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Evaluation of the Dielectric Capability of Ester Based Oils for Power

Transformers
Thesis · June 2008

DOI: 10.13140/RG.2.1.2709.6085
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EVALUATION OF THE DIELECTRIC CAPABILITY OF ESTER
BASED OILS FOR POWER TRANSFORMERS
A thesis submitted to The University of Manchester for the degree of

PhD
in the Faculty of Engineering and Physical Sciences
2007
DANIEL MARTIN
School of Electrical and Electronic Engineering

2
Contents
Chapter 1: Introduction ................................................................................................... 22
1.1 Background to the Use of Oil as a Transformer Dielectric .................................. 22
1.2 Overview and Aims of this Thesis ....................................................................... 26
1.3 Overview of Chapters ........................................................................................... 27
Chapter 2: Literature review ........................................................................................... 31
2.1 Introduction .......................................................................................................... 31
2.2 The use of mineral oil in transformer insulation .................................................. 31
2.3 Introduction to the Oils Used in this Investigation............................................... 33
2.3.1 Nytro 10GBN................................................................................................ 33
2.3.2 Envirotemp FR3 ........................................................................................... 34
2.3.3 Midel 7131 .................................................................................................... 35
2.4 Mechanism of the Dielectric Failure of an Oil ..................................................... 36
2.4.1 Introduction to the Dielectric Failure of Oil ................................................. 36
2.4.2 Introduction to the Bubble Theory of Breakdown ........................................ 37
2.4.3 Particle Initiated Breakdown ........................................................................ 39
2.5 Differences Between Failure Caused by Lightning Impulse and AC Power
Frequency ................................................................................................................... 42
2.5.1 Effect of Polarity on the Lightning Impulse Breakdown Voltage of Oil ..... 42
2.5.2 Effect of Particles on the Lightning Impulse Breakdown Voltage of Oil .... 43
2.5.3 Effect of the Molecular Structure on the Lightning Impulse Breakdown
Voltage of Oil ........................................................................................................ 43
2.6 Summary and Areas Identified for Investigation ................................................. 44
Chapter 3: Methods Used to Measure the Properties of the Oils .................................... 46
3.1 Introduction .......................................................................................................... 46
3.2 AC Dielectric Strength ......................................................................................... 46
3.3 Dielectric Dissipation Factor, Relative Permittivity and DC Resistivity ............. 51
3.4 Water Content....................................................................................................... 55
3.5 Acidity .................................................................................................................. 58
3.6 Lightning Impulse Dielectric Strength ................................................................. 59
3.7 Conclusion ............................................................................................................ 61
Chapter 4: Comparison of the Breakdown Voltages of New Oil.................................... 63
4.1 Introduction .......................................................................................................... 63
4.2 The Statistical Nature of AC and Lightning Impulse Breakdown Voltage .......... 63
4.3 Investigation to Compare the AC Breakdown Voltages of the Oils .................... 64
3
4.3.1 Introduction to the Investigation................................................................... 64
4.3.2 Experiment.................................................................................................... 64
4.3.3 Results for AC Breakdown Test ................................................................... 65
4.3.4 Parameters of the Breakdown Voltage Distributions ................................... 67
4.3.5 Effect of Sample Size on the Accuracy of the Mean Breakdown Voltage... 69
4.3.6 Histograms of the Breakdown Voltages ....................................................... 73
4.3.7 The Use of the Gaussian Distribution to Model Breakdown Voltages ........ 76
4.3.8 Shapiro Wilk Test for Normality .................................................................. 77
4.3.9 Normal Probability Plots .............................................................................. 79
4.3.10 Introduction to the Weibull Distribution .................................................... 81
4.3.11 Adherence to the Weibull Distribution....................................................... 82
4.3.12 Analysis using a Non Parametric Test ........................................................ 85
4.3.13 Investigating the Withstand Voltages of the Oils ....................................... 86
4.4 Investigation to Compare the Lightning Impulse Breakdown Voltages of the Oils87
4.4.1 Introduction .................................................................................................. 87
4.4.2 Discussion of the Results .............................................................................. 88
4.4.3 Probability of Failure at the Breakdown Voltage of an Oil .......................... 90
4.5 Conclusions .......................................................................................................... 91
Chapter 5: Effect of Water on the Breakdown Voltages of New Oil ............................. 93
5.1 Introduction .......................................................................................................... 93
5.2 The Water Uptake Mechanisms of Oil ................................................................. 93
5.2.1 The Process of Dissolution ........................................................................... 93
5.2.2 The Process of Water Uptake by Oil ............................................................ 95
5.3 The Effect of Water on the Dielectric Strength of Oil ......................................... 96
5.3.1 Effect of Water Globules on the Dielectric Strength of Oil ......................... 96
5.3.2 Effect of Dissolved Water on the Dielectric Strength of Oil ........................ 97
5.3.3 Effect on AC Dielectric Strength.................................................................. 97
5.3.4 Effect on Lightning Impulse Dielectric Strength ....................................... 101
5.4 The Preparation of the Wet Samples of Oil Used in this Investigation ............. 102
5.5 Particle Count of Oil .......................................................................................... 105
5.6 Comparison of the Effect of Water on the Mean AC Breakdown Voltages ...... 106
5.7 Comparison of the Effect of Water on the Distribution of AC Breakdown
Voltages .................................................................................................................... 109
5.8 Comparison of the Effect of Water on Lightning Impulse Breakdown Voltages114
5.9 Conclusions ........................................................................................................ 118
4
Chapter 6: Effect of Temperature on the Breakdown Voltages of New Oil ................. 120
6.1 Introduction ........................................................................................................ 120
6.2 Background to the Effect of Temperature on the Dielectric Strength of Oil ..... 120
6.3 Investigation to Compare the Effect of Temperature on the Dielectric Strength of
Oil ............................................................................................................................. 124
6.4 Effect of Temperature on the AC Dielectric Strength of Dry Oil ...................... 125
6.5 Effect of Temperature on the AC Dielectric Strengths of Wet Oil .................... 131
6.6 Effect of Temperature, Applied for One Week, on the AC Dielectric Strengths of
Wet Oil ..................................................................................................................... 137
6.7 Conclusions ........................................................................................................ 146
Chapter 7: Effect of Ageing on the Breakdown Voltages of Oil .................................. 148
7.1 Introduction ........................................................................................................ 148
7.2 Oil Degradation Mechanisms ............................................................................. 148
7.2.1 Oxidation .................................................................................................... 149
7.2.2 Hydrolysis ................................................................................................... 150
7.3 Background to the Accelerated Ageing Schemes Commonly Used to Investigate
the Stability of an Oil ............................................................................................... 150
7.4 Previous Research Investigating the Accelerated Ageing of Esters................... 152
7.5 Accelerated Ageing Investigation ...................................................................... 153
7.6 Analysis of Chemical Transformation ............................................................... 155
7.6.1 Acidity ........................................................................................................ 155
7.6.2 Dielectric Dissipation Factor ...................................................................... 156
7.6.3 Relative Permittivity ................................................................................... 158
7.6.4 Oil Ageing Leading to Sludge .................................................................... 159
7.7 Comparison of the Effect of Ageing on the Dielectric Strength of Oil .............. 161
7.7.1 Comparison of the Effect of Ageing on the Mean AC Breakdown Voltages162
7.7.2 Comparison of the Effect of Ageing on the Distributions of AC Breakdown
Voltages ............................................................................................................... 164
7.7.3 Comparison of the Effect of Ageing on the Lightning Impulse Dielectric
Strength of Oil ..................................................................................................... 167
7.8 Conclusions ........................................................................................................ 170
Chapter 8: Effect of Large Oil Gaps on the Dielectric Strength of Oil......................... 172
8.1 Introduction ........................................................................................................ 172
8.2 Development of Large Electrode Gap Cell ........................................................ 174
8.2.1 Insulation Design ........................................................................................ 175
5
8.2.2 Development of the Electrodes................................................................... 176
8.2.3 Schematic of Circuit ................................................................................... 176
8.2.4 Other Items Used in the Test ...................................................................... 177
8.2.5 Capability of System .................................................................................. 178
8.3 Comparison of the AC Breakdown Voltages of the Oils Using Electrode Gaps of
5mm and 10mm ........................................................................................................ 178
8.3.1 Introduction ................................................................................................ 178
8.3.2 Results of the Small Sample of Breakdown Voltages ................................ 179
8.3.3 Investigation of the AC Dielectric Strengths of the Oils Using a Larger
Sample Size ......................................................................................................... 183
8.4 Influence of Large Electrode Gap on the Mean Dielectric Strength of the Oils 187
8.5 Withstand Voltage of a 20mm Electrode Gap ................................................... 189
8.6 Conclusions ........................................................................................................ 190
Chapter 9: Summary, Conclusions and Further Work .................................................. 192
9.1 Summary of the Work Presented in this Thesis ................................................. 192
9.2 Conclusions, Implications and Future Work ...................................................... 192
9.2.1 AC Breakdown Voltages of Oils Using 1mm and 2mm Electrode Gaps ... 192
9.2.2 AC Breakdown Voltages of Oils Using an Electrode Gap of 5mm ........... 195
9.2.3 Lightning Impulse Breakdown Voltages of Oils Using an Electrode Gap of
3.8mm .................................................................................................................. 196
9.3 Final Conclusions ............................................................................................... 197
9.4 Future Work ....................................................................................................... 197
Appendix A: Tabulated Data of the Breakdown Voltages of New Oil ........................ 199
Appendix B: Tabulated data of the Effect of Water on the Breakdown Voltage of Oil201
Appendix C: Tabulated Data of the Effect of Temperature on the Breakdown Voltage of
Oil.................................................................................................................................. 204
Appendix D: Tabulated Data of the Effect of Ageing on the Breakdown Voltage of Oil209
Appendix E: Tabulated Data of the Breakdown Voltages of Oil Using Electrode Gaps of
5mm and 10mm ............................................................................................................ 212
References ..................................................................................................................... 214
Word count: 54,000
6
Index of tables
Table 1: Physical and thermal properties of the oils investigated in this thesis.............. 24
Table 2: Quantity of oil used to insulate a transformer per kVA rating of transformer
[20] .................................................................................................................................. 32
Table 3: Aromatic content of mineral oil and influence on gassing tendency and
lightning impulse dielectric strength [47] ....................................................................... 43
Table 4: Breakdown voltages of the oils used in this investigation reported by the
manufacturer ................................................................................................................... 47
Table 5: Comparison of ASTM D1816 and IEC 60156 breakdown tests ...................... 47
Table 6: Dielectric dissipation factors of the oils used in this investigation reported by
the manufacturer.............................................................................................................. 53
Table 7: Relative permittivities and volume resistivities of the oils as measured in this
investigation according to IEC 60247 ............................................................................. 54
Table 8: Water solubilities of the oils used in this investigation at ambient temperature
reported by the manufacturer .......................................................................................... 56
Table 9: Acidity levels of the oils used in this investigation, when new, reported by the
manufacturer ................................................................................................................... 59
Table 10: Water content of oils and their relative humidities at room temperature ....... 67
Table 11: The mean, standard deviation, kurtosis and skewness of the sample
populations obtained during the investigation ................................................................ 69
Table 12: Values of re-tested Midel 7131 using 1mm electrode gap ............................. 75
Table 13: Summary of performing the Shapiro Wilk test for normality on the AC
breakdown voltages at 5% significance level ................................................................. 78
Table 14: Breakdown voltage of the oils at 1% probability of failure as modelled by the
Gaussian distribution....................................................................................................... 81
Weibull distribution ........................................................................................................ 85
Table 16: Comparing the withstand voltages of the oils given by non-parametric and
parametric methods ......................................................................................................... 86
Table 17: Breakdown voltage of the oils at 1% probability of failure ............................ 87
Table 18: Mean breakdown voltage, standard deviation and water content of the oils
during the lightning impulse tests ................................................................................... 88
Table 19: Rate of failure at the voltage which causes breakdown .................................. 91
Table 20: Comparison of the water solubility of the oils used in this investigation ....... 94
Table 21: Coefficients of variation for the distributions of AC breakdown voltage,
7
performed using 1mm electrode gap, with varying levels of water .............................. 110
Table 22: Coefficients of variation of the lightning impulse dielectric strengths of oil
with varying levels of water .......................................................................................... 115
Table 23: Viscosity and density of oil as a function of temperature............................. 125
Table 24: Water contents of dry oils used in this investigation .................................... 126
Table 25: Comparing the mean breakdown voltages of the dry oil to the expected mean
breakdown voltage of the oil, using 1mm electrode gap, at room temperature ............ 130
Table 26: Lowest and highest breakdown voltage of the oils, using 1mm electrode gap
....................................................................................................................................... 131
Table 27: Coefficients for calculating water solubilities of oils ................................... 132
Table 28: Water content of samples along with their relative humidity ....................... 134
Table 29: Lowest and highest breakdown voltage of the oils ....................................... 136
Table 30: Breakdown voltage of wet mineral oil, using 1mm electrode gap, maintained
at 70°C for one week ..................................................................................................... 139
Table 31: Water content and breakdown voltages, using 1mm electrode gap, of esters
before heating for one week .......................................................................................... 141
Table 32: Temperature and water content of oils after heating for one week .............. 142
Table 33: Mean breakdown voltage, using 1mm electrode gap, of the esters after heating
for one week .................................................................................................................. 143
Table 34: Mean breakdown voltage, using 1mm electrode gap, of Midel 7131 left to
cool for three weeks after heating ................................................................................. 145
Table 35: Water content of oils after ageing ................................................................. 162
Table 36: Mean lightning impulse breakdown voltages of the oils before and after
ageing for 28 days ......................................................................................................... 168
Table 37: Water content of the oils used in the large electrode gap investigation ....... 180
Table 38: Mean AC breakdown voltages of the oils ..................................................... 182
Table 39: Lowest AC breakdown voltage of the oils.................................................... 182
Table 40: Water content of oils before and after investigation ..................................... 184
Table 41: Mean and lowest breakdown voltages of the oils using a 5mm electrode gap
....................................................................................................................................... 186
Table 42: Comparison of the mean dielectric strengths of the oils and effect of electrode
gap ................................................................................................................................. 188
Table 43: AC Breakdown voltages of new oil .............................................................. 199
Table 44: Breakdown voltages for repeat of Midel 7131 ............................................. 200
Table 45: Lightning impulse breakdown voltages of new oil ....................................... 200
8
Table 46: AC Breakdown voltages of mineral oil as a function of water content ........ 201
Table 47: AC Breakdown voltages of FR3 as a function of water content................... 201
Table 48: AC Breakdown voltages of Midel 7131 as a function of water content ....... 202
Table 49: Lightning Impulse Breakdown voltages of mineral oil as a function of water
content ........................................................................................................................... 202
Table 50: Lightning Impulse Breakdown voltages of FR3 as a function of water content
....................................................................................................................................... 202
Table 51: Lightning Impulse Breakdown voltages of Midel 7131 as a function of water
content ........................................................................................................................... 203
Table 52: AC Breakdown voltages of dry oil as a function of temperature ................. 204
Table 53: AC Breakdown voltages of wet oil as a function of temperature ................. 205
Table 54: AC Breakdown voltages of mineral oil as a function of ageing duration and
catalyst........................................................................................................................... 209
Table 55: AC Breakdown voltages of FR3 as a function of ageing duration and catalyst
....................................................................................................................................... 209
Table 56: AC Breakdown voltages of Midel 7131 as a function of ageing duration and
catalyst........................................................................................................................... 210
Table 57: Lightning impulse breakdown voltages of the oils as a function of ageing
duration and catalyst ..................................................................................................... 211
Table 58: AC breakdown voltages of the oils using an electrode gap of 5mm and 10mm
....................................................................................................................................... 212
Table 59: AC breakdown voltages of the oils using an electrode gap of 5mm ............ 212
9
Index of figures
Figure 1: Sharing of the electric field across a composite insulator ............................... 25

Figure 2: Progression of the transmission voltages and power ratings of electricity
networks since the 1880s [14]......................................................................................... 31
Figure 3: Basic hydrocarbon structures in mineral oil [25] ............................................ 33
Figure 4: Example structure of a molecule which may be expected in mineral oil [25] 34
Figure 5: The generic molecular structure of Envirotemp FR3 [26] .............................. 35
Figure 6: The generic molecular structure of Midel 7131 showing the central carbon
atom and four ester linkages [26] .................................................................................... 36
Figure 7: Coefficient of variation for 459 single breakdown tests according to IEC
60156 [50] ....................................................................................................................... 49
Figure 8: The DPA75 Fully Automatic Insulating Oil Tester ........................................ 49
Figure 9: Block diagram of the DPA100 showing the internal components of the unit
[52] .................................................................................................................................. 50
Figure 10: Example of a cell for measurements on liquids proposed by IEC 60247 [53]
......................................................................................................................................... 52
Figure 11: The ADTR-2K test set and oil heater manufactured by Eltel Industries ....... 55
Figure 12: The XB120 balance, 684 Coulometer and 832 Thermoprep oven used to
measure the water content of oil ..................................................................................... 57
Figure 13: Vials which are used by the Coulometer to measure the water content of an
oil .................................................................................................................................... 57
Figure 14: Lightning impulse generator manufactured by Haefely Test AG which was
used to measure the lightning impulse breakdown voltages of oil ................................. 60
Figure 15: Distribution of mineral oil AC breakdown voltages ..................................... 65
Figure 16: Distribution of FR3 AC breakdown voltages ................................................ 66
Figure 17: Distribution of Midel 7131 AC breakdown voltages .................................... 66
Figure 18: Effect of sample size on the 95% confidence limits of the mean breakdown
voltage of mineral oil ...................................................................................................... 70
voltage of FR3 ................................................................................................................. 71
voltage of Midel 7131 ..................................................................................................... 71
Figure 21: Percentage error of the 95% confidence intervals of the mean breakdown
voltages ........................................................................................................................... 72
10
Figure 22: Histogram for the AC breakdown voltages of mineral oil ............................ 73
Figure 23: Histogram for the AC breakdown voltages of FR3 ....................................... 74
Figure 24: Histogram for the AC breakdown voltages of Midel 7131 ........................... 74
Figure 25: Breakdown voltage distribution of re-tested Midel 7131 .............................. 75
Figure 26: Normal probability plot for the AC breakdown voltages of mineral oil ....... 80
Figure 27: Normal probability plot for the AC breakdown voltages of FR3 .................. 80
Figure 28: Normal probability plot for the AC breakdown voltages of Midel 7131 ...... 81
Figure 29: Weibull probability plot for the AC breakdown voltages of mineral oil....... 83
Figure 30: Weibull probability plot for the AC breakdown voltages of FR3 ................. 84
Figure 31: Weibull probability plot for the AC breakdown voltages of Midel 7131 ..... 84
Figure 32: Distribution of oil lightning impulse breakdown voltages ............................ 89
Figure 33: Rate of water uptake of mineral oil as functions of air relative humidity and
temperature [87] .............................................................................................................. 96
Figure 34: Effect of water on the AC breakdown voltages of FR3 [86] ......................... 98
Figure 35: Effect of water on the AC breakdown voltages of mineral oil and a synthetic
ester [87].......................................................................................................................... 99
Figure 36: Influence of water on the breakdown voltage of mineral oil [89] ............... 100
Figure 37: Dependence of the relative humidity of air on the proportion of Glycerol in
solution in a sealed container [87] ................................................................................ 104
Figure 38: Desiccator and Petri dishes used to control the water content of oil ........... 104
Figure 39: Cumulative number of particles per 100ml of oil........................................ 105
Figure 40: AC breakdown voltages of the esters as functions of water content (ppm) 106
Figure 41: AC breakdown voltages of mineral oil as functions of water content (ppm)
....................................................................................................................................... 107
Figure 42: AC breakdown voltages of oils as functions of relative humidity .............. 108
60156 [50] ..................................................................................................................... 109
Figure 44: Distributions of AC breakdown voltages for mineral oil as functions of water
content ........................................................................................................................... 112
Figure 45: Distributions of breakdown voltages for FR3 as functions of water content
....................................................................................................................................... 113
Figure 46: Distributions of breakdown voltages for Midel 7131 as functions of water
content ........................................................................................................................... 114
Figure 47: Effect of water on the distribution of lightning impulse breakdown voltages
for mineral oil ................................................................................................................ 116
11
for FR3 .......................................................................................................................... 117
for Midel 7131 .............................................................................................................. 117
Figure 50: Effect of temperature on the breakdown voltages of an insulating oil with
different water contents [96] ......................................................................................... 121
Figure 51: Effect of temperature and flow rate on the dielectric strength of mineral oil
[98] ................................................................................................................................ 122
Figure 52: Effect of temperature on oil viscosity [98] .................................................. 123
Figure 53: Breakdown voltages of Proeco as a function of temperature [99] .............. 124
Figure 54: Baur DPA 75 test cell used in this investigation ......................................... 126
Figure 55: ETI TN1 Infra-red thermometer used to measure the temperatures of the oils
in this investigation ....................................................................................................... 127
Figure 56: Distribution of breakdown voltages for dry mineral oil as a function of
temperature.................................................................................................................... 128
Figure 57: Distribution of breakdown voltages for dry FR3 as a function of temperature
....................................................................................................................................... 128
Figure 58: Distribution of breakdown voltages for dry Midel 7131 as a function of
temperature.................................................................................................................... 129
Figure 59: AC breakdown voltages of the esters as functions of water content (ppm) 130
....................................................................................................................................... 131
Figure 61: Theoretical water solubilities for various oils as a function of temperature 132
Figure 62: Distribution of breakdown voltages for wet mineral oil as a function of
temperature.................................................................................................................... 134
Figure 63: Distribution of breakdown voltages for wet FR3 as a function of temperature
....................................................................................................................................... 135
Figure 64: Distribution of breakdown voltages of wet Midel 7131 as a function of
temperature.................................................................................................................... 135
Figure 65: AC breakdown voltages of oils as functions of relative humidity .............. 136
Figure 66: Breakdown voltages of mineral oil heated to 70°C for one week ............... 139
Figure 67: Breakdown voltages of esters at room temperature prior to heating ........... 140
Figure 68: Breakdown voltages of FR3 at room temperature prior to heating and after
heating at 70°C for one week ........................................................................................ 141
Figure 69: Breakdown voltages of Midel 7131 at room temperature prior to heating and
12
after heating at 70°C for one week ................................................................................ 142
after heating at 70°C for one week ................................................................................ 144
Figure 71: Oxidation of mineral oil [104] ..................................................................... 149
Figure 72: Change in the acidities of the oils after thermal ageing without using a
copper catalyst ............................................................................................................... 156
Figure 73: Change in the acidities of the oils after thermal ageing using a copper
catalyst........................................................................................................................... 156
Figure 74: Change in the dielectric dissipation factors of the oils during thermal ageing
....................................................................................................................................... 158
Figure 75: Change in the relative permittivities of the oils during thermal ageing ...... 159
Figure 76: Appearance of new oils, showing mineral oil, Midel 7131 and FR3 .......... 160
Figure 77: Appearance of mineral oil aged for 28 days without copper (left) and with
copper (right)................................................................................................................. 160
Figure 78: Appearance of FR3 aged for 28 days without copper (left) and with copper
(right)............................................................................................................................. 160
Figure 79: Appearance of Midel 7131 aged without copper (left) and with copper (right)
....................................................................................................................................... 161
Figure 80: Mean AC breakdown voltages of the oils after ageing with various catalysts
....................................................................................................................................... 163
Figure 81: Effect of ageing on the distribution of AC breakdown voltages of mineral oil
....................................................................................................................................... 164
Figure 82: Effect of ageing on the distribution of AC breakdown voltages of FR3 ..... 166
Figure 83: Effect of ageing on the distribution of AC breakdown voltages of Midel 7131
....................................................................................................................................... 167
Figure 84: Effect of ageing on the distribution of lightning impulse breakdown voltages
of mineral oil ................................................................................................................. 168
Figure 85: Effect of ageing on the distribution of lightning breakdown voltages of FR3
....................................................................................................................................... 169
of Midel 7131 ................................................................................................................ 170
Figure 87: Effect of particles on the dielectric strength of oil [126]............................. 173
Figure 88: Test cell used in this investigation for large electrode gap experiments ..... 174
Figure 89: Finite element analysis showing the distribution of the electric field around
the test cell..................................................................................................................... 176
13
Figure 90: Schematic of test circuit used to provide up to 300kV to the test cell ........ 177
Figure 91: Laboratory setup showing the AC resonance test set, water resistor and test
cell ................................................................................................................................. 178
Figure 92: Distribution of AC breakdown voltages using an electrode gap of 5mm ... 180
Figure 93: Distribution of AC breakdown voltages using an electrode gap of 10mm . 181
Figure 94: Probability of breakdown with changing voltage using 5mm and 10mm
electrode gaps ................................................................................................................ 181
Figure 95: Breakdown voltages of oils using an electrode gap of 5mm and a sample size
of 30 measurements ...................................................................................................... 185
Figure 96: Cumulative distribution function of the data obtained from the 30
measurement sample size .............................................................................................. 185
Figure 97: Grouping of breakdowns around certain voltages ....................................... 186
Figure 98: Effect of electrode gap on the dielectric strength of oil .............................. 189
14
Abstract
Mineral oil has been used as the liquid insulation of large power transformers for the
past hundred years. A disadvantage to its use is that it can pollute the environment if
spilt. As a result, there has been interest by the Utilities in using ester based transformer
fluids, which are biodegradable and non-toxic. These are of two types, natural vegetable
oils and synthetically produced oils which have similar characteristics. Ideally these oils
should be capable of operating in existing transformers designed to use mineral oil.
In order to use an ester oil in a large power transformer with confidence, the oil’s
dielectric strength must be thoroughly investigated. The dielectric strength of the
vegetable oil should be at least equal to that of the mineral oil to allow straight
replacement. If the dielectric strength of ester oil is less than that of the mineral oil, it
will be for the transformer manufacturer to determine whether modifications to the
design are required. Oil manufacturers publish the mean dielectric strength of their
product; however, this is simplistic because the mean does not indicate the lowest
voltage at which the oil will fail. Furthermore there is no indication of how the working
conditions of the oil inside the transformer affect its dielectric strength.
The breakdown of an oil is caused by some weak link, for instance particles. It is
therefore necessary to understand how the conditions representative of a transformer,
such as water and temperature, affect the impact of these weak links on the dielectric
strength of the oil.
The work presented in this thesis studies the AC and lightning breakdown voltages of
two esters, one natural & one synthetic, under a variety of conditions and compares to
those of mineral oil. The AC breakdown voltages of these oils when new are presented
using electrode gaps of 1mm, 5mm and 10mm. A detailed comparison of their dielectric
strengths is made based on a sample of one hundred AC breakdown voltages for an
electrode gap of 1mm. The effects of water, temperature and oxidation on the
breakdown voltages of the oil are then analysed.
In general this project has found that the AC breakdown voltages, using 1mm electrode
gap, of esters are higher than those of the mineral oil. However, the lightning impulse
breakdown voltages of esters are between 10% and 20% lower. Further work is required
to analyse the dielectric strengths of esters at electrode gaps larger than 1mm.
It is concluded that esters could be suitable replacements for mineral oil in large power
transformers, but further research is required to arrive at a definite conclusion.
15
Declaration
No portion of the work referred to in this thesis has been submitted in support of an
application for another degree or qualification of this or any other university or other
institute of learning
16
Copyright Statement
1. Copyright in the text of this thesis rests with the author. Copies (by any process)
either in full, or of extracts, may be made only in accordance with instructions given
by the author and lodged in the John Rylands University Library of Manchester.
Details may be obtained from the Librarian. This page must form part of any such
copies made. Further copies (by any process) of copies made in accordance with
such instructions may not be made without the permission (in writing) of the author.
2. The ownership of any intellectual property rights which may be described in this
thesis is vested in The University of Manchester, subject to any prior agreement to
the contrary, and may not be available for use by third parties without the written
permission of the University, which will prescribe the terms and conditions of any
such agreement.
3. Further information on the conditions under which disclosures and exploitation may
take place is available from the Head of School of Electrical and Electronic
Engineering.
17
List of publications
Published:
[1] D. Martin, Z. D. Wang, P. Dyer, A. W. Darwin & I. R. James, “A comparative Study of the
Dielectric Strength of Ester Impregnated Cellulose for Use in Large Power Transformers”, 9th
IEEE International Conference on Solid Dielectrics, pp. 294 - 297 , UK, 2007.
[2] D. Martin, I. Khan, J. Dai & Z. D. Wang, “An Overview of the Suitability of Vegetable Oil
Dielectrics for use in Large Power Transformers”, invited paper and seminar presented at the
Euro TechCon, UK, 2006 and TechCon, USA, 2007, both hosted by TJH2b Analytical Services.
[3] D. Martin, Z. D. Wang, A. W. Darwin & I. James, “A Comparative Study of the Chemical
Stability of Esters for Use in Large Power Transformers”, IEEE Annual Report Conference on
Electrical Insulation and Dielectric Phenomena, pp. 493 – 496, USA, 2006.
[4] D. Martin & Z. D. Wang, “A Comparative Study of the Impact of Moisture on the Dielectric
Capability of Esters for Large Power Transformers”, IEEE Annual Report Conference on
[5] D. Martin, Z. D. Wang & I. Cotton, “The Use of Natural and Synthetic Ester-Based Transformer
Oils in Power Transformers”, XIVth International Symposium on High Voltage Engineering,
Paper C-11, China, 2005.
Accepted:
[6] D. Martin & Z. D. Wang, “Statistical Analysis of the ac Breakdown Voltages of Ester Based
Transformer Oils”, awaiting publication by the IEEE Transactions on Dielectrics and Electrical
Insulation.
18
Acknowledgements
Firstly I would like to thank my supervisor, Dr Zhongdong Wang, for her support and
hard work to ensure that this project has been a success. I would also like to take this
opportunity to thank the other members of the School of Electrical and Electronic
Engineering at the University of Manchester. In particular Imadullah Khan and Jie Dai,
who are also investigating the use of vegetable oils, for their contribution of technical
knowledge.
I would like to express my gratitude to Katharine Warrender for all of her time helping
to proofread this thesis.
Many thanks to the sponsors for their advice and technical support. In particular, Alan
Darwin and Ian James of AREVA T & D, Paul Dyer of EDF Energy, Russell Martin
and James O’Neill (formerly) of M & I Materials, Paul Jarman of National Grid, Dave
Walker of Scottish Power, Sue Northcote and the team at TJH2b Analytical Services,
and Tony Byrne of United Utilities.
I also wish to thank the team at Cooper Power Systems for their technical support on
vegetable oils over the years. In particular Helen Athanassatou, John Luksich, Patrick
McShane, Kevin Rapp and Terry Gray (of Langley Engineering).
19
Terminology
The following definitions have been provided to assist the reader, who is assumed to
have an electrical engineering background, in understanding the chemistry discussed in
this thesis.
Aromatic Aromatics are constituents of mineral oil. An aromatic is “a class

