. Thus the suitability of Esterflüssigkeiten for use at low ambient temperatures could
be confirmed. The assumption that by electrically lowering the temperature to,
tangentially loaded cellulose surfaces
enriching water reduces the electrical resistance, could under the conditions as they were defined for the
information given here trying not to be proven. It
is, however, well known that the insulating fluids have lower saturation humidity values for
temperature reduction and therefore have to release water. An obvious reason for the consistently good
values of the electrical resistance
therefore possibly that of the cellulose
delivered water is sufficiently well absorbed so as not to reduce the dielectric strength at the surface.
Since the diffusion times at low temperatures are very high, however, it's much more likely that the causes
in the standard humidity conditions as are customary in transformer practice and were used as a basis in
this work can be found. The thus limited to relatively low values of moisture is not enough very likely to have
a significant effect on the cellulose-related breakdown mechanism. To check this, further tests must be
considered with higher relative humidity values.

summary
7.2 gassing
7.2.1 usability evaluation schemes
The method according to Duval recognized the error in the Esterflüssigkeiten in nine cases out of ten, and is
therefore also suitable for the investigation of discharge problems in the diagnosis of Estereinheiten.
The IEC scheme evaluated the errors in both mineral oil and the synthetic ester in all the tests correctly.
When natural ester only two of four experiments were evaluated correctly. However, it came with this
method also in erroneous error: Only in Esterflüssigkeiten contamination of the insulating liquid was in six
out of ten cases incorrectly reported with oil from the tap changer oil compartment. This means that you also
get a false high probability of leakage diagnosis of the tap changer space in the detection of discharge
errors. When using this method with natural esters investigations have shown that there is a false indication
of the failure of oil oxidation. The synthetic esters, this is not the case.
In the method according to MSS were the esters only six out of ten discharge errors
properly assessed, the possibility of undetected
Discharge errors is high.
The methods according Doernenburg, Rogers and IEEE detected no error because the gas concentrations
were too low. For that further studies with even more heavily loaded liquids are necessary.
For higher gas concentrations, a larger number of samples or disruptive breakdown would have been
necessary. An increase in the dielectric loading of liquids, however, the independence of the measurement
results would risk because with increasing stress Number of course the oil quality and therefore the

Impact on the practice
decrease electrical resistance. This would have been incompatible with the requirement for independent
outcomes.
7.3 Considerations for further investigations
An important change for further study would be to operate at high moisture contents of the fluids to
determine whether the electrical strength then, even
compared to the values without
Cellulose surface deteriorated. Members further to this would be the variation of moisture in oil, in order to
derive a possible depending on the decrease in the breakdown voltage for increasing humidity. Similarly, the
extent to which the cellulose is drawn as it passes through many temperature cycles by the moisture
transients Esterflüssigkeiten, from the perspective of aging, affected up.
The esters are, in practice, to be transported through many additions and disconnections much larger
amounts of water than mineral oil (see Figure 3). one speaks in mineral oil from 10 to 30 ppm water, which
must change at 60 ° C temperature difference between oil and board, there can be up to 400 ppm water at
esters, corresponding to a factor of 10 to 40. This amount of water may no longer negligible in a paper
moisture content of 1 to 2%.
Nevertheless, this requires further investigation, as these aging tests have exceeded the scope of this work.
The impact of the elimination of the free acids from the Estermolekülen require further research as well.
Investigations of acid value at different arc energies are on offer. Also, the effect on the DP value of the
cellulose or the exact compositions of the acids produced have to be examined.

8 impact on the practice
The planning and conduct of investigations had alternative goal statements about the practical utility and the
possibilities of expanding the applications of
Insulating, in particular of
Esterflüssigkeiten to be able to meet.
In particular, this concerned the, at low temperatures may occur electrical problems and the possible and
necessary differences in the viewing and interpretation of results of the gas-in-oil analysis.
8.1 cold start
It should the electrical behavior of an oil-cellulose insulation system in the worst case the tangential field
stress after cooling of a simulated operating on a defined outside temperature, be tested experimentally.
The investigations carried out here have shown that these liquids can easily be used at temperatures of up
to -10 ° C and -20 ° C. Also, a switch-on operation during the cooling is possible, without the electrical
strength of the insulation is impaired.
This is likely due to the fact that the moisture content used in the practice of liquids that were used in the
studies were sufficiently low. The requirements for this were based on the usual practice in the transformer
values in order to make a statement about their usefulness for Estereinheiten at low temperatures.