of organic hydrocarbon compounds characterized by the presence
of one or more benzene derivatives, i.e. a ring-shaped arrangement
of at least five (usually six) carbon atoms” [1]. The electrons are
delocalised around an aromatic ring.
Carboxylic acid An organic acid which is formed by oxidation of a hydrocarbon.
These are detrimental in power transformers because they increase
the rate of degradation of cellulosic insulation.
Fatty acid An organic compound which is a building block of an ester. Fatty
acid molecules have higher molecular weights than the carboxylic
acids created by oxidation, and are less aggressive.
Gassing tendency The ability of an oil to evolve or absorb gas under electrical stress.
To determine this the oil is firstly saturated with hydrogen gas and
secondly an electrical stress is applied across the oil creating
partial discharge. The gassing tendency is expressed as the volume
of gas absorbed or evolved per minute. A negative gassing
tendency indicates that the oil is absorbing the hydrogen whereas a
positive value indicates that the oil is evolving gas. Whether an oil
evolves or absorbs gas is related to the saturation of its
intermolecular bonds. Unsaturated structures absorb hydrogen
under electrical stress.
Interfacial This is a measure of the polarity of an oil compared to that of
tension water. Oil is non-polar and does not easily dissolve with water.
Therefore in a system consisting of an oil and water mixture there
will be a boundary between the water and the oil. The interfacial
tension is a measure of the force required to break this boundary.
This measurement can be used to detect polar contaminants in the
oil because these will dissolve more readily with the water, and so
there will be a weaker boundary between the oil and water.
20
Macromolecule A very large molecule, this term is used to describe those
containing several hundred to many thousands of atoms [2].
Naphthenic A class of organic hydrocarbon compounds characterized by the
presence of carbon atoms arranged as a ring. The difference
between an aromatic and a naphthenic ring is that the electrons are
not delocalised around the ring.
Natural ester The technical name for a vegetable oil.
Olefin An unsaturated hydrocarbon. Olefins have at least one carbon-
carbon double bond which makes them reactive.
Paraffin A class of organic hydrocarbon compounds characterized by the
presence of carbon atoms arranged as a straight chain.
Pentaerythitol A chemical which is often used to manufacture synthetic esters.
Saturated and A saturated hydrocarbon has only single bonds between the
Unsaturated constituent atoms. In contrast, an unsaturated hydrocarbon has
hydrocarbons double or triple bonds. Unsaturated structures tend to be more
reactive than saturated ones.
Synthetic ester An artificially produced ester, in this case an ester with a chemical
structure similar to that of vegetable oil.
Readily Oils biodegrade at different rates. The term readily biodegradable
biodegradable denotes an oil which quickly biodegrades as per the requirements
of a standard test method such as OECD 301 “Guideline for
Testing of Chemicals” [3]. To be classed as readily biodegradable
by this test, an oil must degrade by at least 60% within 10 days of
exceeding 10% degradation and at least 60% degradation must
occur by day 28 of the test.
21
Chapter 1: Introduction
1.1 Background to the Use of Oil as a Transformer Dielectric

Mineral oil, together with cellulose, has been the insulation of choice for large power
transformers over the past century due to its performance, inexpensiveness and wide
availability. Unfortunately mineral oil is harmful to the environment if spilt and is not
readily biodegradable. In recent years there has been interest in non-toxic and readily
biodegradable transformer oils such as those based on esters.
Using esters as transformer dielectrics is by no means a recent innovation. Natural

esters were among the first oils to be used as dielectrics. A team led by George
Westinghouse used caster and linseed oils as dielectric liquids and insulator
impregnants from the late 1880s. One disadvantage, however, was that esters would
quickly oxidise in the presence of air and subsequently gel. Therefore esters were
replaced by more chemically stable oils, such as mineral oil, which Thompson patented
for use in transformers in 1892 [4].
A transformer fluid based on a synthetic ester oil, Midel 7131, was developed in the
1970s and is currently marketed by M & I Materials [5]. Synthetic esters have similar
characteristics to vegetable oils in that they are both non-toxic and readily
biodegradable. Furthermore synthetic esters are highly resistant to oxidation [6] and
have high fire points. Consequently synthetic esters have tended to be deployed in
applications where safety is paramount, such as on trains and offshore.
In the mid 1990s there was renewed interest in ester oils refined from plant products [7].
These natural esters incorporated various anti-oxidants and could be used as the
insulation of distribution transformers as long as the oil was used in an oxygen free
environment. One of these in particular, FR3, has seen wide use and will be examined
in detail in this thesis.
Recently there has been interest in using ester oils as substitutes for mineral oil in large
power transformers. In 2004 a 238kV transformer was developed by VA TECH EBG
which used a synthetic ester, Midel 7131, as the insulating oil. This transformer was
22
supplied to Vattenfall AG and has been installed in an underground power station near
Lake Malgomaj, Sweden. Vattenfall chose an ester to minimise the risk of
environmental contamination [8].
In 2006 it was reported by Martins [9] that two Brazilian Utilities, CELESC and
ELETRONORTE, were experimenting with power transformers filled with FR3.
CELESC is using FR3 in a 138kV 30MVA transformer and two 138kV 40MVA
substation transformers. ELETRONORTE has revised its specification to use FR3 in all
transformers and reactors rated up to 138 kV and has recently ordered a 242kV shunt
reactor from AREVA T & D.
In the United Kingdom EDF Energy has placed an order with AREVA T & D for two
132kV 90MVA transformers. One of these transformers is filled with the FR3 natural
ester [10].
Even though esters are already being used as the dielectric in the aforementioned power
transformers, comprehensive studies are required to understand the impact of using
esters before these oils are extensively adopted as the dielectric of power transformers
in the United Kingdom.
Oil, along with cellulose, forms the insulation of a power transformer. Oil is used
because the electric fields inside a transformer necessitate the need for a fluid with a
high dielectric strength.
The dielectric strength of an insulating oil (in volts per metre) is dependent on the
distance between conductors and generally decreases as the distance increases, which is
known as the large gap effect. Distances between conductors in a transformer tend to be
either “small”, in the orders up to tens of millimetres, or “large”, in the order of tens of
centimetres. Small gaps are found, for example, between sections of the same winding,
whereas an example of a large gap is that between the lead of the winding and the wall
of the transformer tank, which is earthed.
The thermal and physical properties of an oil, which are shown in table 1, are as
important as its electrical properties. The oil acts as the coolant of a transformer. The
23
temperature of the oil at the top of the transformer tank is usually rated at 60°C plus
ambient although the oil can be cooler, depending on load current. There can be hot
spots around the conductors inside the transformer.
The three factors which determine the usefulness of a liquid as a coolant are its thermal
conductivity, specific heat and viscosity. The viscosity of an oil affects the rating of the
pump required to circulate the oil within the transformer. The oil will increase and
decrease in volume as it changes in temperature, determined by its coefficient of
expansion. If an oil with a different coefficient of expansion is used then it must be
verified that the transformer conservator is capable of operating with this oil.
Table 1: Physical and thermal properties of the oils investigated in this thesis
Nytro 10GBN Envirotemp FR3 Midel 7131

Mineral oil Natural ester Synthetic ester
Density(g/ml) 0.89 0.92 0.97
@ 20°C @ 25°C @ 20°C
-4 -4
Expansion coefficient(°C) 7.5 x 10 7.5 x 10 7.5 x 10-4
Viscosity @ 40°C (cSt) 9 32-33 28
Specific heat (J/kg K) 1860 1880 1880

@ 20°C @ 25°C @ 20°C
Thermal conductivity (W/mK) 0.126 0.167 0.144
@ 20°C @ 25°C @ 20°C
Pour Point (°C) -57 -18 – -21 -60
Flash point (°C) 145 330 275
Fire point (°C) 160 360 322
An insulating oil must remain liquid under ambient temperatures to be an effective

coolant. As a transformer may be cold started in the winter, there must not be a
propensity for the oil to freeze when the transformer is idle. The UK Meteorological
Office reports that the average minimum temperature for the winters between 1971 and
2000, depending on region, was between -5°C and +7°C [11]. However, since this is an
average minimum temperature it does not take into account extreme weather events; the
lowest temperature recorded was -27.2°C in Altnaharra, Scotland, 30th December 1995.
The pour points of mineral oil and Midel 7131 are -57°C and -60°C, far lower than the
24
minimum temperature expected in the UK. The pour point of FR3 is between -18°C and
-21°C. This is lower than the average minimum UK temperature however there is the
possibility of an extreme weather event being able to freeze this oil. Rapp et al, of
Cooper Power Systems, studied the behaviour of ester oils near the pour point [12].
They froze an ester using temperatures of -30°C and -40°C for 120 hours. After this
period the ester was allowed to thaw to room temperature. The dielectric strength of this
sample was measured using standard ASTM D1816 and was not found to have changed.
A large amount of cellulose in the form of paper and pressboard insulation is used to
manufacture a transformer. Cellulose acts as an insulator in regions of high electrical
stress, partitions large oil gaps and provides mechanical support. Cellulose is a
macromolecule, with micro-cell voids and channels within the structure, which is
impregnated by the oil. The ability of an oil to effectively impregnate the cellulose is
related to its viscosity which in turn is a function of temperature. Natural esters have
higher viscosities than mineral oil, therefore, longer time is required for them to
impregnate the cellulose. One solution is to heat up the oil decreasing its viscosity. One
manufacturer has resolved this problem by impregnating the transformer cellulose first
with mineral oil, then draining the mineral oil and retrofilling with the ester.
The electric stress in a composite system is distributed across the components as a

function of the dielectric constants of the materials, shown in figure 1 and equation 1.1
where V is the applied voltage, d is the thickness of the material, ε is the relative
permittivity of the material and E is the electric field across the material.
V
E1 ε1 d1
E2 ε2 d2
E3 ε3 d3
Figure 1: Sharing of the electric field across a composite insulator

= where i = 1, 2, 3 (1.1)

25
It is necessary to ensure that the change in the electric field and resulting localised
increases in electric stress caused by the different relative permittivity of a new oil does
not lead to dielectric failure. Even if complete breakdown of the oil does not occur, the
electric field can ionize local regions of the oil. The ions can bombard cellulose and
over time create conductive tracking on the surface of the cellulose leading to insulation
failure. The dielectric strength of ester impregnated cellulose was investigated in this
project and the results were published [13], however this data is not included in the
scope of this thesis.
Over time chemical changes occurring within the transformer change the nature of the
oil. Not only must the dielectric strength of the oil remain high, but by-products of oil
degradation must not damage the cellulosic insulation. Whereas an oil can be changed
or reprocessed, cellulose cannot easily be replaced. Therefore cellulose is often classed
as the weakest link in transformer insulation.
It is common to monitor the condition of the insulating oil to determine when

maintenance should be carried out on the transformer. Various properties of the oil are
measured, such as: breakdown voltage, dielectric dissipation factor, water content,
acidity and particle count. It is essential to determine whether the limits specified for
mineral oil are applicable for an ester oil. For instance, since esters are more
hygroscopic than mineral oil, the limits for water content of mineral oil are not
applicable for an ester.
1.2 Overview and Aims of this Thesis
In the evaluation of the suitability of new oils for use as the insulation of power
transformers, the dielectric strength of the oil is seen as a key determining factor. The
aim of this thesis is to investigate the AC and lightning impulse dielectric strengths of
esters under a variety of conditions and compare to those of a mineral oil commonly
used in UK large power transformers.
The dielectric strengths of the esters have been reported by the manufacturer as
comparable to that of mineral oil when a standardised test method such as ASTM
D1816 or IEC 60156 is used. Unfortunately this only provides a limited comparison
because the oils are tested when new at ambient temperature. This does not take into
26
account the operating environment of the oil inside the transformer and the effect of
contamination, both of which may reduce the breakdown voltage of the oil.
Over time the water content of the oil increases, this can be due to either leaks or
hydrolytic degradation of cellulose, affecting its dielectric strength. Chemical reactions
can change the properties of an oil, hence it is necessary to investigate the stability of an
oil. A change in temperature may further affect the impact of the contamination.
Also it is common for manufacturers to simply state the mean breakdown voltage of
their oil. This does not indicate the overall dielectric performance of the oil since it is, in
fact, a statistically distributed function.
Test standards ASTM D1816 and IEC 60156 require for the breakdown voltage of an
oil to be found using electrode gaps of 2.5mm or less. Since geometries inside
transformers are larger than this, breakdown voltages measured to these standards do
not reflect the withstand voltage of larger oil gaps.
The following research is presented in this thesis:
i) A comparative study of the AC and lightning impulse dielectric strengths of new

esters and mineral oil
ii) The effects of ageing, water and temperature on the dielectric performance of the oils
iii) The dielectric performance of esters and mineral oil using electrode gaps up to
10mm
1.3 Overview of Chapters

The following is a summary of the chapters presented in this thesis:
Chapter 2: Literature review
The literature review provides an overview of the use of oil in the insulation of a power
transformer and the investigated oils.
27
A review of the processes which lead to dielectric failure of oil insulation is given in
order to assist with the explanation of the results in this thesis. Oil breaks down on some
weak link. Therefore the processes which can lead to causing a weak link must be
identified in order to plan the investigations which have been carried out during this
PhD study.
Chapter 3: Methods Used to Measure the Properties of the Oils
Where possible, measurements have been performed in accordance with an appropriate

industry standard. The advantage of this is that it allows the results obtained during
experimentation to be compared with other research. However, since many of these
standards have been developed to test mineral oil, it must be verified that such standards
are appropriate to test esters. This chapter describes the techniques used to measure the
various characteristics of the oils.
Chapter 4: Comparison of Breakdown Voltages of New Oil
The dielectric failure of an oil is a statistically distributed quantity. Therefore in order to

compare the AC and lightning dielectric strengths of oil the overall distribution of
breakdown voltages should be compared rather than simply comparing means. This
investigation was performed on new oil, as delivered by the manufacturer, which had
been treated to remove water and dissolved gas.
This chapter analyses the distribution of one hundred AC breakdown voltages of the oils
to determine if there is a difference in their dielectric performance. In addition this
chapter discusses the applicability of using the Gaussian and Weibull distributions to
estimate the breakdown voltage at a low probability of failure. A sample of five
lightning impulse breakdowns was measured to analyse the performance of the esters
and compare to that of mineral oil.
Chapter 5: Effect of Water on the Breakdown Voltages of New Oil
When in service oil may be exposed to water. This is detrimental because water is
known to reduce the AC dielectric strength of oil insulation. The influence of water on
28
the lightning impulse dielectric strength of oil has not been extensively studied.
The chapter provides an overview of current knowledge about the effect of water on the
breakdown voltage of oil. It goes on to study the impact of water on the AC and
lightning impulse breakdown voltages of esters compared to those of mineral oil.
Chapter 6: Comparison of the Effect of Temperature on the Breakdown Voltages of

New Oil
Chapters four and five only consider the breakdown voltages of oil at room temperature.
This chapter analyses the effect of temperature on the AC breakdown voltages of oil
using temperatures between 30°C and 70°C, chosen to be representative of the
transformer environment. First the effect of temperature on the dielectric strength of dry
oil was investigated. After this, wet oils were tested to analyse how the temperature and
the hygroscopy of the oil together affect the breakdown voltage.
Chapter 7: Comparison of Effect of Ageing on the Breakdown Voltages of Oil
For a transformer oil to be suitable for long term use, it must be confirmed that the
dielectric strength of the oil is not reduced over time as chemical reactions change the
nature of the oil. Since UK power transformers are mostly free breathing, it is necessary
to investigate the impact of oxidation on the oil. Esters can be further transformed by
hydrolytic reactions caused by exposure to water.
To assess the chemical stability of the oils, they were thermally aged at 115°C for up to
one month. The dielectric strengths of the esters were then compared to those of mineral
oil to determine whether ageing affects their performance.
Chapter 8: Effect of Large Oil Gaps on the Dielectric Strength of Oil
Dielectric failure of an oil is initiated by some weak link. As the volume of electrically
stressed oil increases, the probability that a weak will be present in the oil volume also
rises. Therefore the dielectric strength of a large oil gap, in terms of kV/mm, will
decrease as the distance between the electrodes increases. It is necessary to investigate
whether the reduction in dielectric strength of an ester, as the distance between
29
electrodes increases, is comparable to that of mineral oil.
In this chapter the breakdown voltages of the oils are investigated using 5mm and
10mm gaps. A test cell was designed which could function at the voltages required to
initiate breakdown, the development of this system is also outlined.
Chapter 9: Conclusion and Further Work
This chapter provides the conclusions of this thesis and suggests the further work which
is required to investigate the suitability of the esters as replacements for the mineral oil
currently used in UK power transformers.
30
Chapter 2: Literature review
2.1 Introduction
This chapter provides a brief introduction to the dielectric use of oil which forms part of
the insulation of a power transformer.
transformer The mechanisms behind the dielectric failure of
oil are discussed and an overview of the oils used in this investigation is given.
2.2 The use of mineral oil in transformer insulation
Over the past hundredd years advances in technology have permitted the transmission of
electrical energy at ever higher voltages as shown
s in figure 2 [14
14]. The increases in the
transmission voltage have been a result of the growing demand for electrical energy
[15].
Figure 2: Progression of the transmission voltages and power ratings of electricity

networks since the 1880s [14]
Each
ach increase in power transmission or line voltage has required a reappraisal of the
equipment used on the electricity network, in particular the power transformers used to
step up or down the transmission voltage. Kulkari notes this, writing “the insulation
design is one of the most important aspects of the transformer design” [16].
[
31
Transformers require appropriate insulation materials to ensure quality and reliability.
The insulating materials of choice over the past century have been cellulose and mineral
oil [17]. These have optimum dielectric properties, are inexpensive and are widely
available. The oil is used to impregnate cellulosic insulation, insulate ducts between
windings and insulate large open volumes. Both Tschudi and Sokolov note that the
effectiveness and reliability of the insulation of a transformer is dependent on the
dielectric strength of the oil [18,19].
The quantity of oil used, in litres per kVA of transformer rating, required for insulation
has decreased over the years as shown in table 2 [20]. This has been brought about by
economic pressures and a better understanding of the processes which lead to
transformer insulation failure.
Table 2: Quantity of oil used to insulate a transformer per kVA rating of transformer
[20]
Manufacturing year Litres of insulating oil per

kVA of transformer rating
1915 7.5
1945 2
1960 1.2
1977 0.5
Recent Years 0.4
The dielectric strength of the oil must not only be high when new but must remain high
over the working life of the transformer. Various processes occur during the operation
of the transformer which degrade the dielectric performance of the oil such as those
which increase the water content of the oil, form by-products by chemical
transformation and contaminate the oil with particles.
Naphthenic mineral oil has been the dielectric of choice for many years in the power
industry. This type of oil possesses high dielectric strength, is cheap to refine and is
widely available [21]. However mineral oil must not be spilt, contaminating the
environment. The safety data sheet for Nytro 10GBN, the mineral oil used by this
32
project, states that although this oil is of low toxicity, since it is not readily
biodegradable it can bioaccumulate in animals [22]. Consequently there has been
interest by the Utilities in using readily biodegradable
b and non-toxic
toxic ester oils [23]. It is
essential to study the dielectric strengths of esters when determining whether they are
suitable candidates to replace mineral oil.
2.3 Introduction to the Oils Used in this Investigation

nvestigation
The oils investigated by this project were:
Nytro 10GBN which is an uninhibited mineral oil conforming to BS148

supplied by Nynas
Ny [24]. This oil is commonlyy used in UK power transformers
Envirotemp FR3 which is a vegetable oil based product supplied

s by Cooper
Power Systems
Midel 7131 which is a synthetic ester based oil supplied by M & I Materials
2.3.1 Nytro 10GBN
Nytro 10GBN is an uninhibited naphthenic mineral oil. The basic hydrocarbon

structures in a mineral oil are paraffins,
paraffin , naphthenes, aromates and polyaromates, shown
in figure 3 [25].
Figure 3:: Basic hydrocarbon structures in mineral oil [25]

[
33
A mineral oil is a blend of different hydrocarbons refined from crude oil [21].
[
Consequently it is common to report the structure of a mineral oil as the percentages of
paraffinic, naphthenic and aromatic structures in the oil. An example showing the
th
percentage ratios of each type of component structure of one such hydrocarbon
molecule, found in a typical mineral oil, is given in figure 4.
Figure 4: Example structure of a molecule which may be expected in mineral oil [25]
The transformer industry prefers naphthenic to paraffinic oils as naphthenes have better
low temperature performance and are less likely to form waxes. Some aromatic
a
compounds are present. While aromatics increase the lightning impulse dielectric
strength of mineral oil, they can have poor stability to oxidation causing them to be
precipitated as sludge. Sulphur compounds,
compounds which are left over from refining, are
present in mineral oil. Some of these compounds may be mild anti-oxidants
anti oxidants [21].
[
However,
owever, others can react corrosively with the copper in a transformer,
transformer potentially
leading to insulation failure.. The refining
refi process attempts to remove olefins which are
undesirable because their double bond makes them highly reactive forming
form sludge and
acids.
2.3.2 Envirotemp FR3
FR3 is refined from vegetable oil and has the structure given in figure 5 [26
26]. FR3 is
edible seed based and is a mixture of saturated and unsaturated fatty acids of up to 22
carbon atoms long with 1 to 3 double bonds. The base oil can be refined from a variety
of vegetable oils which include soya, sunflower, rapeseed, cotton seed, olive, safflower,
safflower
26]. Currently FR3 is refined from soya bean.
jojoba, lesquerella and verona [26
34
Figure 5: The generic molecular
m structure of Envirotemp FR3 [26]
The properties of the ester will be affected by its structure. A high degree of bond
saturation will increase the oxidative stability of the ester, however this will increase
inc the
viscosity of the oil. The manufacturer has chosen esters with between 1 and 3
unsaturated bonds to give the desired viscosity and oxidative stability.
Anti-oxidants
oxidants and pour point suppressants are added to improve the performance of the
oil. It is notable that the manufacturer of FR3 advises against using this oil in free
breathing transformers because its oxidative stability is lower than that of mineral oil.
2.3.3 Midel 7131
Midel 7131 was developed in 1979 and is a synthetic ester derived from
fro pentaerythitol.
This oil differs from natural esters as it is a tetraester, four fatty acid chains are present
instead of the three in natural esters
ester (figure 6) [26].
Midel
el 7131 is highly stable to oxidation and is recommended by its manufacturer for
use in free breathing transformers.
35
olecular structure of Midel 7131 showing the central carbon
Figure 6: The generic molecular
atom and four ester linkages
linkage [26]
Neither the manufacturer of FR3 nor that of Midel 7131 believe that corrosive sulphur
exists in their ester. This is advantageous since ester filled transformers will not fail due
to the copper sulphide damaging the cellulose insulation.
2.4 Mechanism of the Dielectric

ielectric Failure of an Oil
2.4.1 Introduction to the Dielectric Failure of Oil
Efforts to understand the mechanisms which lead to breakdown have been continuing
for many decades. Malik writes that particular difficulties have been encountered in
analysing oils since the molecular structure of a liquid is not as simple and regular as
that of a solid or gas [27].
The purity
rity of the liquid has a significant impact on the mechanism of dielectric failure
of an oil.. Adamczewski advises that for investigations concerning
erning breakdown of a
liquid, an oil is classed as of low or high purity [28].. Low purity oils are the ones used
for industrial purposes,, such as transformer insulation, and have a natural conduction of
the order of 10-10 to 10-13 Ω-1cm-1. Investigations concerning the physical
cal nature of
high purity, which have conductions of the order of 10-
breakdown require oils of the highest
18
to 10-19 Ω-1cm-1. It was observed by Adamczewski that the breakdown voltage of low
purity liquids depends on the r.m.s. value of the applied voltage while for high purity
liquids it depends on the peakk value of the applied voltage. Adamczewski
damczewski concludes
that this dependence may suggest that the mechanism of breakdown is thermal for
36
liquids of industrial purity, such as those used in this investigation, and electrical for
those of high purity.
A widely reported theory explaining the thermal mechanism of breakdown is the bubble
theory, detailed below. Contaminants, such as water and particles, and field
enhancements around abrasions on the surface of the electrodes are instrumental in the
formation of bubbles.
2.4.2 Introduction to the Bubble Theory of Breakdown
Studies monitoring current pulses and optical phenomena prior to the dielectric failure
of an oil gap advocate the bubble theory of breakdown [29,30,31,32,33]. The bubble
theory was proposed by Watson and Sharbaugh as the cause of dielectric failure of a
liquid in 1960 [34] and has been extended over the years. The theory describes the
creation of a bubble resulting from a pulse of current at the cathode vaporising the
surrounding oil, resulting in breakdown as described:
i. Local discharge occurs at cathode
ii. Discharge vaporises surrounding oil creating bubble
iii. Electric field ionizes bubble creating streamer
iv. Streamer propagates across electrode gap
v. Streamer bridges electrodes forming arc
Qureshi et al studied the formation of the bubbles, which may lead to break down, in
silicone oil with a viscosity of 0.65cSt [35]. Short rectangular pulses between 40ns and
630ns were applied to a point-plane electrode system immersed in silicone oil. The
point electrode was used as the cathode and had a radius of a few micrometres. Shadow
photography was used to measure the radius of the resulting bubble and the time taken
for the bubble to collapse after reaching its maximum radius.
The maximum radius of the bubbles was found to be tens of micrometers and the time
to collapse within several microseconds. Qureshi proposed that the time taken for a
bubble to collapse could be found using equation 2.1 where is the time to collapse, Rm
is the maximum radius of the particle, ρ is the density of the oil and Pa is the ambient air
37
pressure. If it is assumed that the energy of the cavity is constant throughout its
expansion and collapse then the time taken for the cavity to grow and collapse is
symmetrical.

= 0.915 × (2.1)

As the volume of the bubble increases, the vapour pressure of the bubble decreases and
consequently the dielectric strength of the bubble falls according to Paschen’s law,
which is that the breakdown voltage of a gas, Vb, is a function of the product of
pressure, P, and gap length, d (equation 2.2).
= ("#) (2.2)
The electric field ionizes the vapour inside the bubble creating a streamer which is seen
by the external circuitry as a current pulse. Chadband measured this current pulse and
found it to be in the mA region [36].
Despite the observation by Watson and Sharbaugh that bubbles are created at the
cathode, Lundgaard et al write that streamers can be generated at either electrode
although breakdown is usually caused by streamers initiated at the anode because they
penetrate faster and further into the liquid [29].
The propagation of streamers is a complex subject and a generally accepted theory that
can explain all the experimental results has still not been established [37].
The primary shortcoming of the bubble theory is that it does not explain the cause of the
pulse of current which generates the bubble. Chadband writes that this pulse may be
caused by an abrupt application of an excessive voltage, a transient local heating, the
accumulation of a local space charge or the chance arrival of a charged entity which
transiently enhances the local field [38].
Researchers have tended to generate bubbles by using point electrodes to produce a high
level of electric field in a small volume of oil. However, several investigations, detailed
38
in the next section, performed since the 1990s have focused on the influence of particles
on the formation of streamers.
2.4.3 Particle Initiated Breakdown
An extensive study by Miners showed that particles affect the AC dielectric strength of
mineral oil [39]. Miners measured the breakdown voltages of mineral oil, in accordance
with ASTM D1816, doped with varying sizes and concentrations of cellulose, copper
and iron particles. The sizes of the particles were in the order of 10µm and their
concentrations were in the order of 10,000-100,000 per 10ml oil for the cellulose and in
the order of 1,000–10,000 per 10ml oil for the copper and iron.
The first conclusion of this investigation was that copper has a greater effect in reducing
the AC breakdown voltage than iron. Secondly the water content of the oil was an
important factor in the degree of influence of the cellulose on dielectric strength since
the water was found to interact with the cellulose to reduce the breakdown voltage.
The effect of water on the dielectric strength of oil doped with copper and iron was also
studied. However it is difficult to see whether the water and metal particles affected the
breakdown voltage independently or through interaction.
Miners did not offer an explanation for the mechanisms behind the dielectric failure of
oil and how particles and water together affect these mechanisms.
Malik writes that particles experience a force in the presence of an electric field which
is given by equation 2.3 where r is the radius of the particle, εOil is the relative
permittivity of the oil, εparticle is the relative permittivity of the particle and grad E2 is the
gradient, in three dimensional space, of the square of the electric field [27]. The grad
function changes the electric field, which is a scalar quantity, into a vector. Since force
is a vector, it has magnitude and direction, the quantity of the electric field must also be
changed into a vector. Force F is directed towards areas of maximum stress.
& ( 01. )
% = ' ( ) '*+,-./ 2(3# ' (2.3)

1. *+,-./
Thus these particles will align on the high stressed electrode and start forming a bridge.
39
However, Malik notes that particles have been seen to bridge the gap while discharge
occurs in a different region.
The bridge acts as an extension of the electrode and can lead to breakdown. While this
theory explains the reduced breakdown voltage of an oil containing many particles, it
does not explain dielectric failure in oils which do not contain a sufficient number of
particles for them to align and form a bridge.
Chadband [32] proposed the theory that single particles can initiate dielectric failure.
Particles become charged in the presence of an electric field and suddenly discharge on
contact with an electrode. The sudden movement of charge vaporises the surrounding
oil forming a bubble, this bubble being described by Watson as the cause of breakdown.
Furthermore Chadband proposed that non-conductive particles charge to a lesser degree
and more slowly than conductive ones thus creating a smaller discharge.
The importance of water is that it increases the conductivity of hygroscopic insulating

particles which produces a greater discharge. Since copper is more conductive than iron,
Chadband’s theory may explain Miners’ observation that copper particles reduce the
dielectric strength of oil more than iron. At ambient temperature the conductivities of
copper and iron are 63 Sm-1 and 10 Sm-1 [40].
Zinoulis et al estimated the size of a particle which could create the discharge of the
magnitude associated with the onset of negative discharges in point plane systems [41].
The charge acquired by a spherical conducting particle of radius r from a plane
electrode is given by equation 2.4 where ε is the dielectric constant of the fluid. A 10
µm radius conducting particle in a field of 10kV/mm (107 V/m) has a charge calculated
to be 1pC, which is reported to be the charge magnitude associated with the initial
cavity forming pulse in low viscosity liquids [32].
4 = 550( ' 5 (67) (2.4)
Carraz et al studied the effect of single metallic particles on the breakdown of mineral
oil [42]. The dimensions of these particles were between 2mm and 5mm in length and
between 0.2mm and 0.75mm in diameter. These particles were made of tungsten, steel,
copper and aluminium. Carraz videoed the motion of the single particle when AC and
40
impulse voltages were applied. During the AC voltage tests, the particle was seen to
cross the gap.
Breakdown almost always occurred when the particle was in contact with the electrode
of positive polarity at a voltage close to the peak of the AC signal. It could be seen from
the recordings firstly, that a discharge started on the positive side of the particle, then
secondly, a filamentary luminous channel propagated towards the negative electrode.
Carraz hypothesized that during lightning impulses insufficient time is given for the
particles to move to the positive electrode. Carraz postulated that particles in the
vicinity or even in contact with an electrode may cause an enhancement of field at the
tip of the particle which if sufficiently large can initiate a streamer.
Linhjell et al also observed, using shadowgraph imagery, that individual particles can
cause dielectric failure [43].The voltage was supplied to the electrode as an impulse of
1µs front time and a tail time to 50% of 1800µs. Single particles of tungsten, of either
6mm or 12mm diameter, were electrically floating between two plane electrodes of
either 96mm or 150mm separation. The particle was held in the place by using a
polypropylene rod perpendicular to the electrode gap. Polypropylene was chosen as its
permittivity matches that of the oil.
Cameras of type Imacon 790 were used to capture propagating channels prior to
breakdown. Linhjell observed that the discharge begins on the positive side of the
particle and propagates over to the cathode. Linhjell notes that negative discharges
require higher voltages to propagate. When a 12mm particle was located halfway
between a 150mm gap, positive channels required impulses of between 400kV and
500kV to propagate across the gap whereas negative channels required between 500kV
and 600kV.
Linhjell observed that the diameter of the positive channels is smaller that that of the
negative ones, concluding that the energy associated with the positive channel is more
focussed at its tip. Consequently the propagation of a positive channel is more efficient
than that of a negative one.
41
The aforementioned studies have provided evidence that particles can initiate the
processes which cause dielectric failure. Investigations using visible metallic particles
have shown that discharges will occur between the particle and an electrode which leads
to dielectric failure. Zinoulis has theorised that particles with diameters of 10 µm can
also provide the energy to initiate the formation of a bubble although this is yet to be
verified optically [41].
2.5 Differences Between Failure Caused by Lightning Impulse and AC

Power Frequency
The mechanism of dielectric failure of an oil caused by a lightning impulse is different

to failure caused by voltage at AC power frequency. This is due to the different
waveshape. The first difference is that AC is of alternating polarity whereas lightning
impulse is of either positive or negative polarity, there may be a difference in
breakdown voltage depending on polarity. Secondly the durations of the transients are
different. AC is a continuous 50Hz or 60Hz power frequency signal whereas the
lightning impulse signal is defined as an aperiodic 1.2µs/50µs waveform. Consequently
sufficient time may not be available for particles to move into areas of high electrical
stress, or pre-breakdown bubbles to grow adequately large to be ionized by the electric
field, before the electric field diminishes.
2.5.1 Effect of Polarity on the Lightning Impulse Breakdown Voltage of Oil
A positive streamer is usually the cause of dielectric failure when using AC voltage
with symmetrical electrodes. A negative streamer can cause breakdown, however it
requires a stronger electric field to propagate across the gap than a positive one [44].
The geometries of positive and negative streamers are different, negative streamers tend
to be ‘bush like’ whereas positive ones are filamentary.
It is believed by Lesaint and Jung that the filamentary nature of the positive streamer
allows it to propagate across the gap at lower voltages than negative streamers [44].
In the case of a transient of one polarity, such as a lightning impulse, a difference in

breakdown strength can be seen depending on the polarity. Perret observed this
phenomenon when investigating the lightning impulse dielectric strengths of various
42
mineral oils using a point to sphere gap as per ASTM D3300. He noted that the
breakdown voltages using negative polarity impulse were on average 50% higher than
the value using positive impulse [45].
2.5.2 Effect of Particles on the Lightning Impulse Breakdown Voltage of Oil
Lundgaard et al observed that particles do not affect the lightning impulse breakdown
voltage of an oil to the same degree as the AC dielectric strength. They propose this is
because most particles require more time to polarize and discharge to an electrode than
the duration of the lightning impulse [46]. Lundgaard further notes that metallic
particles affect the lightning impulse dielectric strength of oil because these polarize
instantaneously.
2.5.3 Effect of the Molecular Structure on the Lightning Impulse Breakdown

Voltage of Oil
Pahlavanpour and Eklund note that the negative lightning impulse voltage of mineral oil
is related to its gassing tendency, as shown in table 3 [47]. In general mineral oil which
has a high positive gassing tendency has a high negative dielectric strength. This
phenomenon is due to the aromatic content of the oil. As the aromatic content increases
the gassing tendency and negative lightning impulse dielectric strength both decrease.
Table 3: Aromatic content of mineral oil and influence on gassing tendency and
lightning impulse dielectric strength [47]
Aromatic content Impulse breakdown ASTM Gassing tendency

IEC 60590 D3300 needle negative
(%) (kV) (µL/minute)
5 >300 +33
7 282 +26
10 220 +16
10 196 +11
10 148 +4
Devins observed that when polyaromatics are added to the oil, the velocity of the
negative streamers is increased and the streamers subsequently bridge the electrodes at a
lower impulse voltage [48]. The propagation velocity of a streamer is not a determinate
43
factor during AC dielectric failure because the voltage is applied for a longer duration.
Therefore polyaromatics do not affect the AC breakdown voltage to the same degree as
they affect the impulse breakdown voltage. Devins gave two suggestions as to the
properties of the polyaromatics which may cause this: Low ionisation potentials and
large electron trapping cross sections.
The gassing tendencies of FR3 and Midel 7131, performed to standard ASTM D2300,
are -79 µL/min and +29 µL/min respectively. However, since neither ester contains
aromatics the relationship between gassing tendency and negative lightning impulse
dielectric strength observed in mineral oil may not apply.
2.6 Summary and Areas Identified for Investigation

Although the mechanism of breakdown of a liquid has been extensively researched,
there are a variety of factors which affect this process so it is difficult to propose one,
complete, theory explaining breakdown.
Adamczewski has characterized the processes of breakdown as being of two groups,

those affecting industrial purity oils and those affecting high purity ones.
The purity of the liquid reflects the quantity of contaminants such as water and particles,
which initiate breakdown. If the oils are handled in the same manner, it is reasonable to
expect that the purities of the esters will be similar to that of mineral oil. Therefore the
dielectric failure of both esters and mineral oil will be initiated by contaminants.
Consequently it is necessary to explore the relative impact of contamination on the
dielectric strengths of esters and compare to that of mineral oil.
It has been found that the quantity of aromatics in mineral oil influences its lightning
impulse dielectric strength. Two reasons were suggested for this, low ionisation
potentials and large electron trapping cross sections. An ester does not contain
aromatics, and it is difficult to foresee how the molecular structures found in the ester
oil, including additives, affect its lightning impulse dielectric strength.
The chemical stabilities of the oils must be considered because reactions will change the
44
nature of the oil possibly affecting its properties and the reliability of the transformer.
The ester molecules used in FR3 have unsaturated bonds decreasing their resistance to
oxidation. Consequently the manufacturer of FR3 does not recommend that this oil is
used in a free breathing transformer. However, even if a transformer is sealed, there is
the possibility of the oil being exposed to air during maintenance, from leaks or during
the manufacture of the transformer. Therefore it is important to investigate the effect of
oxidation on the dielectric strength of FR3 and compare to that of mineral oil.
The test standard used to measure the breakdown voltage specifies simple
configurations of electrodes, such as two spheres. This presents a difficulty in applying
the results to transformer design as the conductors of a transformer are not shaped as
simply as this. However, the advantage of using industry standard to measure the
breakdown voltage of an oil is that the standard sets the conditions of the test and allows
comparison with other research as it has been conducted under the same conditions. For
this project the breakdown voltages of the oils will be found using industry test
standards, resulting in a review which is comparative but not entirely representative of
the conditions in a transformer.
45
Chapter 3: Methods Used to Measure the Properties of the
Oils
3.1 Introduction
This chapter specifies the methods used to measure various properties of the oils and the
measurement values reported by the manufacturer for their oil when new. Where
possible measurements were performed to a test standard, however, as these standards
have been developed for mineral oil care was taken to ensure that the standards are
appropriate for testing esters.
The test methods for the following properties are discussed in this chapter:
AC dielectric strength
Dielectric dissipation factor, relative permittivity and DC resistivity
Water content
Acidity
Lightning impulse dielectric strength
3.2 AC Dielectric Strength

The dielectric strengths of esters are reported to be comparable to that of mineral oil by
the respective manufacturer, as shown in table 4.
However, as manufacturers tend to use different test methods, difficulties arise when
directly comparing breakdown voltages across oils. American manufacturers quote the
dielectric strength of a liquid to ASTM D1816 “Standard Test Method for Dielectric
Breakdown Voltage of Insulating Oils of Petroleum Origin Using VDE Electrodes”.
European manufacturers quote the dielectric strength to IEC 60156 “Insulating liquids –
Determination of the breakdown voltage at power frequency – Test method”.
46
Table 4: Breakdown voltages of the oils used in this investigation reported by the
manufacturer

Nynas Cooper Power M & I Materials
Systems
Breakdown 40 - 60 35 28-33 >75

voltage (kV)
Standard IEC 60156 ASTM D1816 ASTM D1816 IEC 60156

1mm gap 1mm gap
ASTM D1816 and IEC 60156 specify different types of electrodes, electrode gaps,
voltage ramp rate, stir times between tests and sample sizes, as shown in table 5.
Table 5: Comparison of ASTM D1816 and IEC 60156 breakdown tests
Property ASTM D1816 IEC 60156

Electrode type
Brass 36mm diameter Brass, Bronze or stainless

spherically capped electrodes steel. Either spherical
of the VDE (Verband (12.5mm to 13.0mm diameter)
Deutscher Elektrotechniker) or VDE type 0370 [50]
specification 0370 type [50]
Electrode gap (mm) 1 or 2 2.5

Voltage ramp rate (kV/s) 0.5 2
Number of breakdowns 5 or 10 6
Stir time between tests 1 Optional

(minutes)
McShane et al investigated the suitability of using ASTM D1816 with FR3 and
recommend leaving a 15 minute settling time, longer than per the standard, between
pouring the oil into the test cell and starting the test [49]. The higher viscosity and lower
interfacial tension of FR3 results in the slower expulsion of air bubbles compared to
47
mineral oil necessitating the longer settling time. IEC 60156 advises that the sample
must be checked to ensure that no air bubbles are visible in the electrode gap prior to
testing [50].
Johnson points out that the ASTM D1816 dielectric strength test method is used as a
qualification and acceptance test for an oil to detect contaminants remaining from
refining [21]. Therefore care has to be taken that it is the actual oil being tested, and not
the contaminants. Low breakdown voltages can be caused by free water and conducting
particles which are present in the oil. Johnson notes that this test method will not detect
water in solution.
The breakdown voltage of a liquid is a statistically distributed quantity. The dispersion

of the breakdown voltages is quantified by the coefficient of variation, given by
equation 3.1, which is equal to the standard deviation of the data (σ) divided by the
mean (89 ).
;
7% = <9
(3.1)
Lick writes that all standard test methods, which measure the AC breakdown voltage of
oil, have a bad reproducibility [51]. According to figure 7 the difference between the
coefficients of variation for two breakdown tests can be substantial [50]. There is a
general trend that the coefficient of variation is high when the mean breakdown voltage
is between 40kV and 60kV, according to IEC 60156 using a 2.5mm gap.
Lick notes that the occurrence of breakdown at a low voltage is related to the
probability of a weak link, such as a particle, appearing between the electrodes. When
the quality of the oil is very poor, a weak point always appears between the electrodes,
resulting in a mean breakdown voltage of below 40kV. When the quality of the oil is
high, the probability of a weak point appearing between the electrodes is low, resulting
in a breakdown voltage of above 60kV. Between these extremes it is not predictable
whether the contaminant will cause breakdown or not.
Therefore in this region the coefficient of variation can be high because different causes
48
of dielectric failure, giving different breakdown voltages, can occur within the same
sample.
60156 [50]
A BAUR Prüf und Messtechnik Fully Automatic Insulating Oil Tester DPA75 was used
to determine the AC dielectric strength of oil, shown in figure 8.
Figure 8: The DPA75 Fully Automatic Insulating Oil Tester
The block diagram of a typical oil tester, in this instance the DPA100 which was also
manufactured by BAUR, is given in figure 9 [52].
49
RT = voltage regulator transformer
Comp. = Comparator
Figure 9: Block diagram of the DPA100 showing the internal components of the unit
[52]
The DPA75 oil tester has the advantage of being a totally automated system which
increases the repeatability of the measurements. The unit has a current sensor to switch
off the voltage across the cell once a sustained breakdown occurs.
The current sensor is set by the manufacturer to trip at 4mA within 1ms of breakdown.
This has been found to be a suitable compromise between avoiding false trips and
protecting the liquid. An extremely low trigger level was noted to cause the set to
respond to pre-discharges or voltage fluctuations. These pre-discharges can be due to
the presence of particles or bubbles introduced into the oil during handling. The DPA75
test set has a series of relays which increase the amount of current limiting resistance as
the output voltage rises. This ensures that during test the short circuit current does not
rise to a point where the oil is degraded by the energy of the arc or when the circuitry of
the DPA75 is damaged from excessive levels of current.
For this project the AC dielectric strengths of the oils were found using standard ASTM
D1816. Reporting the breakdown voltages per IEC 60156 was rejected due to the output
voltage limitation of the DPA 75 test set. This unit can provide a maximum output of
75kV. Unfortunately when IEC 60156 was used, new oil did not fail at below 75kV.
ASTM D1816 was chosen because the spacing of the electrodes could be set at 1mm.
50
3.3 Dielectric Dissipation Factor, Relative Permittivity and DC
Resistivity
The dielectric dissipation factor (tan δ) is used to detect impurities such as water,
oxidation products, or other polar contaminants [21].
The tan δ of an insulating material is the tangent of the loss angle. The loss angle is
defined as “the angle by which the phase difference between applied voltage and the
resulting current deviates from π/2 rad when the dielectric of the capacitor consists
exclusively of the insulating material” [53].
Two standards are available, IEC 60247 “Insulating liquids – Measurement of relative
permittivity, dielectric dissipation factor (tan δ) and d.c. resistivity” [53] and ASTM
D924 “Standard Test Method for Dissipation Factor (or Power Factor) of Electrical
Insulating Liquids” [54].
The main difference between these standards is the difference in temperatures used to
perform the measurements. IEC 60247 requires that the tan δ must be measured when
the temperature of the liquid is 90°C whereas for ASTM D974 the temperature of the
liquid can be reported at 25°C, 85°C or 100°C. A benefit of measuring the tan δ at
85°C, 90°C or 100°C is that this is more representative of the operating temperatures of
the equipment [55]. However, practical disadvantages of using these temperatures are
that the oil is difficult to handle due to health and safety considerations and the oil may
start to oxidise. An observation was that the FR3 gelled inside the test cell when it was
tested at 100°C.
Both IEC 60247 and ASTM D974 provide recommendations of the design of the test
cell to be used for measuring the tan δ of insulating liquids. IEC 60247 is more explicit
than ASTM D974 as it provides an actual design, shown in figure 10, whereas ASTM
D974 provides a list of requirements for the cell to conform to. The design proposed by
IEC 60247 conforms to the requirements of ASTM D974, however, a test cell
conforming to the requirements of ASTM D974 may not necessarily conform to IEC
60247.
51
Figure 10: Example of a cell for measurements on liquids proposed by IEC 60247 [53]
IEC 60247 and ASTM D974 recommend applying different voltages to the test cell.
IEC 60247 states that the AC voltage shall be such as to subject the liquid to an
electrical stress between 0.03kV/mm and 1kV/mm. The frequency of the AC voltage
can be between 40Hz and 62Hz. ASTM D974 requires that the electric stress applied to
the liquid shall not be less than 0.2kV/mm with the frequency of the AC voltage being
between 45 and 65Hz.
Generally the tan δ can be converted from one frequency to another, within the range of
40Hz to 62Hz, by using equation 3.2 [53].
A
tan @A& = Btan @A' C A (3.2)