8.2 Gas-in-oil analysis
8.2.1 Gas Production
aggravating the fact that the synthetic ester in principle the same loading produced a smaller quantity of gas
than the other two fluids applicable for practical use. This necessitated a penibleres handling during
sampling and more accurate measurement of pollutant gases. Otherwise, the gas production behavior of the
synthetic ester is similar to that of mineral oil.
The natural ester has a much higher production of ethene (key gas for local overheating) and acetylene (key
gas for arcs). The latter is in practice advantageous because it simplifies the detection of discharges due to
the higher concentration. The former could theoretically distorting effect on the evaluation, at least, however,
none of the five evaluation methods used in this study indicated a thermal fault.
8.2.2 evaluation schemes
The method according to Duval recognized the error in the Esterflüssigkeiten in nine out of ten cases, the
method according to MSS had only six out of ten, a much worse hit rate and the possibility of undetected
errors discharge is high.
The method according to IEC though often rated the error correct, but also shows the esters falsely other,
non-existent errors. As has been reported oil oxidation during natural esters and with any other liquid in all
cases and in both the natural and the synthetic esters of error of contamination by insulating from the tap
changer room was shown false positive. Therefore, the limits of IECAuswertungsverfahrens for oil oxidation
have to be reconsidered for the natural ester because this method consistently incorrectly pointed out this
error.

For the methods according to Doernenburg, Rogers and IEEE gas concentrations generated in the tests
carried out were too low to enable error detection.
Thus, all schemes used here are, in practice, be used with caution, only the method by Duval gave
consistent results.

Summary
9 Summary
This paper reports on the behavior of cooled, natural and synthetic esters, compared with mineral oil on
their dielectric strength in connection with a creepage distance with pressboard and identified through
frequent breakdowns, gases dissolved in oil.
To get results on this task, a test setup and an appropriate sample form and a test program have been
developed and implemented. Before and after the application of AC voltage, the dissolved gases in the
liquids were determined. This was followed by an analysis of the data obtained and an interpretation.
A goal of the work, enabling an expansion of the applications of Esterflüssigkeiten could be achieved,
by showing that the
alternative insulating media in connection with cellulose, after cooling to -25 ° C (synthetic ester) and -10 ° C
(natural ester) showed no deterioration in the electrical resistance. The assumption that this could be on the
cellulose surface of the case due to addition of water, could not be confirmed under the circumstances.
It was assumed at the beginning that would let notice a significant reduction in the breakdown voltage by
lowering the temperature. This was based on the moisture content of the liquid in connection with the used
cellulose.
When decrease in the temperature and the water absorption capacity of the oil drops and it was assumed
that, liberated in the cooled state water collects on the cellulose surface, before it is absorbed by the paper
and leads to a reduction of the electrical resistance. This assumption could not be confirmed with the
experiments carried out. The breakdown voltage of the experimental arrangement used changed with the

Summary
Temperature is not significant. Also, there was not when cooled, as anticipated, to a heaping strike through
to the surface of cellulose. This behavior was observed in both mineral and both used Esterflüssigkeiten.
One possible explanation for the continued good electrical resistance that the existing moisture content -
typically values, as required in the operation of a transformer - was too small to reach the state of
Verfeuchtung the paper surface adopted.
Since it is in the present work is a study of operational situations and
-conditions negotiated were higher, not permitted to operate,
Humidity values not investigated. It is believed that for such high humidity values requires that the electrical
resistance would be reduced even at room temperature without cooling.
9.2 gassing
When gassing was initially assumed that there would be differences in, generated by discharges medium
energy when applied Error Error gases between mineral oil and the Esterflüssigkeiten. This assumption was
confirmed by the results of the investigations.
It comes in both the natural and the synthetic ester in a significant increase of the gas ethyne, this increase
in natural ester is more pronounced. Furthermore, the natural ester a much stronger increase of the gas
ethene was recorded as mineral oil and the synthetic ester.
The use of various recognized evaluation schemes showed that these are not all unconditionally usable.
The method according to Duval is working correctly (nine out of ten errors correctly identified), although the
method for MSS operating correctly, but not reliable as they diagnosed properly only six out of ten error
cases. Although the method according to IEC is reliable, there were ten of

Summary
properly assessed ten mistakes, but in addition has often (six out of ten) falsely contamination by step
switch oil exclusively to the natural ester, but there in four out of four cases in both Esterflüssigkeiten falsely
detected oil oxidation. Methods for Doernenburg, Rogers and IEEE no statement can be made, as this
whether the detected no errors at low gas concentrations.