Unfortunately it is not common to report the frequency of the AC supply when

measuring the tan δ, which is either 50Hz or 60Hz depending on location. According to
equation 3.2 the tan δ of an oil measured using 50Hz will be 20% higher than when
measured at 60Hz.
52
Although experimental conditions can be used which fulfil the criteria of both IEC
60247 and ASTM D974, different temperatures are required which will cause
dissimilarities in the measurement. The tan δ of a material increases with temperature
and is generally exponential [53].
Care must be taken when comparing the tan δ of different oils supplied by different
sources because it is not usual for them to report the conditions of the test. Therefore
sometimes it may be uncertain whether dissimilarity in the values is due to differences
in test conditions or is actually characteristic of the oil. The tan δ of the oils is given in
table 6.
Table 6: Dielectric dissipation factors of the oils used in this investigation reported by
the manufacturer
Dielectric <0.1 0.1 1-3 <3

dissipation factor
(%)
Standard BS 5737* ASTM D924 ASTM D924 IEC 60247

90°C 100°C 100°C 90°C
*
Standard superseded by IEC 60247
It can be seen that tan δs are higher for esters than mineral oil, which is caused by
differences in the molecular structures of the oils. Oxygen is bonded into the molecular
structure of an ester. This causes the molecule to be polar and leads to an increase in its
tan δ. This is in contrast to mineral oil because molecules containing oxygen are classed
as the products of oxidation, which the refiner attempts to remove. Direct comparison of
dielectric dissipation factor between oils is therefore not a valid indicator of
contamination as esters are expected to have higher dielectric dissipation factors than
mineral oil.
The relative permittivity and volume resistivity of the oils are given in table 7 which
were measured according to IEC 60247 at 25°C. The relative permittivity was measured
using an electrical stress of 1kV/mm at a frequency of 50Hz.
53
The resistivity of the oils was found using a DC electrical stress of 250V/mm. The time
of electrification is important because the current flow through the oil decreases as
charge carriers migrate to the electrodes. The conventional arbitrary time of
electrification according to IEC 60247 is 1 minute. It must be assumed that the rate of
decrease of charge migration is similar for all oils for a comparison to be valid.
Although the resistivity of the esters is lower, they are in the same order of magnitude
as the mineral oil. It may be expected for mineral oil of this resistivity, according to
Adamczewski, that the process of breakdown will be thermal [28]. Since the resistivity
of the esters is similar to that of mineral oil, this implies that the process of dielectric
failure of these oils will also be thermal.
These esters have a higher relative permittivity than mineral as shown in table 7. The
higher relative permittivity of the esters is caused by the polar nature of the ester
molecule. When oil is used with cellulose in composite insulation, the electric stress is
shared across the materials as a function of their relative permittivities, shown in figure
1. As the relative permittivity of these esters is higher than that of the mineral oil, the
electric stress will be lower across the oil when it is an ester as opposed to being mineral
oil.
Table 7: Relative permittivities and volume resistivities of the oils as measured in this
investigation according to IEC 60247
Mineral oil Envirotemp FR3 Midel 7131
Relative permittivity 2.2 3.2 3.2

@ 25°C @ 25°C @ 25°C
Volume resistivity 51x1012 12x1012 20x1012

(Ωcm) @ 25°C @ 25°C @ 25°C
An ADTR-2K Automatic Dielectric Constant Tan Delta and Resistivity Test Set
manufactured by Eltel Industries was used to measure the dielectric dissipation factor,
relative permittivity and DC resistivity of the oils (figure 11).
54
Figure 11: The ADTR-2K test set and oil heater manufactured by Eltel Industries
The Eltel unit was supplied with an oil heater to control the temperature of the sample
while testing. The test cell used by the oil heater conforms to the design given in IEC
60247 and to the requirements outlined in ASTM D974.
All measurements were performed using IEC 60247 however an oil temperature of
25°C was used. A low temperature was chosen so that the oil could be safely handled.
Furthermore when the tan δ of FR3 was measured at 100°C, it was found that this ester
gelled in between the electrodes. Prior to a measurement being taken the sample was
visually checked to be free of air bubbles. The measurement was performed once the
thermometer on the test cell displayed 25.0°C although it is noted that the accuracy of
the temperature control is ±2°C.
The Eltel machine can measure an oil DC resistivity of up to 1000TΩcm. The accuracy
of this measurement is ±2% between 1GΩcm and 10TΩcm, ±5% between 10TΩcm and
100 TΩcm, then ±10% above this. The accuracy of the relative permittivity
measurement is ±0.1% and the accuracy of the tan δ measurement is ±1% of the reading
±0.0001.
3.4 Water Content
Esters are more hygroscopic than mineral oil, as shown in table 8. Excessive water will
affect the dielectric properties of an oil. Thus, it is important to quantify water levels
before and after investigations.
55
Table 8: Water solubilities of the oils used in this investigation at ambient temperature
reported by the manufacturer
Mineral oil Envirotemp FR3 Midel 7131
Water solubility at 55 1100 2700

ambient temperature
(ppm)
A Metrohm AG 684 KF Coulometer and 832 Thermoprep oven were used to determine
the water content of the oil (figure 12). The procedure is as follows:
i. A sample of oil weighing two grams is collected in a vial, a picture of the vials
is shown in figure 13.
ii. The sample is weighed using a Precisa XB120 precision balance, accurate to
within 0.1 mg. The XB120 is calibrated with the supplied weight before use.
iii. The vial is placed in the oven, which heats the sample to 140°C vaporising any
water.
Dry air passes through the sample, at 50ml per minute, transferring the steam to the
coulometer. The machine is programmed to perform the measurement over five
minutes. However, if more than five minutes is required, the machine extends the
measurement duration until all of the water has been extracted from the sample.
56
Figure 12: The XB120 balance, 684 Coulometer and 832 Thermoprep oven used to
measure the water content of oil
Figure 13: Vials which are used by the Coulometer to measure the water content of an
oil
The coulometer performs the titration with the chemical Hydranal AG-H, which is
suitable for use with long chain hydrocarbons such as ester and mineral oil.
Unfortunately AG-H was found to be unsuitable for aged FR3 because aged FR3
contains ketones, created by oxidation. These ketones are volatile enough to vaporise on
heating to 140°C in the oven, and along with the water are transferred by the dry air into
the coulometer. Once inside the coulometer the ketones react with the Hydranal AG-H
producing more water. The coulometer is then seen to give disappearing end points. A
suitable reagent, compatible with this model of coulometer, could not be found.
Mineral oil also creates ketones during oxidation. However these ketones did not
noticeably affect this measurement. One possible explanation is that ketones, being
polar, dissolve poorly in mineral oil instead forming sludge, whereas they are soluble in
FR3. Consequently when mineral oil is sampled many of the ketones formed will not be
contained in the sample having settled to the bottom of the vessel as sludge. In FR3,
57
where all of the ketones are in solution, they will be sampled along with the oil.
The unit can measure quantities of water in the order of micrograms; however care must
be taken to reduce measurement errors caused by background moisture. Small quantities
of water, usually between 50µg and 100 µg, are present as condensation in the vials. A
two gram sample of mineral oil with a water content of 5ppm will have 10 µg of water
present. Since the background moisture readings are more than the quantity of water
present in the oil, it is difficult to accurately determine the real water content of the oil.
Consequently an empty vial is prepared to measure the background moisture level.
Once the background moisture level is known, it can be subtracted from the measured
water level of the sample inside the vial. However, this method assumes that
background moisture is constant across vials. Metrohm advise that to decrease the
variation between background moisture levels of the vials they should be stored open in
the laboratory for at least 24 hours before use, should be stored at the same temperature
as the measurements are to be performed at and that the operator wear gloves when
handling the vials.
3.5 Acidity
Carboxylic acids are created in oil by chemical reactions. The acid value of a sample is
the mass of a base in milligrams, in this case potassium hydroxide, required to
neutralise the acid in one gram of the sample. This method does not determine the exact
nature of the acids in the sample so does not indicate their structures or
aggressivenesses. Therefore care must be taken when comparing the acid values of
different types of oil.
The acid values for the oils are given in table 9 according to two standards, ASTM
D974 “Standard Test Method for Acid and Base Number by Color-Indicator Titration”
[56] and IEC 61099 “Specification for Unused Synthetic Organic Esters for Electrical
Purposes” [57]. These standards are similar as they titrate 0.1 mol/l potassium
hydroxide solution with a sample of the oil and report the mass of potassium hydroxide
required to neutralise the acid in the oil. Acidity indicators are added to the potassium
hydroxide. An acidity indicator is a chemical which changes colour depending on the
pH of the solution, allowing the acidity or alkalinity of the solution to be determined.
The standards call for different indicators. ASTM D974 uses a solution of methyl
58
orange indicator whereas IEC 61099 uses a solution of alkali blue indicator.
Table 9: Acidity levels of the oils used in this investigation, when new, reported by the
manufacturer
Acidity level <0.01 0.022 <0.03

(mg KOH/g) ASTM D974 ASTM D974 IEC 61099 9.11
A Metrohm AG 686 Titroprocessor and 665 Dosimat were used to measure the
quantities of acids as per standard IEC 62021 “Insulating liquids – Determination of
acidity – Part 1: Automatic potentiometric titration” [58].
These machines obtain the acid value electronically, as opposed to IEC 61099 and
ASTM D974 which require an operator to assess a change of colour of the acidity
indicator. Similarly to IEC 61099 and ASTM D974, the mass of potassium hydroxide
required to neutralise one gram of oil is given when following IEC 62021. However, the
procedure used to determine when the acid has been neutralised is different. IEC 61099
and ASTM D974 require for the operator to manually titrate the alkali solution to the oil
and the neutralisation value is when the indicator changes colour. The procedure
advocated by IEC 62021 is to titrate volumes of alkali into the oil and measure the
resulting pH until the pH has increased to 11.5. The machine then determines the
volume of potassium hydroxide which had been titrated with the oil when the pH of the
oil was 7.
3.6 Lightning Impulse Dielectric Strength
Transformer insulation will be subjected to overvoltages, such as those caused by

lightning surges. Lightning overvoltages are characterised by a short front duration,
ranging from a fraction of a microsecond to several tens of microseconds, which then
decreases to zero [15]. The standard lightning impulse is a full lightning impulse having
a virtual front time of 1.2 µs and a virtual time to half-value of 50 µs [59].
A 10 stage impulse generator manufactured by Haefely Test AG, shown in figure 14,
was used to provide lightning impulses. The unit can provide up to 2.4MV.
59
Figure 14: Lightning impulse generator manufactured by Haefely Test AG which was
used to measure the lightning impulse breakdown voltages of oil
The energy of the discharge from the generator is related to the voltage per stage and
the number of stages being charged, as shown by equation 3.3 where C is the
capacitance per stage, V is the voltage per stage and n is the number of stages being
charged. The maximum output of energy is 15kJ per stage.
&
DE(2F = ' 7 ' D (3.3)
It is desirable to keep the energy of the arc low to minimise damage to the electrodes
and oil. Therefore the generator was operated with a high number of stages in the
circuit. The more stages in circuit the fewer volts per stage. It can be seen from equation
3.3 that the energy of the discharge is proportional to the square of the voltage.
Therefore as the voltage per stage decreases the energy of the arc quickly drops. The
lowest voltage per stage that the unit could be charged to was around 20kV. Below this
point the triggering mechanism could not reliably produce a discharge at the required
voltage.
60
For this project the lightning impulse dielectric strengths of the oils were found using
standard ASTM D3300-94 “Test Method for Dielectric Breakdown Voltage of
Insulating Oils of Petroleum Origin Under Impulse Conditions” with the spherical
electrode configuration [60]. The main points of this standard are:
• Spherical 12.7mm diameter brass electrodes
• Electrode gap of 3.8mm
• Standard 1.2µs/50µs lightning impulse
• Impulse polarity can either be positive or negative
• The voltage of the first impulse is at least 40kV below the expected breakdown
voltage
• The oil withstands three impulses before the voltage of the impulse is raised
• Oil stand time of at least 30 seconds between impulses
• The voltage of the impulse is increased in steps of 10kV
• Five breakdowns per sample
The test cell could withstand negative impulse voltages up to 300kV however external
flashover occurred at 170kV using positive impulses. This is explained by the fact that
positive polarity voltages cause air to fail at lower voltages than those of negative
polarities [27]. Consequently the lightning impulse breakdown voltages of the oils were
found using negative polarities.
3.7 Conclusion
Before a property of an ester is measured according to a standard the following points

must be considered:
1. Whether the procedure of the standard will correctly measure the property. An
example is that the higher viscosity of esters will result in the slower expulsion
of air after pouring into the test vessel. When a standard designed to test mineral
oil suggests a standing time this may be required to be increased to correctly test
an ester.
61
2. Whether the property can be directly compared across different oils. An example
is the dielectric strength, which can be directly compared across oils. However,
the dielectric dissipation factor cannot be directly compared across oils because
they are of different polarities. If the dissipation factor of an oil is being
measured to detect polar contamination, this value should only be compared to
that of the same type of oil.
3. Health and safety assessments must be carried out and risks reduced where
possible. IEC 60247 specifies that the dielectric dissipation factor, resistivity and
relative permittivity should be measured at 90°C. In order to negate the risks of
handling hot oil this measurement was performed at 25°C. Heating the sample
up to 90°C, performing the measurement and then allowing the sample to cool
down to ambient temperature was considered. However, the test cell is a 2.5kg
block of stainless steel and was found to take an impractically long time to cool.
62
Chapter 4: Comparison of the Breakdown Voltages of New
Oil
4.1 Introduction
It is usual for the AC or lightning impulse dielectric strength of an oil to be reported as

the mean breakdown voltage measured using an industry standard. The mean
breakdown voltage of the oil is then compared to that of other oils to judge its
performance. Reporting the mean is simplistic when comparing the dielectric strengths
of different oils because many of the failures will occur at voltages below the mean. It is
more valuable to report the voltage at which the oil is unlikely to fail.
One hundred breakdown voltages were measured using the DPA75 oil tester in order to
analyse the dielectric strengths of the oils at low probabilities of failure. Weibull and
Gaussian distributions were applied to the distributions of breakdown voltages in order
to comment on the accuracy of using these distributions to model the data.
4.2 The Statistical Nature of AC and Lightning Impulse Breakdown

Voltage
The breakdown voltage of a dielectric material is a statistically distributed quantity
corresponding to a probability of failure. The probability of failure is a function of the
applied electric stress. This probability is affected by the individual probabilities of the
processes which lead to dielectric failure, such as:
• The probability that an initiating event within the electrically stressed oil volume
creates a bubble
• The probability that the bubble ionizes and forms a streamer
• The probability that the streamer bridges the electrodes and causes breakdown
The factors which cause the initiating event leading to breakdown can be the water and
dissolved gas content of the oil, particles suspended in the oil or the geometry and
condition of the electrodes [28,61]. Dielectric failure of oil has been previously
described as due to a weak link in the insulation [62]. Thus the dielectric strength of an
63
oil is dependent on weak links, such as impurities in the oil, rather than the oil itself.
Adamczewski notes that the dielectric strength of an oil can improve with repeated
breakdowns as discharges remove these weak links [28].
In order to determine whether the probability of failure of an ester is different to that of

mineral oil, the overall distribution of breakdown voltages must be analysed and not
just the mean. If the dispersions of the breakdown voltages of two oils differ despite
similar means then one oil may be more likely to fail at a given voltage than the other.
Since dielectric failure is a function of risk, the lowest voltage when an oil fails is
estimated at an acceptable probability of failure, which is known as the withstand
voltage [64,63]. Statistical techniques have been used extensively to estimate the
dielectric strength of insulation at low probabilities of failure [16,64,65,66,67,68,69].
These techniques involve the use of a parametric distribution, which is commonly the
Gaussian or Weibull distribution [70]. In order to use such a distribution it must be
verified that the distribution can accurately model the data.
4.3 Investigation to Compare the AC Breakdown Voltages of the Oils
4.3.1 Introduction to the Investigation
The aim of this investigation was to analyse whether, despite similar mean breakdown
voltages, the lowest breakdown voltages of the esters are similar to those of mineral oil.
This is accomplished by using sample sizes of at least 100 observations. The Weibull
and Gaussian distributions are then used to analyse the data to verify the accuracy of
using such distributions to estimate a failure voltage at a low risk.
4.3.2 Experiment
The oils were individually degassed and dried at less than 1kPa for 2 days at 80°C, then
were given a further day to cool to ambient temperature under vacuum conditions. A
Baur DPA75 oil tester was used to measure AC breakdown voltages as per ASTM
D1816 using brass partially spherical electrodes set at 1mm gap. The rate of rise of the
voltage was 0.5kV/s. All measurements were performed at room temperature. To give a
large sample of data, at least 20 sets of 5 breakdowns were obtained to give a minimum
64
of 100 points of data. In total 100 breakdowns were obtained for mineral oil and FR3
and 105 breakdowns were obtained for Midel 7131. The same sample of oil was used
throughout the breakdowns. The DPA75 oil tester has flash detection to reduce oil
degradation caused by multiple breakdowns.
4.3.3 Results for AC Breakdown Test
The results are plotted in figures 15 to 17. The breakdown voltages are tabulated in
Appendix A. The mean breakdown voltages of the esters, in this case, are higher than
that of the mineral oil. The distributions for mineral oil and FR3 show a slight upwards
trend. This can be explained by Adamczewski’s observation that repeated breakdowns
remove impurities from the oil and electrode surface.
60
Mean breakdown voltage = 39kV
Breakdown voltage 1mm gap (kV)
50
40
30
20
10
0
1 11 21 31 41 51 61 71 81 91
Breakdown voltage (nth observation)
Figure 15: Distribution of mineral oil AC breakdown voltages
65
60 Mean breakdown voltage = 41kV

50
40
30
20
10
0
1 11 21 31 41 51 61 71 81 91
Figure 16: Distribution of FR3 AC breakdown voltages
60
50
40
30
10
0
1 11 21 31 41 51 61 71 81 91 101
th
Breakdown voltage (n observation)
Figure 17: Distribution of Midel 7131 AC breakdown voltages
It is known that the relative humidity of an oil affects its breakdown voltage. Therefore,
the moisture levels of the oils were obtained by Karl Fischer titration (Metrohm 684
Coulometer with 832 Thermoprep oven) and are given along with the relative humidity
in table 10. The relative humidity of an oil is a better indicator of the wetness of the oil
and its effect on the dielectric properties than absolute moisture content. From the
66
results given in chapter five it is unlikely that these low levels of water would affect the
mean breakdown voltage of the oils.
There was a concern that these oils may pick up moisture as the investigation
progressed, but this was found not to have occurred. There was no noticeable increase
in the moisture content of mineral oil while the Midel 7131, the most hygroscopic oil,
showed an increase of 25ppm. At room temperature an increase of 25ppm of water in
this ester equates to a 1% increase in relative humidity. Low moisture uptake rates can
be explained by the relatively short experiment duration which was roughly six hours in
a sealed oil bath.
Table 10: Water content of oils and their relative humidities at room temperature
Oil Water content Oil relative humidity

@ 20°C
(ppm) (%)
Mineral oil 9 17
FR3 35 3
Midel 7131 59 2
4.3.4 Parameters of the Breakdown Voltage Distributions
The parameters of the distribution can be quantified by the following terms: Mean,
variance, skewness and kurtosis, which are described below.
The mean of the sample of breakdown voltages is shown in equation 4.1 where 89 is the
mean of value 8 and n is the number of values in the sample.
∑<
89 = (4.1)
H
The statistical dispersion of the breakdown voltages is given by the variance (I ' ) which
is the square of the standard deviation. The standard deviation is shown in equation 4.2.
67
∑(<0<9 )
I=J (4.2)
H0&
The skewness, shown in equation 4.3, is a measure of the asymmetry of the distribution
where n is the number of observations, 8 is the observation, 89 is the mean value and σ
is the standard deviation, and is a function of the difference between the median and
mean values of the distribution. The median value of a distribution is the middle value
when the observations of the distribution are ranked in increasing order of magnitude. A
skewness of zero indicates that the median and mean values of the distribution are equal
and therefore the distribution is symmetrical. If the skewness is positive the mean
exceeds the median whereas when negative the median exceeds the mean.
H < 0<9 )
KLEMDENN = (H0&)(H0') ∑ ;
(4.3)
The kurtosis is a measure of the quantity of outliers of a distribution, given in equation

4.4. A normally distributed sample will have a kurtosis of 3. If the kurtosis of a sample
is greater than 3 then there will be more outliers than expected from a normally
distributed sample. A distribution with a kurtosis higher than 3 is called leptokurtic. If a
sample has a kurtosis lower than 3 then there will be fewer outliers than a normally
distributed sample, which is called platykurtic.
H(H&) < 0<9 U )(H0&)

OP(QRNSN = T(H0&)(H0')(H0)) ∑ ;
V − (H0')(H0)) (4.4)
The mean, standard deviation, kurtosis and skewness of the sample populations are
given in table 11. These values will be used to discuss the analysis of the data using
Gaussian and Weibull distributions.
68
Table 11: The mean, standard deviation, kurtosis and skewness of the sample
populations obtained during the investigation
Oil Mean Standard Kurtosis Skewness

deviation
(kV) (kV)
Mineral oil 39 3.7 4.36 -0.73
FR3 41 5.3 3.01 -0.60
Midel 7131 47 6.2 3.98 -0.82
4.3.5 Effect of Sample Size on the Accuracy of the Mean Breakdown Voltage
The parameters of the breakdown voltage distributions, shown in table 11, can be used
to estimate the effect of the sample size on the accuracy of the mean breakdown
voltage. This section analyses the effect of the sample size on the accuracy of the mean
of a distribution of breakdown voltages in order to establish an appropriate sample size
to be used to measure the dielectric strengths of the oils in this project.
The mean value calculated from a sample of data only provides an estimate of the true
mean. The precision of this estimate can be quantified by an error term. The magnitude
of this error term depends on the following three factors:
1. The sample size

2. The variability of the data
3. The level of confidence
The error term is added to, and subtracted from, the sample mean to give the confidence
limits, between which the true mean is likely to lie. The confidence level is the
probability of the true value lying within these bounds and is usually set by statisticians
to be 95%. If a higher confidence level is used then the confidence interval, as well as
the error term, will also become larger.
When it is reasonable to assume that a variable is approximately normally distributed

then the confidence interval can be estimated using equation 4.5, where D is the number
of observations, 89 is the sample mean, σ is the standard deviation and t is a measure of
uncertainty based on the number of observations within a sample which is found from a
69
table of percentage points. As the number of observations increases, t tends towards
1.96 which is the number of standard deviations within which 95% of the data falls in a
Gaussian distribution.
Y;
89 ± R( D > 1 (4.5)
√H
The effect of the sample size on the confidence interval is also dependent on the
standard deviation of the population. Using the parameters of the failure distributions
obtained in this investigation and equation 4.5, the confidence limits of the distributions
can be estimated as a function of the sample size, shown in figures 18 to 20.
80
70
60
50
Voltage (kV)
40 Mean breakdown
voltage
30
95% Confidence limits
20
10
0
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Sample size (n)
voltage of mineral oil
70
80
70
60
50
Voltage (kV) 40 Mean breakdown
voltage
30
20
10
0
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Sample size (n)
voltage of FR3
80
70
60
50
Voltage (kV)
40 Mean breakdown
voltage
30
20
10
0
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Sample size (n)
voltage of Midel 7131
Since the confidence limits are dependent on the standard deviation, which is similar for
all three oils, there is little difference between the effects of the sample size on the
confidence interval for the three oils. An assumption of equation 4.5 is that the
population is approximately normally distributed. This is an imprecise term and it is not
easy to conclude how ‘un-normal’ a sample has to be before significant deviations from
71
the confidence interval are seen.
The 95% confidence limits can be expressed as a percentage error of the mean
breakdown voltage. This percentage error is shown as a function of the sample size in
figure 21.
20
15
Percentage error (%)
10 Mineral oil
FR3
5 Midel 7131
0
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Sample size (n)
Figure 21: Percentage error of the 95% confidence intervals of the mean breakdown
voltages
It can be seen that the percentage error is large for a small sample size and reduces as
the sample size increases. At low sample sizes the gradient of the curve is steep,
gradually reducing as n tends to infinity and the error tends to zero. It is common in
statistics to obtain a sample size of between twenty and thirty measurements. If sample
sizes higher than thirty measurements are obtained then the resultant increase in
precision may not justify the experimental time required to obtain the extra
measurements. This analysis demonstrates that there would be a sizable error, around
15%, in the mean breakdown voltages of the oils if a sample size of five measurements,
as per ASTM D1816, were used.
Although the mean breakdown voltage of the esters is higher than that of the mineral
oil, this gives no indication of the dielectric performance of the esters at voltages below
the mean voltage. The following section analyses the breakdown voltage data using
histograms in order to quantify the failures at voltages below the mean.
72
4.3.6 Histograms of the Breakdown Voltages
The breakdown voltages are displayed as histograms in figures 22 – 24. When analysing
the histograms the following conclusions can be made:
The lowest breakdown voltages, at the 1% breakdown level, were all similar
around 25kV
Despite Midel 7131 having a higher mean voltage than the other two oils, the
lowest breakdown voltage is not higher. This is a concern because this implies
that simply reporting the mean breakdown voltage of this oil does not
necessarily indicate that the withstand strength of this oil is better than that of
mineral oil.
35
30
25
Frequency (n)
20
15
10
0
20 25 30 35 40 45 50 55 60
Breakdown voltage (kV)
Figure 22: Histogram for the AC breakdown voltages of mineral oil
73
35
30
25
Frequency (n)
20
15
10
0
20 25 30 35 40 45 50 55 60
Figure 23: Histogram for the AC breakdown voltages of FR3
35
30
25
Frequency (n)
20
15
10
0
20 25 30 35 40 45 50 55 60
Figure 24: Histogram for the AC breakdown voltages of Midel 7131
The Midel 7131 was re-tested, using another sample, by another student to verify that
74
the skewness of the distribution was not due to an unusual event such as operator or
equipment error. The values are given in figure 25 and table 12. The skewness of the
second sample is higher than that of the first. Consequently the high skewness of the
first sample may not be due to chance.
60
50
40
30
20
10
0
1 11 21 31 41 51 61 71 81 91
Instance (nth)
Figure 25: Breakdown voltage distribution of re-tested Midel 7131
Table 12: Values of re-tested Midel 7131 using 1mm electrode gap
Sample of Midel Mean Standard Kurtosis Skewness

7131 (kV) deviation
(kV)
1st sample (used 47 6.2 3.98 -0.82

in this analysis)
2nd sample (re- 38 5.8 4.68 -1.07

test)
The mean breakdown voltage of the second sample is 9kV lower than that of the first. It
is difficult to conclude whether this difference is due to the statistically distributed
nature of breakdown, i.e. by chance, or if this difference is due to an actual effect such
as the oil being in a different condition or variability due to the operator.
The next part of the thesis discusses the use of the Gaussian and Weibull distributions to
estimate a withstand voltage for the oils.
75
4.3.7 The Use of the Gaussian Distribution to Model Breakdown Voltages
The Gaussian distribution arises when a variable is measured for a large number of
nominally identical objects where the variation may be assumed to be caused by a
number of factors, each exerting a small positive or negative random influence on an
individual object [71].
The probability density function of the Gaussian distribution is given in equation 4.6
[72]. The Gaussian distribution uses the value (8), mean (89 ) and variance (I ' ) of the
data as parameters.
(`a`] )
') & 0_ c
%(8; 8;
]I = ;√'^ E b (4.6)
Once the mean and variance of the sample of breakdown voltages is known, the
distribution can be used to estimate the breakdown voltage at a chosen probability. The
estimated breakdown voltage at an acceptably low probability of failure is termed the
withstand voltage. The withstand voltage is, therefore, a design parameter which varies
according to the probability of failure deemed acceptable for each specific insulation
design.
The drawback to using the Gaussian distribution to model a distribution is that it makes
certain assumptions about the data. These assumptions are that the data is symmetrically
distributed around the mean, and that there are a certain number of outliers. Data
symmetry is quantified by the skewness and the quantity of outliers is given by the
kurtosis. Given that the standard deviation of the data is calculated from the entire
sample of data, and that it is only the area of the graph to the left of the mean which is
used to estimate the withstand voltage, asymmetry will reduce the accuracy of the
withstand voltage estimation if the Gaussian distribution is applied.
If the adherence of a distribution of breakdown voltages to the Gaussian distribution is

assumed, following on from the assumption of this distribution, then the variation in
breakdown voltages may be caused by a number of factors exerting a small positive or
negative random influence on the oil. Since breakdown in oil is due to some weak link,
it is easy to understand how a negative random influence can reduce the breakdown
76
voltage. However, it is difficult to see how a weak link could have a positive influence
on the breakdown voltage.
The data of the samples are skewed which will reduce the accuracy of using the
standard deviation to estimate the withstand voltage. The kurtoses of the samples are
greater than 3, indicating that the breakdown voltages are leptokurtic.
The Gaussian distribution assumes that skewness = 0 and kurtosis = 3. Due to the
samples being skewed and leptokurtic the accuracy of the Gaussian distribution in
estimating failure at low probabilities will be reduced.
It is likely that the withstand voltage of Midel 7131, as calculated using the Gaussian
distribution, will be more inaccurate than those of the other two oils because Midel
7131 has the most skewed distribution.
The normality of the distribution of breakdown voltages can be verified either

mathematically using a Shapiro Wilk test or graphically using normal probability plots.
If the samples are found to confirm to normality it supports the usage of the Gaussian
distribution to estimate mean breakdown and withstand voltages.
4.3.8 Shapiro Wilk Test for Normality
The Shapiro Wilk test assesses the likelihood of the hypothesis that a sample is
normally distributed being correct [71,73,74,75]. The statistic calc w is calculated for
the sample and is then compared to a tabulated value, tab w, to estimate the probability
that the distribution is normal. If this probability is greater than a threshold value, the
level of significance, then it is likely that the hypothesis of normality is correct. If this
probability is lower than the level of significance, then the assumption of this
hypothesis may not be correct and consequently, the hypothesis that a sample is
normally distributed is rejected.
By convention a significance level of 5% is used though other levels of significance can

be used. However, incorrect conclusions may be drawn from the test. If a higher level of
significance is used then there is a greater possibility of incorrectly rejecting the
hypothesis that a sample is normally distributed. If a lower level is used then there is a
77
greater possibility of incorrectly accepting that a sample is normally distributed.
This test firstly ranks the sample of n observations in increasing order referring to them
as x(1), x(2) and so on up to x(n). Secondly the test calculates a value, b, using equation 4.7
where a1, a2,... are coefficients specified by the test.
d = 3& B8(H) − 8(&) C + 3' B8(H0&) − 8(') C + ⋯ (4.7)
Lastly the test statistic, calc w, is calculated by equation 4.8 where s is the standard
deviation of the n observations.

M = (H0&)g (4.8)
Calc w is then compared to tab w, which is taken from a table of percentage points, to
give the probability that a sample is normally distributed. Tab w is determined by the
sample size. If the probability that the sample is normally distributed is greater than the
significance level, then it is reasonable to assume that the distribution is normal.
It can be seen in table 13 that this test rejects the hypotheses at the 5% significance level
that the breakdown voltages of these oils are normally distributed. The result that these
oils do not conform to normality can be explained by the fact that they all have skewed
distributions. The rejection of normality results in the fact that the Gaussian distribution
cannot accurately model breakdown. Therefore using this distribution to estimate a
withstand voltage at a low probability of failure will not provide a meaningful result.
Table 13: Summary of performing the Shapiro Wilk test for normality on the AC
breakdown voltages at 5% significance level
Oil Calc w Probability that sample Conformance to

is normally distributed normality
Mineral oil 0.96 0.009 REJECTED
FR3 0.97 0.018 REJECTED
Midel 7131 0.95 0.001 REJECTED
78
4.3.9 Normal Probability Plots
Normal probability plots are used to compare the sample of data to an expected
Gaussian distribution using the mean and standard deviation calculated from the data
(figures 26 – 28).
The gradient of the trend-line of the esters is less than that of the mineral oil indicating
that the breakdown voltages of esters are more dispersed. Thus even though the esters
have higher mean breakdown voltages than mineral oil the estimated withstand voltage
may not also be higher. This is observable in the distribution for FR3 because despite
the mean breakdown voltage being higher than that of the mineral oil, the 1%
breakdown voltage of FR3 was about 4kV less than that of mineral oil. Although Midel
7131 has the highest mean voltage, the first quantile is around the same voltage as the
first quantile of the other oils.
All three oils show deviations at the tails, demonstrating that the Gaussian distribution
may be inaccurate at low probabilities. The data deviates from the distribution at 5% to
10% depending on the oil. It is a concern that the lowest breakdown voltages deviate
above the trend-line because this indicates that the probability of the oils failing at these
voltages is higher than estimated using the Gaussian distribution.
This deviation may be explained by the theory that breakdown is caused by weak links.
For instance, if a particle is in a suitable position it may initiate the formation of the
bubble. The bubble may or may not ionize forming a streamer. The streamer may or
may not bridge the electrodes and cause failure. If the initiating particle is not in a
suitable position then the initiation of dielectric failure will occur on the next weakest
link, which may be at a higher voltage. Therefore it is more likely that the oil will fail as
the voltage is ramped upwards towards the mean breakdown voltage than above this.
The Gaussian distribution uses the mean and standard deviation of the data, which is
calculated over the entire sample, to produce one distribution. The breakdown voltage
of the oils at 1% probability of failure, as estimated using the Gaussian distribution, is
given in table 14.
79
0.997
0.99
0.98
0.95
0.90
0.75
Probability
0.50
0.25
0.10
0.05
0.02
0.01
0.003
25 30 35 40 45 50 55 60
Figure 26: Normal probability plot for the AC breakdown voltages of mineral oil
0.997
0.99
0.98
0.95
0.90
0.75
Probability
0.50
0.25
0.10
0.05
0.02
0.01
0.003
25 30 35 40 45 50 55 60
Figure 27: Normal probability plot for the AC breakdown voltages of FR3
80
0.997
0.99
0.98
0.95
0.90
0.75
Probability
0.50
0.25
0.10
0.05
0.02
0.01
0.003
25 30 35 40 45 50 55 60
Figure 28: Normal probability plot for the AC breakdown voltages of Midel 7131
Gaussian distribution
Oil Breakdown voltage at 1% probability of failure

(kV)
Mineral oil 32
FR3 28
Midel 7131 33
4.3.10 Introduction to the Weibull Distribution
Unfortunately the Gaussian distribution becomes inaccurate at low probabilities because

it is unable to model data which has skewness or outlying points. This distribution does
not attempt to model the processes which cause failure.
In 1951 Weibull published his analysis on providing a distribution that was suitable for
modelling the processes which lead to failure [76]. Weibull used the example of a chain
consisting of n links. When a load, 8, is applied to a single link the probability of failure
of the link is given by P. In order to find the probability of the overall chain failing, Pn,
81
one must assume that if any one of the links fail then the whole chain has failed. Non-
failure of the chain, (1 – Pn), is equal to the probability of simultaneous non-failure of
all the links. Thus (1 – Pn) = (1 – P)n. The weak link model has been extensively used to
explain the dielectric failure of oil [28]. Non-failure of an oil gap is therefore based on
the probability that none of the individual components of the oil fail.
Equations for the probability density and cumulative distribution functions are given in
4.9 and 4.10. The shape of this distribution is defined by the alpha (α) and beta (β)
parameters. %(8) is the probability of failure at voltage 8. When the failure probability
is 0.632, the α parameter is equal to voltage 8. Since α = 8, %(8) = 1 − E 0& ,
%(8) = 0.632. The β parameter is a measure of the spread of breakdown voltages. The
larger β is, the smaller the range of breakdown voltages.
` o
m 0
%(8; k; l) = 8 m0& E p (4.9)
no
` p
%(8) = 1 − E 0o , 8 ≥ 0 (4.10)
The Weibull distribution can be expected to provide a more accurate model of the
breakdown voltage distribution than the Gaussian distribution because it does not make
assumptions of the skewness and kurtosis.
Both Nelson & Shaw [77] and Lick et al [78] have used this distribution to estimate
withstand voltages of insulation. Nelson and Shaw studied the AC dielectric strength of
mineral oil impregnated cellulose. They found the AC breakdown voltage for thirty
samples and used the Weibull distribution to estimate the 1% breakdown value. Lick et
al studied the AC dielectric strength of large oil gaps, of up to 30mm. They measured
the voltage of 25 breakdowns and used the Weibull distribution to estimate the 1%
failure value.
4.3.11 Adherence to the Weibull Distribution
Figures 29 to 31 show the adherence of the failure distributions for each oil to the
Weibull model. On first sight the sample data tends to adhere more closely to the
Weibull distribution than the Gaussian. This is because the Weibull function calculates
82
the skewness and kurtosis rather than assumes them to be a fixed value. This allows the
Weibull function to take into account that the dielectric failure of an oil may be affected
by different phenomena, e.g. particles, free water or gas bubbles, to different degrees at
different applied voltages.
As with applying the Gaussian distribution, the accuracy of the Weibull distribution
reduces with decreasing probability. The points at the lower end of the distributions
deviate from the theoretical value at that probability. This may be due to the influence
of a single weak link or to the combined effect of several weak links. Both esters
perform similarly to mineral oil, with the 1% Weibull value being between 101.4 and
101.5 equating to between 25kV and 32kV. The breakdown voltage of the oils at 1%
probability of failure, as estimated using the Weibull distribution, is given in table 15.
0.99
0.96
0.90
0.75
0.50
0.25
Probability
0.10
0.05
0.02
0.01
0.003
1.3 1.4 1.5 1.6 1.7 1.8
10 10 10 10 10 10
Figure 29: Weibull probability plot for the AC breakdown voltages of mineral oil
83
0.99
0.96
0.90
0.75
0.50
0.25
Probability
0.10
0.05
0.02
0.01
0.003
1.3 1.4 1.5 1.6 1.7 1.8
10 10 10 10 10 10
Breakdown voltage, (kV)
Figure 30: Weibull probability plot for the AC breakdown voltages of FR3
0.99
0.96
0.90
0.75
0.50
0.25
Probability
0.10
0.05
0.02
0.01
0.003
1.3 1.4 1.5 1.6 1.7 1.8
10 10 10 10 10 10
Figure 31: Weibull probability plot for the AC breakdown voltages of Midel 7131
84
Weibull distribution

(kV)
Mineral oil 29
FR3 26
Midel 7131 30
4.3.12 Analysis using a Non Parametric Test
The results of the breakdown voltage estimated by both Gaussian and Weibull
distributions become inaccurate at low probability. The disadvantage of using these
distributions, which are parametric, is that they assume that the mechanism of
breakdown can be modelled by their equations.
Other statistical methods are available which do not attempt to model a process, which
are known as non parametric tests. These tests can be superior to their parametric
counterparts as these do not assume that the data belongs to a distribution. The simplest
non-parametric method is to order the observations from smallest to largest, count the
number of observations and assume that there is an equal probability of each
observation occurring. Thus the probability of failure at a given voltage can be
estimated.
The comparison of these three methods, shown in table 16, reveals that the withstand
voltages at probabilities of 5% and below, are less than predicted by both parametric
distributions. This is a concern since this demonstrates that a margin of error is required
when estimating the withstand voltage of oil using the Gaussian or Weibull
distributions.
85
Table 16: Comparing the withstand voltages of the oils given by non-parametric and
parametric methods
Probability Non parametric Gaussian distribution Weibull distribution

(%) (kV) (kV) (kV)
Mineral oil
50 40 39 41
10 35 36 37
5 32 35 35
2 30 33 33
1 25 32 29
FR3
50 41 41 43
10 34 34 36
5 30 32 33
2 29 30 29
1 24 28 26
Midel 7131
50 48 47 50
10 38 39 42
5 36 37 39
2 29 35 34
1 24 34 30
At the 1% risk of breakdown, the Weibull distribution tends to give closer results to that
of the non-parametric test than the Gaussian distribution. Since neither Weibull nor
Gaussian distribution accurately provide the voltage at 1% risk of failure from a sample
size of 100 data, it is clear that estimating the voltage at 1% probability of failure from a
5 point data sample as per ASTM D1816 will be so inaccurate as to be of limited use.
4.3.13 Investigating the Withstand Voltages of the Oils
The withstand voltage is defined as a voltage where the risk of failure is acceptably low.
However the distributions of the oil breakdown voltages are leptokurtic in terms of
kurtosis so the possibility of extreme, unforeseen, low voltage failures is always present.
The lowest breakdown voltage of the esters is comparable to that of the mineral oil
(table 17) with only 1kV difference. Applying both Gaussian and Weibull distributions
to the esters and mineral oil provided results close to one another, however the samples
86
tended to fit better to the Weibull distribution than the Gaussian. Midel 7131 gave the
largest difference between the results when applying the non-parametric, Weibull and
Gaussian distributions. This is due to Midel 7131 having the most skewed distribution
which decreases the accuracy of the Gaussian function.
Table 17: Breakdown voltage of the oils at 1% probability of failure

(kV)
Mineral oil 25
FR3 24
Midel 7131 24
4.4 Investigation to Compare the Lightning Impulse Breakdown

Voltages of the Oils
4.4.1 Introduction
The probability of an oil failing is a not only a function of the magnitude of the voltage,
but is also related to the duration that the voltage is applied for. The processes which
lead to dielectric failure require time to act, for instance an impurity requires time to
move into an area of high electric stress to cause a discharge or a bubble requires time
to expand and form a streamer.
When the AC breakdown voltage is measured, particles can have sufficient time to
move under the influence of the electric field and cause breakdown. However, in the
case of a lightning impulse, the duration under voltage is much shorter (rise time =
1.2µs and time to half value = 50µs) so there is the possibility that events may not have
sufficient time to initiate breakdown before the transient has passed.
This was noted by Nelson and Shaw who comment that the processes which require a
considerable period of time, such as particle migration, do not have sufficient time to
initiate breakdown under an impulse transient [77]. Nelson remarks that the chemical
nature of an oil can have some bearing on failure [79]. The aromatic content of a
mineral oil will have an effect on its lightning impulse dielectric strength.
87
Lundgaard et al observed that most particles do not affect the lightning impulse
breakdown voltage because these require more time to polarize and discharge to an
electrode than the duration of the lightning impulse [46]. However, they write that
metallic particles affect the lightning impulse dielectric strength because these polarize
instantaneously.
Lightning impulses are applied in discrete steps with the oil either withstanding or
failing the transient. The probability of failure at a specific voltage of lightning impulse
can be found by treating the distribution of lightning impulse dielectric strength of an
oil as binomial because it is a sequence of experiments where the oil either does or does
not withstand an applied voltage.
The lightning impulse dielectric strengths were found using standard ASTM D3300.
The electrode arrangement used consisted of two 12.7mm diameter brass spheres set to
a spacing of 3.8mm. The oils were dried overnight at 80°C in a vacuum below 1kPa.
The water content of the oils, along with the respective percentage saturation and mean
breakdown voltage are given in table 18.
Table 18: Mean breakdown voltage, standard deviation and water content of the oils
during the lightning impulse tests
Oil Water content Water content Mean breakdown Standard deviation

%RH voltage
(ppm) @ 20ºC (-kV) (kV)
Mineral oil 5 10 196 4.0
FR3 26 2 181 4.2
Midel 7137 77 3 165 2.6
4.4.2 Discussion of the Results
The voltages of five breakdowns, as per the requirement of the standard, are given in
figure 32. The sample size is limited to five breakdowns for the following two reasons:
Firstly whereas the energy of the arc was limited by the DPA 75 during AC voltage
88
measurements, the energy of the arc created by the Haefely impulse generator could not
be kept minimal and had previously been seen to pit the surfaces of the electrodes.
Since abrasions on the electrodes will distort the electrode field and can influence
dielectric failure, large sample sizes were not investigated.
Secondly while the DPA 75 is a compact automated unit which can be operated in
minimal space with minimal operator intervention, the lightning impulse generator
requires the main high voltage laboratory and an operator. The labour effort was not
practicable.
220
200
Breakdown voltage 3.8mm gap (-kV)
180
160
140
120
100
Mineral oil FR3 Midel 7131
Oil
Figure 32: Distribution of oil lightning impulse breakdown voltages
It is difficult to conclude if there is a significant difference between the results of the

mineral oil and the FR3 because of the dispersion and precision of the data. The voltage
was raised in steps of -10kV and most of the data for FR3 is within 10kV of the
minimum breakdown voltages of mineral oil. The mean lightning impulse dielectric
strength of the Midel 7131 is approximately 30kV lower than that of the mineral oil.
This difference cannot be explained by high levels of water nor from a large standard
deviation, shown in table 18. However, the data can be analysed further, in the next
section, to investigate the probability of dielectric failure at each voltage to conclude
whether the lightning impulse dielectric strength of Midel 7131 is indeed lower than
that of mineral oil.
89
4.4.3 Probability of Failure at the Breakdown Voltage of an Oil
A drawback to using the standard deviation is that it does not indicate the number of
withstands at the mean voltage of failure. The rate of failure of an oil, at a given
voltage, may be a better indicator of the performance of an oil because it takes into
account a withstand as well as a breakdown.
The standard, ASTM D3300, requires that the following points are adhered to:
• The voltage of the first lightning impulse is at least 40kV below the expecting
breakdown voltage
• The oil withstands three impulses before the voltage of the impulse is raised
• The voltage of the impulse is increased in steps of 10kV
• Five breakdowns are obtained per sample
The rate of failure for mineral oil at the -200kV level of impulse was 5/5, shown in table
19. In contrast the rate of failure at 190kV, the previous step, was 0/3. Therefore it
appears that there was a sudden change between the oil remaining as an insulator and
the oil breaking down.
The performance of the FR3 was similar to that of the mineral oil. The rate of failure at
190kV of FR3 was 5/5 whereas the probability of failure at the previous step, 180kV,
was 0/3.
The rate of failure of the Midel 7131 at 170kV was 5/9. The five flashovers occurred
on the 2nd, 5th, 7th, 8th and 9th impulses. If the Midel 7131 had not flashed over on the 2nd
impulse then as it did not flashed over on the 3rd impulse, and because only three
withstands are required at a voltage level, the voltage would have been increased to
180kV and a higher breakdown voltage would have been recorded.
The lightning impulse dielectric strength of Midel 7131 is therefore between 20kV and
30kV less than that of mineral oil. This analysis shows the practical difficulties of
drawing conclusions from small samples of data.
90
Table 19: Rate of failure at the voltage which causes breakdown
Oil Voltage level of impulse Rate of failure, calculated Rate of failure, calculated
generator which oil failed from the data, at the from the data, at the
on voltage level which the voltage level prior to
oil failed on failure
(-kV)
Mineral oil 200 5/5 0/3
FR3 190 5/5 0/3
Midel 7131 170 5/9 0/3
4.5 Conclusions
The mean of the AC breakdown voltages for both esters, calculated from a sample of
100 measurements, are higher than that of the mineral oil. The mean AC breakdown
voltages are as follows: 41kV for FR3, 47kV for Midel 7131 and 39kV for mineral oil.
The breakdown voltages were found using ASTM D1816 with a 1mm oil gap.
It can be seen from the histograms that the distributions of AC breakdown voltages are
skewed. Midel 7131 had the most skewed distribution. The skewness of the oils was
sufficient to cause them to fail the Shapiro Wilk test for normality. Since the Gaussian
distribution cannot model skewness, it will not reliably estimate the breakdown voltage
at a low probability.
As measured, the breakdown voltages for 1% probability of failure are 25kV for
mineral oil, 24kV for FR3 and 24kV for Midel 7131. Consequently the breakdown
voltages of esters, at this probability, are not less than that of mineral oil. It is notable
that although the mean breakdown voltage of Midel 7131 is the highest out of these
samples (47kV) its 1% breakdown voltage is not higher than that of the other two.
The Weibull distribution tended to be more accurate in modelling the breakdown

voltage at low probabilities than when applying the Gaussian distribution. This can be
explained by the fact that the Gaussian distribution assumes that the skewness is 0 and
the kurtosis is 3 whereas the Weibull distribution does not make these assumptions.
91
The mean lightning impulse dielectric strengths were: -200kV for mineral oil, -190kV
for FR3 and -170kV for Midel 7131. The lightning impulse breakdown voltages were
measured using ASTM D3300 using the 12.7mm spherical electrode configuration and
3.7mm oil gap.
The lightning impulse dielectric strength of the FR3 was found to be comparable to that
of the mineral oil. The dielectric strength of the Midel 7131 was found to be 30kV less
than that of the mineral oil. There are three suggestions for the dielectric strength of
Midel 7131 being lower:
i. Firstly this may be due to the statistical nature of failure. The test procedure
requires only three withstands on each step before the voltage is raised. If the
probability of failure is low it may be that the oil will fail at this voltage, but
more than three impulses are required to observe failure.
ii. Secondly conductive particles are known to affect the lightning impulse
dielectric strength. The particles in Midel 7131 may be more conductive than the
other two oils and therefore affect the lightning dielectric strength to a greater
degree.
iii. Thirdly the molecular nature of the constituents of Midel 7131 may affect the
process of breakdown. Compounds with large electron trapping cross sections or
low ionisation potentials affect the propagation of streamers through the oil.
92
Chapter 5: Effect of Water on the Breakdown Voltages of
New Oil
5.1 Introduction
This chapter gives an overview of current knowledge of the effect of water on the
breakdown voltage of oil, then studies the impact of water on the breakdown voltages of
the esters compared to mineral oil.
It is well established that water decreases the breakdown voltage of an oil [80,81,106].
Over time and without intervention the wetness of an oil increases, which can be caused
by the following processes:
i. Water is produced chemically by the degradation of cellulosic insulation
ii. Water can leak through poorly maintained seals
iii. Water leakage into the tank can be caused by poor working practices during
maintenance
Water can exist in oil in either dissolved or in the form of globules. A globule exists
when the local oil volume becomes saturated and cannot further dissolve water.
5.2 The Water Uptake Mechanisms of Oil
5.2.1 The Process of Dissolution
Since water molecules are polar, and oil molecules are largely non-polar, only a small
amount of water can dissolve in an oil.
The reason for this is that water dissolves by forming hydrogen bonds between itself
and the polar part of the solute. If the solute is not polar then these bonds cannot form
and thus the water and solute do not easily dissolve. Although oil is generally
considered to be non-polar there will always be a small quantity of polar structures in
the oil, both in impurities contained within the oil and within the oil itself.
93
Once there is more water in the oil than the oil can dissolve, free water begins to form.
The solubility of an oil is a function of temperature, thus one might reasonably assume
temperature to have an effect on breakdown voltage. Therefore the effect of temperature
on breakdown voltage is studied in chapter six.
Esters, as shown in table 20, are much more hygroscopic than mineral oil. This is
explicable because ester molecules are more polar than mineral oil, hence hydrogen
bonds form more readily between the polar part of the ester molecule and water.
Table 20: Comparison of the water solubility of the oils used in this investigation
Oil Solubility @ 20°C