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attachment
11 Appendix
samples impregnation
The samples were finished cut, kerosene oven dry and supplied vacuum packed with desiccant and
impregnated as follows:
1. Layers in a glass vessel and loaded with a metal object
2. introduction into the vacuum oven and placing the inlet tube
3. closing the cabinet and application of the vacuum (<1 mbar, typ. 0.4 mbar)
4. Vacuum Hold for 1 hour
5. admitting the insulating liquid is at least 2 cm higher up the mirror as the top sample
6. Vacuum holding for 4 hours
7. Vacuum crushing, wherein the air inlet a, filled with dry silica gel, desiccant cartridge (volume 1
liter) occurs
8. rest period 48 hours
Thereafter, the samples were combined with the test vessel filled either tested immediately subjected (for
tests in room temperature), or together with the test vessel filled of the heat treatment.

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T ECHNICAL U NIVERSITY G RAZ

I INSTITUTE FOR H OCHSPANNUNGSTECHNIK

for Earning a Doctor of Technical Sciences

Dipl. Ing. Robert Eberhardt

1. Assessor: O.Univ.-Prof. Dipl.-Ing. Dr. techn. Hc Michael Muhr

Institute of High Voltage Engineering and System Management

Graz in September 2011

the dissertation, thank.

learning, in particular Bettina Wieser for their patience with me.

Graz, in September 2011

Dissertation Robert EBERHARDT iii

Graz, 07.09.2011 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,

September 7th, 2011 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,

Dissertation Robert EBERHARDT iv

This thesis deals with a comparative study of

in connection with cellulose in inhomogeneous fields,

either at low temperatures as well as

temperature to AC breakdown with ramp-shaped voltage.

esters, transformer, high voltage;

Dissertation Robert EBERHARDT v

at low Temperatures and room temperature.

to a typical transformer operating temperature (test temperature +60 ° C).

Transformer oil, Transformerboard, pressboard, ester synthetic, natural ester

transformer, high voltage, gas in oil, DGA, dissolved gas analysis;

Dissertation Robert EBERHARDT vi

1 Introduction ................................................. .................................................. ........ 1

1.1 Problems for an insulation system at low temperatures ........... 7

1.2 Objectives and organization of this work ............................................ ....... 8th

2 Properties of insulating and pressboard ............................. 10

2.1 General Temperature and gas formation mechanisms of liquids ............................................

2.1.1 Temperature behavior ................................................. .......................... 10

2.1.2 Gas formation ................................................. ......................................... 13

2.2 Petroleum ................................................. .................................................. .. 15

2.2.1 Composition and manufacture ............................................... ..... 16

2.2.2 Temperature and gas production behavior of oil ........................ 19

2.3 Synthetic esters ................................................ ..................................... 21

2.3.1 Composition and manufacture ............................................... ..... 23

2.3.2 Temperature and gas formation behavior of synthetic esters ..... 24

2.4 Natural esters ................................................ .......................................... 26

2.4.1 Composition and manufacture of soybean oil .................................. 27

2.4.2 Temperature and gas formation behavior of natural esters ......... 30

2.5 Cellulose ................................................. .................................................. .. 31

2.5.1 Production and structure of cellulose for transformers ................ 33

2.5.2 Gas formation behavior of cellulose ............................................... .... 35

2.6 The oil - cellulose - insulation ............................................ ................... 35

2.7 More gas production operations ................................................ ................... 36

2.8 Dielectric behavior ................................................. ................................ 36

2.8.1 Dielectric behavior of liquids ............................................. 36

2.8.2 Dielectric behavior of impregnated cellulose ............................. 42

2.9 Behavior of the fluids at low temperatures ................................. 44

3 Task ................................................. ........................................... 46

Dissertation Robert EBERHARDT vii

3.2 Experimental design and considerations for cooling ............................. 48

3.3 Selection of fluids ............................................... ........................... 50

3.4 Experimental Design ................................................. ....................................... 51

3.5 Procedure ................................................. .................................................. ...... 51

3.6 Evaluation ................................................. ............................................... 53

4 Studies of alternative liquids at low temperatures .. 54

4.1 Experimental setup ................................................. ........................................ 54

4.2 Dielectric studies of the cooled oil-cellulose insulation 55

4.3 DGA - Dissolved Gas Analysis - gas-in-oil analysis ................................. 57

4.3.1 The sampling ................................................ .......................... 58

4.3.3 The gas analysis by gas chromatograph ........................................ 60

5.2.2 Gas formation in the experiments in absolute values (ppm) ..................... 84