(ppm)
Mineral oil 55
FR3 1100
Midel 7131 2700
A small quantity of water dissolves into mineral oil. This is because the water is able to
bond with aromatic structures within the oil and with polar impurities remaining from
refining [82].
Kóréh et al studied the existence of water in transformer mineral oil, at room

temperature, using infrared spectroscopy [83]. They found that dissolved water exists in
oil in two distinct states. The first state, at water levels of below 10ppm, is when the
water is dispersed as single molecules. The second state, at water levels between 10ppm
and 50ppm, is when the water begins to form small clusters of molecules.
Kóréh believes that at concentrations of below 10ppm a water molecule is completely

surrounded by oil molecules, preventing hydrogen bonds from forming between the
water molecules. At concentrations above 10ppm the molecules of water are in a
suitable proximity for them to form hydrogen bonds between themselves and thus
clusters begin to form.
94
5.2.2 The Process of Water Uptake by Oil
When an oil is exposed to air, water will diffuse between the oil and the air. The water
content of the air is usually expressed in terms of relative humidity, which is defined as:
The percentage relation between the actual amount of water vapour in a given volume
of air at a definite temperature and the maximum amount of water vapour that would be
present if the air were saturated with water vapour at that temperature [84].
The relative humidity of oil is expressed by equation 5.2 as the percentage relation
between the mass of water (W) dissolved in a given volume of oil at a definite
temperature and the mass of water that would be present if the oil were saturated with
water at that temperature (W0).
t
s = t × 100% (5.2)
u(v)
The water content of an oil will equilibrate with the water content of the air. Oil is a
blend of compounds with each having an individual hygroscopy. Consequently the
water must not only equilibrate between the air and oil but between the individual
components of the oil itself.
Fofana et al studied the water uptake of mineral oil and showed that, depending on
relative humidity and temperature, it can take days for the water content of mineral oil
to equilibrate with the air, shown in figure 33 [87]. There is a trend that the oil
conditioned at 60°C reaches a lower relative water content than when conditioned at
23°C. Fofana suggests that the scatter could be related to the difference in the initial
relative water content of the oils and comments that additional investigations are needed
before drawing further conclusions.
95
Figure 33: Rate of water uptake of mineral oil as functions of air relative humidity and
temperature [87]
5.3 The Effect of Water on the Dielectric Strength of Oil
5.3.1 Effect of Water Globules on the Dielectric Strength of Oil
The effect of water globules on oil breakdown has been studied by Garton and Krasucki
[85]. They photographed a globule being distorted by an electric field, with both ends
being pulled outwards to the electrodes. Eventually the globule becomes unstable and
expands explosively. Total breakdown of the gap occurred just before the water
channels bridge the electrodes.
Garton and Krasucki measured the magnitude of the electric field required to produce
instability in a water globule. Based on their results, they proposed equation 5.1 where
ST is the surface tension acting on the boundary of the globule in dyn/cm, ε is the
relative permittivity of the oil, R is the radius of the bubble in cm and ECrit is the electric
field required to cause instability in volts per cm.

|
wxY = 487.7 }v volts/cm (5.1)
The authors used the values of ST = 43dyn/cm and ε = 2 to propose that a bubble with a
radius of 0.05µm becomes unstable in an electric field of 1MV/cm. A water bubble of
this volume contains around 107 molecules.
96
Garton and Krasucki recognise that small bubbles of water are unlikely to exist for an
appreciable time in an oil not saturated with water.
Even though Kóréh has observed that clusters of water molecules may exist in mineral
oil, they do not estimate their maximum sizes [83]. Garton and Krasucki showed that
water globules can cause breakdown, however, the sizes of globule mentioned, 0.05µm,
will contain 107 water molecules. Although Kóréh provides evidence that a small
number of water molecules may form a cluster, no evidence that a cluster can be formed
of 107 molecules is provided.
5.3.2 Effect of Dissolved Water on the Dielectric Strength of Oil
The reason for the effect of dissolved water on the breakdown voltage of oil is less well
understood than the effect of suspended water globules. Since the quantity of dissolved
water usually increases during the working life of the oil it is important to analyse the
role of water on reducing the dielectric strength of the oil.
5.3.3 Effect on AC Dielectric Strength
Cooper Power Systems investigated the effect of water on the AC breakdown voltage of
FR3 and report that water reduces the breakdown voltage of FR3 less than that of
mineral oil, as shown in figure 34 [86]. The breakdown voltage was measured using
standard ASTM D1816, the same one used in this project, although the authors used a
different electrode gap which was 2mm. It can be seen that the breakdown voltage of
the mineral oil quickly falls as its water content increases to 50ppm. The breakdown
voltage of the FR3 only begins to fall after its water content is higher than 300ppm.
97
Figure 34: Effect of water on the AC breakdown voltages of FR3 [86]
There is a general trend that the reduction in dielectric strength of an oil is related to the
relative humidity of an oil rather than the absolute water content. As an example of the
significance of the relative humidity: At ambient temperature, 30ppm of water
represents approximately 60% saturation of the mineral oil and 1% saturation of the
synthetic ester. It would therefore be expected that the effect of 30ppm water on the
breakdown voltage would be large for the mineral oil and negligible for the synthetic
ester.
Fofana et al studied the effect of water on the AC breakdown voltages of mineral oil
and a synthetic ester using standard IEC 60156 [87]. The water content of the oil was
increased by placing a sample of the oil into a desiccator and allowing the oil to take up
water from the air. The relative humidity of the air was controlled by a solution of
glycerol. It can be seen in figure 35 that the breakdown voltages of the oils are
decreased by the water. The breakdown voltages U1 and U2, shown in figure 35,
correspond to the limits for the breakdown voltages of unused and used oils as
suggested by the IEC (International Electrotechnical Commission) [55,88]. The water
contents R1 and R2 are the water levels which would reduce the breakdown voltages of
the oils to the suggested limits of U1 and U2.
98
Figure 35: Effect of water on the AC breakdown voltages of mineral oil and a synthetic
ester [87]
Chadband hypothesized that water affects the breakdown voltage of an oil by

influencing the conductivity of microscopic particles suspended in the oil [35]. When
these particles become more conductive they can produce a larger discharge at an
electrode and thus increase the likelihood of bubble initiated breakdown. This
phenomenon was observed by Miners who studied the effect of particles on the AC
breakdown voltage of mineral oil [39]. Miners investigated the dielectric strength of oil
contaminated with different levels of water, of up to 30ppm, and 45 µm particles of
cellulose. He concluded “the reduction of the dielectric strength of oil, due to the
presence of cellulose particles, was amplified at higher moisture content”.
Vincent et al studied the effect of water on the breakdown voltage of mineral oil using
very clean oil [89]. The oil was cleaned using a 0.2µm filter until the cumulative
particle count was less than 200 particles smaller than 5µm in a volume of 100ml. The
breakdown voltages, shown in figure 36, were measured using the following
configurations of electrodes, gap sizes and voltage applications:
• ASTM D1816 with VDE electrodes set at 2mm apart and 0.5kV/s ramp rate
• ASTM D1816 with VDE electrodes set at 2mm apart and 1 minute step by step
voltage application (listed as “ASTM mod” in figure 36)
• Coaxial electrodes set at 0.5mm apart and 1 minute step by step voltage
99
application
• Coaxial electrodes set at 2mm apart and 1 minute step by step voltage
application
The coaxial electrodes set at a gap of 0.5mm had a surface area of 65cm2 and the type
set at a gap of 2mm had a surface area of 330.7cm2. One of the curves was taken from
another study, performed by Sinz [90]. This used a configuration of coaxial electrodes
set a gap of 1mm.
Figure 36: Influence of water on the breakdown voltage of mineral oil [89]
The most striking result of this investigation was that water does not appear to have
affected the breakdown voltage of the oil using standard ASTM D1816 over the studied
range of water.
The geometry of the electrodes, size of gap and method of voltage increase can be seen
to affect the degree to which water reduces the breakdown voltage. Vincent proposes
that the differences in the effect of the water are due to the statistical nature of
breakdown with the risk of breakdown being dependent on the surface area of the
electrodes and the volume of the oil under stress. The more oil that is stressed the
greater the chance of the occurrence of breakdown.
The difference between the “ASTM” and “ASTM mod” methods is that for the ASTM
100
method the voltage is applied as a 0.5kV/s ramp whereas it is applied in a step by step
format for the ASTM mod. Vincent believes that the difference in the effect of water
between the ASTM methods is caused by the longer time under voltage in the “ASTM
mod” method, which gives the contaminants more time to move close to an electrode
and initiate breakdown.
Returning to the theory of particle initiated breakdown proposed by Chadband, it may

be reasonable to conclude that water has not affected the breakdown voltages performed
to ASTM D1816 because the oil is relatively free of particles. However, although the oil
used in this investigation was “clean” it still had 200 particles smaller than 5µm per
100ml of oil.
Therefore it is difficult to conclude for the measurements using the other electrodes
whether breakdown is explicable by the particle theory proposed by Chadband or if
water has affected the breakdown voltages alone.
5.3.4 Effect on Lightning Impulse Dielectric Strength
Despite a thorough literature search during this PhD study little data has been found
considering the impact of water on the lightning impulse breakdown voltage of oil.
Both Linhjell [46] and Chadband [36] propose the theory that particles affect the
dielectric strength of oil. Linhjell studied the effect of particles on the lightning impulse
dielectric strength of oil. He concluded that only conductive particles affect breakdown
because these polarize instantaneously and cause breakdown whereas non-conductive
ones do not have sufficient time to have an effect.
Chadband put forward the theory that water is absorbed by hygroscopic insulating
particles, which increases their conductivity thus increasing their impact in reducing the
breakdown voltage of an oil. Therefore while non-conducting particles do not affect the
lightning impulse dielectric strength of oil, once they absorb water they may become
conductive enough to have an effect.
Perret studied the effect of water on the lightning impulse breakdown voltage of
transformer oil. The oil was firstly passed through a 5µm porosity filter. He prepared the
sample by mixing 0.06% (by volume) of water with a naphthenic mineral oil then
101
shaking them together for four hours. Perret found the mean breakdown voltage of the
mineral oil contaminated with water to be 134kV, higher than the oil in its state at
delivery, which was 123kV. He therefore concluded that water has no affect.
This method of preparation was rejected by Du [91]. She argued that to add an excess of
water to a sample, shake it up and leave to stand overnight was an improper method
because the diffusion process of water is very slow and letting the oil stand overnight
does not guarantee full dissolution.
It is important that the process of dissolution leads to the water becoming properly
dispersed, existing, as observed by Kóréh, as single molecules or as clusters of more
than one molecule [83]. If shaken, although the water bubbles may be too small to be
visible, they may not be dispersed as the clusters reported by Kóréh.
Du further notes that although water is heavier than oil, small water bubbles can exist
near the upper body of the oil due to surface tension. Since only the oil within the
electrically stressed volume breaks down, it is possible that the added water may not
actually be dispersed within the electrified volume.
Perret’s study would have been more persuasive if he had used multiple samples of oil
with differing quantities of water. Since particles affect the dielectric strength of oil, as
proposed by Chadband [36], it is plausible that because Perret filtered his oil before use
he would not have observed the effect of water because there were few particles in his
oil.
5.4 The Preparation of the Wet Samples of Oil Used in this

Investigation
Du advises that care must be taken when preparing wet samples of oil [91]. She argued
that firstly it is difficult to control such small quantities of moisture with a pipette or
syringe and secondly uniform dissolution is not guaranteed. A solution of glycerol was
used in this investigation to increase the water content of the oils. Glycerol solution
increases the water content of oil by controlling the relative humidity of the air around
the oil. The oil then absorbs moisture from the air to achieve equilibrium. However, it is
necessary, not only to allow the water content of the oil to equilibrate with the air, but
102
also to equilibrate throughout the oil. ASTM have published a standard, D5032
“Standard Practice for Maintaining Constant Relative Humidity by Means of Aqueous
Glycerin Solutions”, to advise on the use of glycerol to vary the relative humidity of the
air [92].
The relative humidity of the air can be expressed as the percentage relation between the
vapour pressure of the water (p) and the maximum vapour pressure of the water at
saturation (p0), shown in equation 5.3.

s = (5.3)
u(v)
Vapour pressure is defined by Persuad as the “partial pressure exerted by the vapor of a
substance in the gaseous phase of a closed heterogeneous system at equilibrium with
condensed phases (i.e., solid or liquid) of the substance present in the system” [93].
When the condensed phase is in solution the vapour pressure of the condensed phase
can be explained by Raoult's law:
The vapour pressure of a substance in equilibrium with a solution containing the

substance is equal to the product of the mole fraction of the substance in the solution
and the vapour pressure of the pure substance at the temperature of the solution.
This assumes that the solution is concentrated and the components do not interact.
Raoult’s law is expressed in equation 5.4, where P is the resulting vapour pressure, x is
the mole fraction of component a in solution and Pa is the vapour pressure of pure a at
the same temperature and pressure as the solution [94].
" = 8~ "~ (5.4)
The vapour pressure of water in a solution of glycerol is therefore dependent on the

molar fraction of the water. Consequently the relative humidity of the air is controlled
by the proportion of glycerol in solution, shown by Fofana in figure 37 [87].
103
Figure 37: Dependence of the relative humidity of air on the proportion of Glycerol in
solution in a sealed container [87]
Six Petri dishes were used to give a large surface area for moisture uptake, shown in
figure 38. After conditioning, the oil from the six Petri dishes was bottled and stored for
one week to allow further diffusion of the moisture to create a high degree of
consistency throughout the sample.
Figure 38: Desiccator and Petri dishes used to control the water content of oil
104
The first samples, of 2% relative humidity, were obtained by vacuuming the sample to
less than 10mbar in a Heraeus vacuum oven as it was found that this was not achievable
using the desiccator. The exact water content of each oil was determined by Karl
Fischer analysis. A Metrohm 684 Coulometer with 832 Thermoprep oven were used to
provide water readings. Although the coulometer gives readings with a high degree of
accuracy care is required to reduce the impact of variations in background moisture in
introducing errors. Two measurements were taken then averages found.
5.5 Particle Count of Oil
Particles appear to be instrumental in the effect of water on reducing the breakdown

voltage of oil. Therefore the number and size of the particles in new oil, obtained from
the barrel, was counted.
The particle counts were measured using a HIAC Royco 8000A Eight Channel Particle
Counter with a HIAC Royco ABS2 Automatic Bottle Sampler, operated by TJH2b
analytical services. A graph showing the cumulative number of particles per 100ml of
oil is given in figure 39. Since the oils used to analyse the effect of water on their
dielectric strengths were conditioned in a desiccator, their particle contents are likely to
have been higher due to handling the oil and exposing the oil to the air.
100000
Cumulative number of particles per 100mL
90000
80000
70000
60000
50000
of oil
Mineral oil
40000
FR3
30000
20000 Midel 7131
10000
0
2-5μm >5-15μm >15-25μm >25-50μm >50-100μm >100μm
Size of particle
Figure 39: Cumulative number of particles per 100ml of oil
105
Since the oils have higher particle counts than the oil used by Vincent (fewer than 200
particles smaller than 5µm per 100ml of oil) it is likely that water will have an
observable effect on the AC dielectric strength of these oils using standard ASTM
D1816.
5.6 Comparison of the Effect of Water on the Mean AC Breakdown

Voltages
A Baur DPA75 oil tester was used to measure AC breakdown voltage as per standard
ASTM D1816, using partially spherical electrodes and 1mm gap. However, twenty
breakdowns were measured rather than the minimum five to give a fuller distribution.
The results are given in figures 40 & 41.
60
50 FR3 Midel 7131
40
Error bars = Mean ± 1 standard deviation
30
20
10
0
0 500 1000 1500 2000
Water content (ppm)
Figure 40: AC breakdown voltages of the esters as functions of water content (ppm)
106
60

50
40
30
20
10
0
0 10 20 30 40
Water content (ppm)
The results confirm the expected correlation between water solubility and breakdown
voltage (ppm) and clearly demonstrate that the esters can absorb more water than
mineral oil before their mean AC breakdown voltages are affected.
The results for the FR3 are similar to those provided by the manufacture in figure 34.
The dielectric strength of FR3 provided by the manufacturer is around 34kV/mm up to a
water content of 300ppm, after which the dielectric strength begins to fall and is
approximately 20kV/mm at 500ppm of water.
Figure 42 shows that esters also have higher mean breakdown voltages than mineral oil
at a given percentage relative humidity. Since the dielectric capabilities of these oils in
terms of relative humidity differ it indicates that there are other factors, not just the
relative humidity, which influence the breakdown voltage of a wet oil.
107
Breakdown voltage 1mm gap (kV) 60
Mineral oil
50 FR3
40 Midel 7131
30 Error bars = Mean ± 1 standard deviation
20
10
0
0 20 40 60 80 100
Water content (%RH)
Figure 42: AC breakdown voltages of oils as functions of relative humidity
The results for the mineral oil and Midel 7131 are different to those reported by Fofana
in figure 35. Fofana shows that the mean breakdown voltage of the ester, as a function
of relative humidity, is less than that of the mineral oil. In contrast, the mean breakdown
voltages of Midel 7131, with varying levels of water, were found to be higher than those
of the mineral oil. The hygroscopy of the ester used by Fofana is 2700ppm at 20°C, the
same as for Midel 7131. Consequently the breakdown voltages of oil cannot be
explained solely in terms of relative humidity.
As discussed earlier, Chadband proposed the theories that particles can cause dielectric
failure and that water affects the breakdown voltage of oil by increasing the
conductivity of hygroscopic insulating particles. When these particles are more
conductive they can cause a larger discharge at an electrode.
The connection between the hygroscopy of an oil, suspended particles and the
breakdown voltage may be that when the oil is more hygroscopic more water is
dissolved by the oil and less water is adsorbed by the particles. Thus the hygroscopic oil
keeps the particles drier and less conductive.
This section has analysed the effect of water on the mean breakdown voltage of a
distribution. The next section investigates the degree of impact of water on the
108
dispersion of breakdown voltages.
5.7 Comparison of the Effect of Water on the Distribution of AC

Breakdown Voltages
In addition to investigating the effect of water on the mean dielectric strength of oil it is
essential to analyse the effect of water on the distribution of breakdown voltages and in
particular the lowest points of the distribution. The dispersion of the breakdown voltage
distributions is quantified by the coefficient of variation (CV%) which is given by
equation 5.5 where σ is the standard deviation of the sample and 89 is the mean
breakdown voltage.
;
7% = (5.5)
<9
Comparing with the coefficients of variation shown in figure 43 it is seen that the
coefficients of variation of both esters, shown in table 21, are generally not in excess of
those of the mineral oil. Therefore the dispersions of breakdown voltages of esters are
likely to be similar to those of mineral oil.
60156 [50]
109
Table 21: Coefficients of variation for the distributions of AC breakdown voltage,
performed using 1mm electrode gap, with varying levels of water
Oil Water content Mean breakdown Standard Coefficient of

voltage deviation variation
(kV) (kV) (%)
Mineral oil 5ppm, 10%RH 29 4.5 16

7ppm, 12%RH 22 4.0 18
14ppm, 25%RH 20 4.1 21
17ppm, 31%RH 15 3.8 25
19ppm, 35%RH 17 4.2 25
20ppm, 36%RH 16 4.9 31
28ppm, 51%RH 7 2.9 41
FR3 31ppm, 3%RH 34 3.7 11
70ppm, 6%RH 40 4.4 11
117ppm, 11%RH 39 5.2 13
146ppm, 13%RH 36 6.4 18
273ppm, 25%RH 38 5.8 15
339ppm, 31%RH 38 7.5 20
420ppm, 38%RH 25 5.7 23
532ppm, 48%RH 24 5.0 21
881ppm, 80%RH 8 0.8 10
Midel 7131 76ppm, 3%RH 44 5.3 12
168ppm, 6%RH 38 9.1 24
312ppm, 12%RH 40 10.7 27
539ppm, 20%RH 42 10.8 26
644ppm, 24%RH 38 10.6 28
799ppm, 30%RH 30 8.4 28
1188ppm, 44%RH 14 3.0 21
1569ppm, 58%RH 11 2.1 19
1921ppm, 71%RH 10 1.4 14
There is a general trend that the CV% increases as the water content of the oil increases.
In the case of the two esters, the CV% is then seen to reduce at very high relative
humidities. For the mineral oil, which did not reach such high levels of relative
humidity, this is not seen. The mineral oil differs from the esters again in that its
breakdown voltage steadily reduces as the relative humidity and CV% increase whereas
the CV% of the esters starts to increase while the breakdown voltage is plateaued.
Commenting on the relation between breakdown voltage, measured according to IEC

60156 using a 2.5mm gap, and CV%, shown in figure 43, Lick noted that there is a
general trend that the CV% is high when the mean breakdown voltage is between 40kV
and 60kV [51]. Lick comments that the occurrence of breakdown at a low voltage is
related to the probability of a weak link appearing between the electrodes. When the
quality of the oil is very poor, a weak point always appears between the electrodes,
resulting in a mean voltage of below 40kV. When the quality of the oil is high, the
110
probability of a weak point appearing between the electrodes is low, resulting in a
breakdown voltage of above 60kV. Between these extremes it is not predictable whether
the contaminant will cause breakdown or not resulting in a high coefficient of variation.
Lick’s explanation can be applied to the impact of water on the CV% of the oil. When
the oil is dry there are few weak links so the probability of a weak link appearing
between the electrodes is low. When water is added to an oil the number of weak links
increases. At low quantities of water it is unpredictable whether the water causes
breakdown or not. At high quantities of water, water always causes breakdown. The
terms of “high” and “low” quantities of water are relative for an oil and are determined
by the hygroscopy of the oil.
The use of weak link theory to explain the effect of water on the breakdown voltage of
oil would support the hypothesis that breakdown is not caused by a uniform dispersion
of water within the oil. If breakdown were caused by uniform dissolution, then there
would always be a weak link in the oil. Therefore it would not be unpredictable whether
water causes breakdown or not.
The distributions of breakdown voltages as functions of water content are given in

figures 44 – 46.
For mineral oil, except for the wettest (28ppm) sample, the lowest breakdown voltages
tend to be grouped between 10kV/mm and 20kV/mm. Despite the CV% increasing with
rising water content, the actual dispersion of the data (σ) falls until there is very little
variation in the individual breakdown voltages, at 28ppm.
This corresponds to the proposals of Lick regarding the weak link theory. The large
spread at low water content would seem to imply that few weak links are present so that
the weakest link in the electrically stressed volume and hence the breakdown voltage is
variable. It is known that the oil under investigation contains particles, which are
suggested by Chadband to cause breakdown dependent on their conductivity. Variation
in the conductivity of these particles would explain the dispersion of breakdown
voltages seen at low relative humidity. However, at high water content the particles are
more conductive, hence they always cause breakdown at a, more uniform, low voltage.
111
1
0.9
0.8 5ppm 10%RH
7ppm 12%RH
0.7
Cumulative probability
14ppm 25%RH
0.6
17ppm 31%RH
0.5 19ppm 35%RH
0.4 20ppm 36%RH
0.3 28ppm 51%RH
0.2
0.1
0
0 10 20 30 40 50 60
ac breakdown voltage 1mm gap (kV)
Figure 44: Distributions of AC breakdown voltages for mineral oil as functions of water
content
The results for the FR3 are shown in figure 45. Except for the two wettest samples of
FR3 the lowest breakdown voltages of this oil were around 30kV, higher than those of
the mineral oil. Only when the oil becomes wet, over 339ppm, are the lowest mean
breakdown voltages reduced.
The CV% of the breakdown voltages peaks for water contents in the region of 339ppm
to 532ppm. However, the mean breakdown voltage of the sample with 339ppm has not
been reduced by the water. Therefore this is the region where although water can affect
an individual breakdown, the probability of the effect occurring is not large enough to
affect the mean. For the sample with the highest water content, similarly to the mineral
oil, there is little dispersion in the data.
112
1
0.9
0.8 31ppm 3%RH
70ppm 6%RH
0.7
117ppm 11%RH
0.6
146ppm 13%RH
0.5
273ppm 25%RH
0.4
339ppm 31%RH
0.3
420ppm 38%RH
0.2
532ppm 48%RH
0.1
881ppm 80%RH
0
0 10 20 30 40 50 60
Figure 45: Distributions of breakdown voltages for FR3 as functions of water content
The lowest breakdown voltages of the Midel 7131, shown in figure 46, are between
10kV and 20kV. This is significant because although the mean breakdown voltages of
Midel 7131 are 10kV to 20kV higher than that of the mineral oil, the lowest breakdown
voltages of Midel 7131 are approximately equal to that of the mineral oil.
The coefficients of variation of the breakdown voltages of Midel 7131 are higher than
that of the other two oils. This may indicate that the effect of water on its dielectric
strength is more unpredictable when compared to the other two oils; although the mean
breakdown voltage is high, there is a greater chance of it breaking down at a low
voltage.
The outcome of this is that the insulation designer must be aware that although the mean
breakdown voltage of Midel 7131 is high when the oil is wet, the lowest breakdown
voltages are not.
113
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 10 20 30 40 50 60
76ppm 3%RH 168ppm 6%RH

1188ppm 44%RH 1569ppm 58%RH
1921ppm 71%RH
Figure 46: Distributions of breakdown voltages for Midel 7131 as functions of water
content
Further research will be required to ascertain the cause of the weak links and determine
whether the cause is due to the methodology of the experiment or due to a property of
the oil.
5.8 Comparison of the Effect of Water on Lightning Impulse

Breakdown Voltages
The lightning impulse breakdown voltage was measured as per standard ASTM D3300-
94. A Haefely 10 stage impulse generator was used to provide a 1.2µs/50µs negative
voltage waveshape. The test cell was fitted with spherical 12.7mm diameter brass
electrodes set to a gap of 3.8mm. A low voltage transient was applied and raised in
steps of -10kV until 5 flashovers were observed. The results are given in table 22.
The scatters of the distributions, shown in table 22, are low in terms of the coefficient of
variation compared to those of the AC breakdown voltage distributions. It is in contrast
to the AC breakdown voltages that water over the levels investigated does not appear to
have affected the dispersion. Lick attributed AC failure to weak leaks such as
114
contaminants [51]. Under AC voltage contaminates can move into the electrically
stressed volume and initiate breakdown. Since the duration of a lightning impulse is
very short compared to AC, weak link contaminates will not have sufficient time to
move far in the electric field [79]. Therefore, if a weak link is to cause failure then it
must already be in the electrically stressed volume at a suitable location.
Devins has noted that aromatic compounds decrease the lightning impulse breakdown
voltage of mineral oil [48]. Therefore a weak link of oil, under lightning impulse, may
be molecular as well as a particle.
Table 22: Coefficients of variation of the lightning impulse dielectric strengths of oil
with varying levels of water
Oil Water content Mean dielectric Standard Coefficient of

strength deviation variation
(ppm) (kV) (kV) (%)
Mineral oil 5ppm -205 2.1 1

7ppm -196 4.0 2
14ppm -190 0.5 0
17ppm -169 3.0 2
FR3 26ppm -181 4.2 2

70ppm -166 5.4 3
117ppm -187 6.7 4
273ppm -174 3.3 2
339ppm -180 1.1 1
Midel 7131 77ppm -165 2.7 2

168ppm -172 3.9 2
312ppm -169 2.7 2
539ppm -169 0.5 0
644ppm -171 7.0 4
The effect of water on the distributions of lightning impulse breakdown voltages is

shown in figures 47 to 49.
The breakdown voltages of mineral oil appear to decrease as the water content
increases. At 17ppm, or 31% relative humidity, the lightning impulse breakdown
voltage of mineral oil was seen to be approximately the same as the esters.
115
The mean lightning impulse breakdown voltage of mineral oil is decreased less by the
water than its AC breakdown voltage. Between 5ppm and 17ppm the AC breakdown
voltage was halved (from approximately 30kV to 15kV) whereas the lightning impulse
breakdown voltage was reduced by about a sixth (from 205kV to 169kV).
1
5ppm 10%RH
0.9
7ppm 12%RH
0.8
0.7 14ppm 25%RH

0.6 17ppm 31%RH
0.5
0.4
0.3
0.2
0.1
0
150 160 170 180 190 200 210 220
Negative breakdown voltage 3.8mm gap (-kV)
for mineral oil
The lightning impulse breakdown voltage of the FR3, as shown in figure 48, has not
been reduced by a water content of up to 339ppm.
116
1
0.9
0.8
26ppm 2%RH
0.7
70ppm 6%RH
0.6
0.5 117ppm 11%RH
0.4 273ppm 25%RH
0.3 339ppm 31%RH

0.2
0.1
0
150 160 170 180 190 200 210 220
Negative breakdown voltage 3.8mm gap (-kV)
for FR3
The mean lightning impulse breakdown voltage of the Midel 7131, as shown in figure
49, has not been reduced by a water content of up to 644ppm.
1
0.9
0.8 77ppm 3%RH
0.7
168ppm 7%RH
0.6
312ppm 12%RH
0.5
539ppm 22%RH
0.4
644ppm 26%RH
0.3
0.2
0.1
0
150 160 170 180 190 200 210 220
Negative breakdown voltage 3.8 mm gap (-kV)
for Midel 7131
117
5.9 Conclusions
In terms of percentage saturation water affects the AC dielectric strengths of esters less
than that of mineral oil. The mean and lowest breakdown voltages of FR3 were superior
to those of mineral oil. However, although the mean breakdown voltages of Midel 7131
were higher than those of mineral oil at the same relative humidity, its lowest
breakdown voltages were only comparable to those of mineral oil.
Since it has been observed in this investigation, and by Fofana, that the dielectric
performance of these oils as a function of relative humidity differs, there are likely to be
other factors, not just the hygroscopy, which influence the breakdown voltage of a wet
oil.
Garton and Krasucki showed that water globules can cause breakdown, however, the
sizes of globule mentioned, 0.05µm, will contain 107 water molecules [85]. Kóréh
provides evidence that a small number of water molecules may form a cluster, however,
no evidence that a cluster can be formed of 107 molecules is provided [83].
Chadband believes that water affects the conductivity of hygroscopic insulating

particles [36]. When these particles are wet they initiate breakdown at a lower voltage.
This seems consistent with the application of Lick’s suggestions [51] regarding the
weak link theory to explain the change of coefficient of variation with relative humidity
seen in the investigation of AC breakdown voltage.
Chadband’s theory may also provide an explanation as to why water affects the
dielectric strength of an ester less than that of mineral oil: Since esters are more
hygroscopic than mineral oil they absorb a greater proportion of the water, hence
keeping the particles drier. When the particles are dry they remain non-conductive and
therefore there is less of an affect on the breakdown voltage of the oil.
Water, over the range studied, appears to have affected the lightning impulse dielectric
strength of the mineral oil although it has not affected the lightning impulse dielectric
strength of the esters.
The result for the mineral oil may be explained by Linhjell [43] and Chadband [36].
118
Linhjell proposes that only conductive particles affect the lightning impulse dielectric
strength of oil because these polarise instantaneously in the short duration of the
lightning impulse. Chadband proposes that water increases the conductivity of particles
suspended in oil.
Since esters are more hygroscopic than mineral oil more water would be dissolved by
the ester and less adsorbed by the particles, therefore the particles suspended in esters
are drier and less conductive. It may be that higher relative humidities than were
investigated would be required to observe a change in the lightning impulse dielectric
strengths of the two esters.
119
Chapter 6: Effect of Temperature on the Breakdown Voltages
of New Oil
6.1 Introduction
During transformer operation an oil will heat up and cool down due to the load cycle of
the transformer, hotspots around conductors and thermal variations within the
transformer insulation system. It is therefore necessary to examine the degree of impact
that temperature has on the dielectric strengths of the esters compared to mineral oil.
This chapter investigates the effect of different levels of temperature, between 30°C and
70°C, representative of the temperature of the oil within a transformer on the
breakdown voltage of new oil.
6.2 Background to the Effect of Temperature on the Dielectric

Strength of Oil
Several researchers have investigated the effect of temperature on the dielectric strength
of mineral oil.
Adamczewski believed that the dielectric strength of a liquid should decrease with
rising temperature since the density and viscosity of the oil decrease with temperature
[28]. Therefore, there are less oil molecules per unit volume and charge carriers become
more mobile. However, the data provided by Adamczewski shows that the breakdown
voltage as a function of temperature is flat between 20°C and 75°C, indicating little
influence is to be expected at the temperatures studied in this investigation.
Blume [61] and Clark [95] both independently show increases in breakdown voltage
with temperature for mineral oil. Blume noted an increase from 25kV to 35kV between
20°C and 100°C and Clark shows an increase from 32kV to 34kV between 20°C and
100°C. Neither Blume nor Clark comment on the statistical significance of their results
so it is difficult to determine whether this apparent increase in dielectric strength is
actually due to the change in temperature. Comparison with Clark’s results is not
possible in this investigation as the variations found by him (32kV – 34kV) would not
120
appear statistically significant with the context of these results as they are too small
relative to the spread of the data.
Musil et al believe that the AC breakdown voltage of insulating oil is dependent on the
relative humidity of the oil which will change with temperature [52]. Musil cites
research, published previously in German by Holle [96], reporting the effect of
temperature on the breakdown voltage of an insulating oil which is shown in figure 50.
Figure 50: Effect of temperature on the breakdown voltages of an insulating oil with
different water contents [96]
Beyer and Borsi studied the dielectric strengths of Midel 7131 and silicone fluids using
varying levels of water and temperature [81,97]. In their experiments the breakdown
voltage of the ester increased from 25kV to 30kV from 20°C to 60°C then fell back to
25kV between 60°C and 100°C.
Beyer and Borsi report a major difference between the effect of water on the dielectric
strength of mineral oil and Midel 7131. This is that the “dielectric strength (of mineral
oil) may be described as a function of relative humidity, thus all breakdown data at the
different temperatures and different absolute humidity contents can be in mutual
dependence. This is not possible... with ester fluid”. Furthermore, although there is not a
121
proportional relationship between the relative humidity and the breakdown voltage of
Midel 7131, there is still a general trend that the lower the relative humidity the higher
the dielectric strength.
Since there did not appear to be a mutual dependence between the relative humidity and
breakdown voltage of Midel 7131, Borsi concluded that the breakdown of this fluid was
not due “to physical dissolving of the water” [81]. Borsi attempted to explain his results
by theorizing that the shape of the ester molecule influences the mobility of the
electrons within the oil which affects dielectric failure. Unfortunately no further
evidence has been found supporting or contradicting this theory.
Jayaram studied the breakdown voltage of Voltesso 35, a mineral oil, using different
flow rates and temperatures [98]. The breakdown voltage of the oil was found using
standard ASTM D1816. The dielectric strength of the oil was observed to increase with
rising temperature, as shown in figure 51.
Figure 51: Effect of temperature and flow rate on the dielectric strength of mineral oil
[98]
The water content of the oil was 35ppm which is around 70% humidity at room
temperature. The results of the breakdown voltages measured at temperatures of up to
around 100°C are in agreement with those of Holle shown in figure 50. However,
Jayaram does not consider the role of relative humidity and instead suggests that the
change in breakdown voltage is due to physical processes such as viscosity, interfacial
tension and density, with the effect of temperature on viscosity shown in figure 52.
Jayaram believes that the decrease in breakdown voltage at around 100°C is due to the
122
water vaporising more easily and forming steam.
Figure 52: Effect of temperature on oil viscosity [98]
Wasserburg investigated the breakdown voltages of the Proeco TR20 synthetic ester
using temperatures between 20°C and 120°C and reported no change in dielectric
strength, shown in figure 53 [99]. The dielectric strength of the oil was measured using
standard IEC 60156. Although Wasserfall gives the water content of the samples tested,
75ppm, 210ppm and 500ppm, the relative humidity is not provided.
This is unfortunate since there is a general principle that the breakdown voltage of an oil
is dependent on its relative humidity and not absolute water content. Proeco is a
synthetic ester and these can be highly hygroscopic. As an example Midel 7131, another
synthetic ester, can absorb 2700ppm at room temperature. If a sample of Midel 7131
had absorbed 500ppm of water at room temperature, it would only be 19% saturated.
Referring to the breakdown voltages of Midel 7131 as a function of relative humidity in
figure 42, this percentage saturation is not high enough to affect its breakdown voltage,
the same may be true for Proeco.
123
Figure 53: Breakdown voltages of Proeco as a function of temperature [99]
6.3 Investigation to Compare the Effect of Temperature on the

Dielectric Strength of Oil
When an author has claimed that temperature has affected the dielectric strength of oil,
they tended to explain their results by one of two following theories: One is that the
change in temperature has affected the relative humidity of the oil which in turn affects
the dielectric strength of the oil. The other is that the change in temperature has affected
the physical characteristics, such as density or viscosity, of the oil. It may be possible
that both theories explain an effect of temperature on the dielectric strength of an oil.
However, since an oil fails on the weakest link it may be that one mechanism will be
more prominent than the other for oils of the quality used in this investigation.
To ascertain the degree of effect of temperature on the dielectric strengths of the oils,
the investigation progressed in the following steps:
1. The effect of different levels of temperature between 30°C and 70°C on the
dielectric strength of dry oil. This will determine whether a change in physical
properties such as density and viscosity affect the dielectric strengths of the oils
over this temperature range
2. The effect of different levels of temperature between 30°C and 70°C on the
dielectric strength of oil with relatively high levels of water. This will determine
whether a change in the relative humidity of an oil will affect its dielectric
124
strength
This range of temperature was chosen for investigation because, disregarding hotspots,
it is similar to the normal operating temperature of oil in a power transformer.
6.4 Effect of Temperature on the AC Dielectric Strength of Dry Oil
The first step was to determine whether temperature affects the dielectric strength of dry
oil. This was to investigate whether thermal properties, such as viscosity or density,
affect the dielectric strength of these oils. Table 23 shows the kinematic viscosity and
density of the oils as a function of temperature.
Table 23: Viscosity and density of oil as a function of temperature
Oil & source Temperature Kinematic Density

viscosity
(°C) (mm2 /s) (kg/m3)
Mineral oil 20 20 885

Nynas 40 9 874
60 5 863
80 3 852
FR3 20 70 920
Cooper Power 40 32 907
60 18 894
80 11 880
Midel 7131 20 70 970

M & I Materials 40 28 956
60 14 941
80 8 926
The DPA 75 test cell, shown in figure 54, was filled with oil and placed in an oven
under vacuum of less than 10mbar, heated to 70°C, overnight. The vacuum was applied
to dry the oils.
125
Figure 54: Baur DPA 75 test cell used in this investigation
Prior to the dielectric strength being measured, the water contents of the oils, shown in
table 24, were found by using the Karl Fischer titration method performed by the
Metrohm 684 Coulometer and 832 Thermoprep oven.
Table 24: Water contents of dry oils used in this investigation
Oil Water content Relative humidity

@ 20°C
(ppm) (%)
Mineral oil 1 2
FR3 125 11
Midel 7131 116 4
Once the test cell was removed from the oven it was sealed to prevent the ingress of
water into the oil. The dielectric strengths of the oils were found using the Baur DPA 75
oil tester and standard ASTM D1816. The standard calls for a series of five breakdowns
but the Baur DPA75 oil tester calculates the coefficient of variation for a series of five
breakdown voltages and if this is greater than 10% the DPA75 will measure a further
five breakdown voltages giving a sample size of ten.
The temperature gauge on the DPA 75 oil tester was found to be unsuitable for
measuring temperatures higher than around 40°C so an infra-red type thermometer was
used (ETI TN1), shown in figure 55.
126
Figure 55: ETI TN1 Infra-red thermometer used to measure the temperatures of the oils
in this investigation
An advantage of using this thermometer rather than an immersion type is that the
temperature of the oil can be measured without removing the lid of the test vessel. If the
test cell were opened between measurements there would be a possibility of the water
content of the oil increasing.
The breakdown voltage of the oil was continually found as the oil cooled inside the test
cell. The temperature of the oil and test cell was measured after each series of 5 or 10
breakdowns. The distribution is given rather than the mean breakdown voltage because
it is necessary to ensure that a change of breakdown voltage is not within the scatter of
the measurements. The distributions of breakdown voltages are given in figures 56 – 58.
The temperature at the beginning and end of a series of 5 or 10 breakdowns was

measured using the thermometer. The temperature of the oil at each breakdown was
estimated by linearly interpolating this between the start and end temperatures. As an
example, if the temperature of the oil was 60°C at the start of the investigation and after
5 breakdowns was found to have cooled to 55°C. The fall in temperature is 5°C,
therefore, if this temperature drop is interpolated linearly across 5 breakdowns then it is
estimated that the oil drops 1°C for every breakdown. It is appreciated that the rate of
change of temperature is not, in fact, linear but it is considered to be a reasonable
approximation as the temperature drop between sets of breakdowns is relatively small
when compared to the overall reduction in temperature during the course of the
experiment.
127
60
Sample size = 85
Breakdown voltage 1mm gap (kV) a 50
40
30
20
10
0
20 30 40 50 60 70 80
Temperature (°C)
Figure 56: Distribution of breakdown voltages for dry mineral oil as a function of
temperature
60
Breakdown voltage 1mm gap (kV) a
Sample size = 75
50
40
30
20
10
0
20 30 40 50 60 70 80
Temperature (°C)
Figure 57: Distribution of breakdown voltages for dry FR3 as a function of temperature
128
60
Sample size = 75
Breakdown voltage 1mm gap

50
40
(kV) a 30
20
10
0
20 30 40 50 60 70 80
Temperature (°C)
Figure 58: Distribution of breakdown voltages for dry Midel 7131 as a function of
temperature
It can be seen that temperature has not affected the dielectric strengths of the oils. Thus,
it can be concluded that physical properties, such as density or viscosity, have little or
no impact on the dielectric strengths of the oils over this temperature range.
The expected breakdown voltages for the oils with these water contents are given in
figures 59 and 60.
The mean breakdown voltages of the samples are compared to the mean breakdown
voltages expected for the oil with the given water content at room temperature, shown
in table 25. It can be seen that the mean breakdown voltage of each oil is very similar to
that expected for the same oil with the given water content at room temperature.
129
Table 25: Comparing the mean breakdown voltages of the dry oil to the expected mean
breakdown voltage of the oil, using 1mm electrode gap, at room temperature
Oil, water content Mean breakdown voltage Expected mean breakdown voltage for
and relative humidity the oil with this water content at room
at 20°C temperature, taken from figures 59 & 60
(kV/mm) (kV/mm)
Mineral oil 31 ≈30

(1 ppm, 2% RH)
FR3 35 ≈35
(125 ppm, 11% RH)
Midel 7131 35 ≈40

(116 ppm, 4% RH)
60
50 FR3 Midel 7131
40
30
20
10
0
0 500 1000 1500 2000
Water content (ppm)
Figure 59: AC breakdown voltages of the esters as functions of water content (ppm)
130
60
Breakdown voltages 1mm gap (kV)

50
40
30
20
10
0
0 10 20 30 40
Water content (ppm)
The lowest and highest breakdown voltage of the oils is shown in table 26. The lowest
breakdown voltage of the esters is slightly higher than that of the mineral oil. The
highest breakdown voltages are similar.
Table 26: Lowest and highest breakdown voltage of the oils, using 1mm electrode gap
Oil, water content and relative Lowest breakdown voltage Highest breakdown voltage
humidity at 20°C (kV/mm) (kV/mm)
Mineral oil 23 41
(1 ppm, 2% RH)
FR3 25 40
(125 ppm, 11% RH)
Midel 7131 24 43
(116 ppm, 4% RH)
6.5 Effect of Temperature on the AC Dielectric Strengths of Wet Oil
Holle proposes that temperature changes the relative humidity of insulating oil which
can affect the dielectric strength of the oil. This would not have been observable in the
previous section because the water contents of the oils were too low to noticeably affect
the dielectric strength of the oil.
131
Theoretical water solubilities of an oil can be expressed in the form in equation 6.1,
where rs is the solubility, A & B are coefficients and T is the temperature in Kelvin.

log (g = − (6.1)

Various sources propose coefficients for mineral oil and esters, given in table 27. Figure
61 shows the theoretical solubilities of the oils as functions of temperature. It is notable
that the oils do not increase in solubility at the same rate. Between 20°C and 70°C the
solubility of mineral oil increases about six times whereas it only approximately
doubles for the esters.
Table 27: Coefficients for calculating water solubilities of oils
Oil and source Coefficient A Coefficient B
Mineral oil, Doble [100] 7.0895 1569
FR3, Doble [26] 5.3318 684
Midel 7131, calculated from 5.417 582

manufacturer data
10000
Theoretical water solubility (ppm)
1000
100
Mineral oil
FR3
10
Midel 7131
1
0 20 40 60 80 100
Temperature (°C)
Figure 61: Theoretical water solubilities for various oils as a function of temperature
The relative humidity of an oil is expressed by equation 6.2 as the percentage relation
132
between the mass of water (w) in a given volume of oil at a definite temperature and the
mass of water (w0) that would be present if the oil were saturated with water at that
temperature.
t
s = × 100% (6.2)
tu(v)
Samples of oil had their water levels increased using the desiccator and glycerol
solution as outlined in chapter five.
It takes time for the water content of an oil to equilibrate with the humidity of the air.
Furthermore since an oil is a blend of compounds each having an individual hygroscopy
the water content must not only equilibrate between the air and oil but between the
individual components of the oil itself.
Fofana studied the moisture uptake of mineral oil and showed that, depending on
relative humidity and temperature, it can take many days for the water content of
mineral oil to equilibrate with the air [87]. The fastest rate of water uptake tended to be
within the first week after which the water content begins to plateau.
The water content of each oil is given in table 28. After measuring the water content,
the oils were heated to 70°C in the DPA 75 test cell and maintained at this temperature
for two hours. The temperature of the oil and test cell was measured with the infra-red
thermometer and the test cell was then transferred to the DPA 75 oil tester. The
breakdown voltage of the oil was continually measured as it cooled while the
temperature of the test cell and oil was found between samples of breakdown voltages.
The electrode gap was set to 2mm because on occasion the DPA75 oil tester does not
reliably measure the breakdown voltage, and displays an error message, at voltages
below 10kV. To assist with readability, the results are given in figures 62 to 64 in terms
of dielectric strength (kV/mm) where the breakdown voltages have been divided by
two. The experiment was halted once the temperature of the oil reached 30°C, which
was after about four hours.
133
Table 28: Water content of samples along with their relative humidity
Oil Moisture level Relative humidity @ Relative humidity @

30°C 70°C
(ppm) (%) (%)
Mineral oil 23 28 7
FR3 590 50 27
Midel 7131 1000 32 19
60
Mean dielectric strength = 16kV/mm
50
Dielectric strength 2mm gap
Sample size = 105, water content = 23ppm
40
@ 30°C @ 70°C
(kV/mm) a
30 Oil relative humidity = 28% Oil relative humidity = 7%
20
10
0
20 30 40 50 60 70 80
Temperature (°C)
Figure 62: Distribution of breakdown voltages for wet mineral oil as a function of
temperature
134
60
50 Sample size = 105, water content = 590pm

40 @ 30°C @ 70°C
Oil relative humidity = 50% Oil relative humidity = 27%
(kV/mm) a
30
20
10
0
20 30 40 50 60 70 80
Temperature (°C)
Figure 63: Distribution of breakdown voltages for wet FR3 as a function of temperature
60
50
Sample size = 115, water content = 1000ppm
40
(kV/mm) a
30 @ 30°C @ 70°C
Oil relative humidity = 32% Oil relative humidity = 19%
20
10
0
20 30 40 50 60 70 80
Temperature (°C)
Figure 64: Distribution of breakdown voltages of wet Midel 7131 as a function of

temperature
Interestingly, temperature again does not appear to have affected the breakdown
voltages of the oils in contrast to the findings of Holle.
Figure 65 shows how the mean dielectric strength of these oils reduces with increasing
relative humidity. Despite the expected increase in relative humidity due to falling
temperature, figures 62 – 64 do not show reduced breakdown voltages at lower
temperatures. Instead the mean breakdown voltage in each case is similar to the
135
expected breakdown voltage for that oil with the same water content (ppm) at ambient
temperature, taken from figures 59 and 60.
60
Mineral oil
50 FR3
40 Midel 7131
30 Error bars = Mean ± 1 standard deviation
20
10
0
0 20 40 60 80 100
Water content (%RH)
Figure 65: AC breakdown voltages of oils as functions of relative humidity
The lowest and highest breakdown voltages of the esters, shown in table 29, are similar
to that of mineral oil. The lowest breakdown voltage of FR3 is slightly less than that of
mineral oil, but in terms of relative humidity the FR3 was more saturated.
Table 29: Lowest and highest breakdown voltage of the oils
Oil, water content and relative Lowest breakdown voltage Highest breakdown voltage
humidity at 20°C (kV/mm) (kV/mm)
Mineral oil 10 25
(23 ppm)
FR3 7 27
(590 ppm)
Midel 7131 9 22
(1000 ppm)
According to Musil the dielectric strength of an oil is affected by its relative humidity.
The relative humidity of an oil is calculated from its water content and not actually
136
measured. Consequently it may be that in the short period of the heating and cooling
cycle the water did not have sufficient time to equilibrate with the components of the oil
at the new temperature.
6.6 Effect of Temperature, Applied for One Week, on the AC

Dielectric Strengths of Wet Oil
The investigation was repeated, however, the oils were maintained at 70°C for one week
to determine whether time is required to allow the relative humidity of the oil to
properly equilibrate at 70°C.
Care was taken when selecting the level of water which would be required for the
investigation. It is shown in figure 65 that the breakdown voltage of mineral oil tends to
decrease quite steadily between 10% and 50% relative humidity whereas the breakdown
voltages of the esters tend to be fairly stable up to between 20% and 30% relative
humidity, and then fall after. The breakdown voltage of the Midel 7131 levels out at
around 40% relative humidity.
The different trends of the mineral oil and esters imply that, whereas for mineral oil any
change of relative humidity within the range 10% - 50% should cause a significant
change in breakdown voltage, in the case of esters a significant change is only to be
expected within a much narrower range; 20% - 40% for Midel 7131 and upwards of
30% for FR3.
From equation 6.1 for a given water content, the relative humidity of Midel 7131 will
approximately halve on heating from ambient temperature to 70°C.
Using Midel 7131 as an example; a relative humidity at ambient temperature of 40%,

which would cause a significant reduction in breakdown voltage, equates to a relative
humidity at 70°C of only 20%, which would not be expected to cause a significant
reduction in breakdown voltage.
Consequently, in order to provide a maximum change of breakdown voltage between

room temperature and 70°C, the following relative humidities were selected for the
esters:
137
The relative humidity of FR3 was to be 50% at room temperature, which will then
reduce to 25% at 70°C. This equates to around 500ppm of water.
The relative humidity of Midel 7131 was to be 40% at room temperature, which will
then reduce to 20% at 70°C. This equates to around 1000ppm of water.
The oils were firstly conditioned at room temperature in the DPA 75 test cell using the
desiccator and glycerol solution. Once the water content of the oil was considered to be
high enough to affect its dielectric strength, the oil along with the DPA 75 test cell was
transferred into an air circulating oven to maintain the oil at a temperature of 70°C for
one week.
It is recognised that during this period the water will equilibrate between the oil and the
air in the headspace of the cell causing the loss of some water by the oil. To avoid
further loss of water by the oil through the introduction of dry air, the test cell was not
opened until the breakdown voltage measurements had been completed. The water
content of the oil was found to change slightly, by a few percent relative humidity,
between the oil being sealed with electrical tape and being opened at the end for the
water content of the oil to be measured.
The exact temperature of the mineral oil before the Baur DPA 75 oil tester was started
was 61°C. The temperature of the oil bath was 47°C at the end of the test but it is not
expected that this would have affected the relative humidity over the duration of the
experiment, around thirty minutes, as the previous experiments imply that more time is
required. The water content of the mineral oil was found, just before the breakdown
voltages were measured, to be 42ppm, giving a relative humidity at 61°C of 19%. Ten
breakdown voltages were measured, shown in figure 66.
138
35
47°C
30

25
20
15 61°C Standard deviation = 3.2kV
10
0
1 2 3 4 5 6 7 8 9 10
Figure 66: Breakdown voltages of mineral oil heated to 70°C for one week
The mean breakdown voltages of the oil averaged from ten breakdowns was 26kV,
shown in table 30. This mean breakdown is higher than the value (<10kV) which would
be expected for this water content (ppm) of mineral oil at room temperature.
However, 26kV correlates to the expected breakdown voltage of mineral oil at 19%
relative humidity. This confirms that the breakdown voltage of mineral oil is a function
of its relative humidity. Furthermore this confirms that sufficient time must be given for
oil to equilibrate with its water at the new temperature to affect its breakdown voltage.
Table 30: Breakdown voltage of wet mineral oil, using 1mm electrode gap, maintained
at 70°C for one week
Oil and water Mean breakdown Expected Expected

content voltage and breakdown voltage breakdown voltage
standard deviation for this oil with this for this oil with this
(42ppm) water (19%) relative
content humidity
Mineral oil 26 kV <10 kV ≈25kV
42ppm σ = 3.2kV
19% RH
@ 61°C
139
The next part of the investigation was to determine whether, similarly to the mineral oil,
time is required for the water to properly equilibrate with an ester and to affect its
breakdown voltage.
Samples of wet ester were prepared using the desiccator and glycerol solution, and their
water contents were found to 420ppm for the FR3 and 1198ppm for the Midel 7131.
Before heating the breakdown voltages of the samples were measured, and are given in
figure 67.
35 FR3
FR3
Midel 7131 Mean breakdown voltage = 24kV
30
25
20
15
10
Midel 7131
0
1 2 3 4 5 6 7 8 9 10
Figure 67: Breakdown voltages of esters at room temperature prior to heating
The breakdown voltages of the oils are compared to those expected for the oils with
these water contents in table 31. The expected mean breakdown voltage is read from the
graphs showing the effect of water on the breakdown voltages of oil in figure 59.
140
Table 31: Water content and breakdown voltages, using 1mm electrode gap, of esters
before heating for one week
Oil Water Relative Mean breakdown Expected mean breakdown voltage

content humidity voltage & Standard for the oil with this level of water at
deviation ambient temperature
(ppm) (%) (kV) (kV)
FR3 420 38 24, σ = 6 ≈25 – 30
Midel 1198 44 14, σ = 2 ≈10

7131
The samples, along with the DPA75 test cell, were then heated to 70°C and maintained
at this temperature for one week in the air circulating oven. The mean of ten breakdown
voltages was found. Figure 68 compares the mean breakdown voltages of FR3 before
and after heating. It can be seen that the mean breakdown voltage has increased by
12kV.
50 Mean breakdown voltage of FR3

after heating = 36kV
45
40
35
30 Increase in
mean
25
20
15
Mean breakdown voltage of FR3
10 prior to heating = 24kV
5
0
1 2 3 4 5 6 7 8 9 10
Figure 68: Breakdown voltages of FR3 at room temperature prior to heating and after
heating at 70°C for one week
The mean breakdown voltage of Midel 7131 also increased when heated, by 10kV, as
shown in figure 69.
141
35 Mean breakdown voltage of Midel
7131 after heating = 24kV
Breakdown voltage 1mm gap (kV) 30
25
20 Increase in
mean
15
10

0
1 2 3 4 5 6 7 8 9 10
after heating at 70°C for one week
The water content of the esters was measured after their breakdown voltages were
found, and are given in table 32.
Table 32: Temperature and water content of oils after heating for one week
Oil Temperature Water content Relative

humidity
(°C) (ppm) (%)
FR3 68.8 360 17
Midel 7131 70 1093 21
Several attempts were necessary because it was found that it was difficult to keep the
water content of the oil constant during the heating process. The water content of the oil
fell slightly, 60ppm for FR3 and 105ppm for Midel 7131. It is thought that most of this
lost water had evaporated into the air headspace above the oil in the test cell. When air
is heated, it also becomes more hygroscopic. Some of the air may have leaked out of the
test cell, because the air and oil expand due to the heat, removing some of the water
vapour.
Table 33 compares the mean breakdown voltage of the esters, after heating, to the
142
expected breakdown voltage for these oils with this water content both in terms of ppm
and relative humidity, given are both given in figures 59 & 65.
Table 33: Mean breakdown voltage, using 1mm electrode gap, of the esters after heating
for one week
Oil Mean breakdown Standard Expected mean breakdown Expected breakdown

voltage deviation voltage for the oil with this level voltage for the oil at this
of water at ambient temperature relative humidity
(kV) (kV) (kV) (kV)
FR3
360ppm 36 7 ≈40 ≈40
RH = 17%
Midel 7131
1093ppm 24 4 ≈15 ≈40
RH = 21%
The mean breakdown voltage of FR3 is higher, and is around that expected for this
relative humidity, when the ester had been heated for one week. However the
breakdown voltage of this ester with 360ppm of water at room temperature is also
expected to be around 36kV so it is difficult to conclude whether the change in
temperature alone has caused this.
A major difference between the effect of water on the breakdown voltages of mineral
oil and esters is that whereas the mean breakdown voltage of mineral oil shows a steady
decline as its water content increases, the mean breakdown voltages of the esters are flat
up to a certain level of water (around 20% relative humidity) and then sharply decrease.
The mean breakdown voltage of the Midel 7131 heated for one week was found to be
higher than that expected for this ester with this water content at room temperature
although it is lower than that expected for this relative humidity.
The sample was placed in a dark cupboard for three weeks to observe whether its mean
breakdown voltage returned to that expected for this oil at room temperature. The mean
of ten breakdown voltages was recorded and is shown in figure 70. The water content of
the oil was 1035ppm, 58ppm lower than the water content of the oil after heating.
It is notable that the mean breakdown voltage of the sample is the same as the mean
143
breakdown voltage before the sample was heated for one week. Since the probability of
failure is related to the number of weak links in the oil, and only the temperature has
changed significantly, the number of weak links in the oil after cooling should not be
different than before the oil was heated.
Thus the lower than expected mean breakdown voltage after heating is unlikely to have
been caused by contamination entering the oil during heating.

7131 after heating = 24kV
30
25
Decrease
20
Increase in in mean
mean
15
10 After cooling, mean

breakdown voltage
5 returns to 14kV
Mean breakdown voltage of Midel
0
1 2 3 4 5 6 7 8 9 10
Midel 7131 Heated Midel 7131 Midel 7131 cooled after heating
after heating at 70°C for one week
The mean breakdown voltage of this sample, shown in table 34, is again similar to the
breakdown voltage expected for this oil with this water content.
144
Table 34: Mean breakdown voltage, using 1mm electrode gap, of Midel 7131 left to
cool for three weeks after heating
Oil Water Relative Mean Expected mean breakdown

content humidity breakdown voltage for the oil with this
voltage level of water at ambient
temperature
(ppm) (%) (kV) (kV)
Midel 7131 1035 38 14 ≈10
This evidence supports Beyer and Borsi’s view that the effect of water on the dielectric
strength of the synthetic ester cannot be explained by relative humidity alone.
Chadband supports the hypothesis that breakdown can be initiated by microscopic

particles [36]. He proposes that water increases the conductivity of hygroscopic
insulating particles and thus these particles initiate breakdown at a lower voltage than
when dry.
Since esters are more hygroscopic than mineral oil they absorb a greater proportion of
the water, hence keeping the particles drier. When the particles are dry they remain non-
conductive and therefore there is less of an affect on the breakdown voltage of the oil.
It may be possible to attribute the effect of temperature on the breakdown voltages of

these oils on the changing equilibrium, due to temperature, of water between the oil and
suspended particles.
When oil is heated it becomes more hygroscopic. Consequently the equilibrium position
for the distribution of water between the oil and particles will change, and thus so will
the conductivity of the particles. The hygroscopy of a particle will also increase with
temperature. However, since the breakdown voltage of a wet oil generally increases
with temperature this infers that the hygroscopic particles are becoming less conductive,
so are being dried by the oil. Therefore although the hygroscopy of a particle will
increase with rising temperature, it does not appear to increase as quickly as that of the
oil.
It was observed that the breakdown voltage of mineral oil is a function of relative
humidity. The mean breakdown voltage of this oil, at 61°C with a relative humidity of
145
19%, was 26kV, similar to the breakdown voltage of the oil at room temperature with a
relative humidity of 19%, around 25kV. This implies that the conductivities of the
particles are similar when the relative humidities of the samples, at differing
temperatures, are the same.
In contrast the effect of temperature on the breakdown voltage of the Midel 7131 was
not found to be a function of relative humidity. The breakdown voltage of this oil, at
70°C with a relative humidity of 21%, was around 15kV lower than expected for the oil
at ambient temperature with this relative humidity. This implies that the conductivities
of the particles are not similar when the relative humidity of Midel 7131, at differing
temperatures, is the same.
This may be caused by the relative increase in hygroscopy of the oils. Between 20°C
and 70°C the solubility of mineral oil increases about six times whereas it only
approximately doubles for the Midel 7131. Therefore, because the comparative change
in hygroscopy is higher; mineral oil may actually dry a particle more over this
temperature range than the Midel 7131.
6.7 Conclusions
Heating the oils to 70°C and maintaining at this temperature for two hours did not
change their breakdown voltages. Heating the oils to 70°C and maintaining at this
temperature for one week did change their breakdown voltages. Therefore a sufficient
duration to allow equilibrium is clearly important in the effect of temperature on the
breakdown voltage of an oil.
Musil [52] and Beyer & Borsi [97] advocate the theory that the dielectric strength of
mineral oil is a function of the relative humidity of the oil, and so is dependent on
temperature. These investigations support this view, however the oil had to be
maintained at the new temperature for a length of time, longer than two hours, before a
change in breakdown voltage was observed. This is because it takes time for water and
oil to reach a new state of equilibrium at a different temperature. Since the relative
humidity of an oil is calculated rather than measured, it is difficult to know how much
time is required to ensure that equilibrium is achieved.
146
This investigation found that the breakdown voltages of the esters are not strictly related
to their relative humidity, which was also noted by Beyer and Borsi when they studied
an ester [97]. They suggest that the shape of the ester molecule may affect the process
of breakdown, however do not cite any literature backing up their theory.
There has been a tendency in previous investigations to ignore the effect of the particles
and focus on the oil and water. Future research must investigate discharges from these
particles and whether water does increase the magnitude of these discharges.
These results do not test Chadband’s theory that water affects the breakdown voltage of
an oil by changing the conductivity of microscopic particles suspended within the oil.
To test this theory, the oils will require filtering to remove particles from the oil and re-
tested. A system will need to be developed that will allow water to diffuse into the oil
without adding particles.
In a transformer water exists in equilibrium between the cellulose and the oil.
Consequently the research must be extended to analyse how a change in temperature
affects the hygroscopies of these materials, the resultant movement of water between
them, and the effect of this water on the breakdown voltage of the oil.
147
Chapter 7: Effect of Ageing on the Breakdown Voltages of Oil
7.1 Introduction
Over time chemical reactions will degrade an oil. Consequently it is important to
understand how the oils degrade and the likely impact on their dielectric strengths.
When an insulating oil degrades the problems caused can usually be divided into two
areas:
1. Worsening dielectric performance of oil as an insulator caused by increases in the

quantity of particles of insoluble sludge and water content [101].
2. By-products of ageing affecting the overall insulation of the transformer. There is a

consensus of opinion that the by-products formed during oil ageing, such as water and
acids, affect the rate of cellulose degradation [102]. Over time cellulose can become
brittle and crack. It is often described as the weakest link in transformer insulation as it
cannot easily be replaced whereas the oil can be changed or reprocessed.
This chapter investigates the effects of ageing on the dielectric strengths of esters
compared to mineral oil.
7.2 Oil Degradation Mechanisms
Lewand writes, “It must be emphasized... that the properties of a natural ester cannot be
correlated directly to that of a mineral oil as the chemistries of the two types of liquids
are very different” [26]. Therefore in order to compare the chemical stabilities of these
liquids from the results of this investigation, it is necessary to understand the
mechanisms behind chemical ageing of each oil.
The primary mechanism behind the degradation of mineral oil is oxidation. However,
an ester can either hydrolyse or oxidise.
148
7.2.1 Oxidation
Oxygen can be present in a transformer from several sources. It may be introduced via
direct contact with the air if the transformer is free breathing, via leaks through seals, or
it may already be dissolved in the oil. Most UK power transformers are free breathing
with the air dried through a breather.
Hodges and Sabau write that oxidation of mineral oil is a progressive chemical process
in which hydrocarbon molecules are attacked by oxygen and broken down to a
multitude of various oxygenated compounds, including hydroperoxides, alcohols and
organic acids [103,104]. These compounds are polar, and increase the hygroscopy and
dielectric dissipation factor of the oil [82,105,106]. During oxidation the aromatic
structures in naphthenic base oils form asphaltenes which are precipitated as sludge
[104].
The rate of oxidation is dependent on temperature with the rate doubling approximately
every 7°C [107]. Oxidation of mineral oils is complex because a typical oil is composed
of several thousand isomeric hydrocarbons. Oxidation is initiated by the formation of
peroxides and hydroperoxides which react further to produce alcohols and ketones. The
reaction continues and produces carboxylic acids and aldehydes, as shown in figure 71.
The reaction rates of the oxidative process are increased by catalytic metals such as
copper and iron.
Figure 71: Oxidation of mineral oil [104]
Ester oils oxidise creating alcohols, ketones, aldehydes and carboxylic acids which,
unlike the by-products of the oxidation of mineral oil, are not precipated. Shahidi writes
149
“as the oxidation of an ester proceeds, the oxygenated compounds polymerize to form
viscous material that, at a particular point, becomes oil insoluble leading to oil
thickening and deposits” [108].
7.2.2 Hydrolysis
The COOC linkage in esters is prone to hydrolytic degradation. Hydrolysis is the

reaction of the ester with water forming a carboxylic acid, and is given by the following
chemical equation [108].
In the case of an unoxidised vegetable oil the 'R' is a long chain of carbon atoms. For
FR3 the 'R' chain is between 18 and 22 carbon atoms long. Solomons shows that the
acidity of a carboxylic acid is dependent on its molecular structure [109]. Carboxylic
acids having long chains of carbon atoms tend to be less aggressive than short chain
carboxylic acids [110,111].
The aggressivenesses of acids found in transformer oils have been studied by Sokolov
and McShane et al. Sokolov aged cellulose in different types of acid which are
commonly found in aged mineral oil and, from monitoring changes in degree of
polymerization of the cellulose, concluded that low molecular weight acids are
responsible for accelerating the ageing of cellulose [19]. The FR3 test guide states that
long chain fatty acids created by hydrolysis are “mild and non-corrosive compared to
the short chain organic acids found in mineral oil” [87].
McShane et al aged thermally upgraded Kraft paper in FR3 for 4000 hours at 170°C in a
sealed system and concluded that the long chain acids created by hydrolysis of FR3 may
actually be beneficial to the longevity of the cellulose as this process consumes water
[21,112]. A low water content is desirable in a transformer because water degrades the
cellulose insulation and has been shown to reduce the dielectric strength of the
insulating oil.
7.3 Background to the Accelerated Ageing Schemes Commonly Used to

Investigate the Stability of an Oil
It is common to test the stability of an oil using an accelerating ageing method. These
150
methods use elevated temperatures and can employ pressure, catalysts and oxygen
atmosphere to increase the rate of reaction.
When selecting an ageing method it is important to consider whether the method is

appropriate for testing esters. Two ageing methods which have been used to grade the
performance of esters are ASTM D2112-01a “standard test method for oxidation
stability of inhibited mineral insulating oil by pressure vessel” [113] and ASTM D2440-
99 “standard test method for oxidation stability of mineral insulating oil” [114].
D2112-01a measures the time taken for an oil to react with a given volume of oxygen.
D2440-99 defines oxidation stability as the propensity of oils to form sludge and acid
products during oxidation” [114].
These methods only focus on the end results and do not investigate how the oil degrades
or affects the operation of the transformer. Both ASTM D2112 and D2440 have a clause
stating, “There is no proven correlation between oil performance in this test and
performance in service” [113,114].
ASTM D2112-01a is intended as a rapid method to evaluate the oxidative stability of

mineral oil, and uses the reactive conditions provided by oxygen under pressure,
catalytic copper and a temperature of 140°C. Lewand performed this test on FR3,
finding that this ester had reacted with the oxygen after only 17 minutes, compared to
between 195 and 220 minutes for the mineral oil [26].
The conditions of this test are harsh in order to quickly evaluate the oxidative stability
of mineral oil. It is considered that this test method is unsuitable for the purpose of this
investigation because it oxidises the oils too rapidly, and it cannot be guaranteed that the
oxidative reactions occurring during this test would be representative of those occurring
in a free breathing transformer.
ASTM D2440-99 may not be appropriate to test an ester because they do not form
precipitate sludge and the resulting acids may be less corrosive than mineral oil.
It is difficult to extrapolate reaction rates of an oil during ageing at high temperatures to

conditions realistic for a transformer because the temperature profile of an oil is
151
dependent on loading, which changes throughout the day and year, localised hotspots
around conductors and temperature variations due to oil circulation. Old transformers
may contain free water, metallic and cellulosic particles, the effect of which may not be
simulated in an accelerated ageing test [115].
7.4 Previous Research Investigating the Accelerated Ageing of Esters
Several researchers have published results on the ageing of FR3. Both Oommen and
Lewand found that FR3 gels when standard ASTM D2440 is applied, with Oommen
suggesting that FR3 may be susceptible to oxidation [116,26]. Lewand reports that the
manufacturer of FR3 does not consider ASTM D2440 to be relevant because this test
evaluates the sludge content whereas FR3 does not sludge. Furthermore, Lewand
recognises that accelerated ageing tests are not an actual measure of in-service
performance. McShane was critical of Oommen's study as McShane felt that Oommen
had only investigated the oxidative stability of the oil which did not reflect its true
performance in the transformer environment [117].
Despite this criticism, Oommen's study demonstrates that the anti-oxidant content of an
ester should be monitored and action taken when required. The rate at which the anti-
oxidants are consumed is dependent on the working conditions of the oil, thus it is
difficult to estimate how quickly these anti-oxidants are consumed in service.
Rapp et al studied the effect of ageing on FR3 and report that the dielectric strength of
FR3 was retained after 4000 hours of ageing at 150°C in a sealed container [118,119].
However, since the test cell was sealed there would have been minimal oxidation.
Cooper Power Systems does not recommend that FR3 is used in a free breathing
transformer and therefore has not investigated the effect of ageing using an atmosphere
containing oxygen. This may be a simplistic assumption because an oil will be exposed
to air during activities such as transformer manufacture or maintenance. Furthermore air
may be introduced during the life of the transformer through leaks such as due to faulty
seals.
Cooper Power Systems commenced field trials of four small transformers filled with
FR3 in 1996. Two were free breathing 25kVA single phase 7200V/240V pole
152
transformers and two were sealed 225kVA 3 phase 4160V/240V transformers. The free
breathing transformers had a 1.65 mm diameter vent hole.
The two sealed transformers have been continuously loaded at about 90% and are part
of the power system at one of Cooper's factories. The free breathing transformers
underwent various indoor test cycles before being placed outdoors in 2002. Since then
they have been energized at 7200 volts continuously and each day loaded at 100% for 8
hours, then no load for 16 hours. Top oil temperatures of the free breathing units ranged
between 60°C – 75°C for one and 85°C – 105°C for the other.
The oil has been regularly sampled and although oxidation and hydrolysis have
occurred from the commencement of this test, the operation and performance of the
transformers have not been affected [120]. The importance of this test is that, despite
the accelerated ageing investigations performed by Oommen and Lewand suggesting
poor resistance to oxidation, FR3 is proving to be an effective dielectric over prolonged
periods, eleven years to date.
These transformers did not, however, contain cellulosic insulation. Therefore this
investigation has not studied the interaction between cellulose and FR3.
Borsi aged samples of Midel 7131 in open vessels at 150°C for 1000 hours with copper,
steel and aluminium chips. He concluded that there was no significant reduction of
breakdown strength and the dielectric dissipation factor had increased by about a
hundred times [81]. Synthetic esters are generally highly stable with regard to oxidation.
According to the manufacturer, M & I Materials, Midel 7131 has been successfully used
in small free breathing transformers for nearly 30 years [5].
7.5 Accelerated Ageing Investigation
The aim was to monitor the chemical change of each oil and study whether these
changes affected the dielectric capabilities of the oils. A goal was to keep the ageing
conditions similar to the environment of the transformer so that the chemical reactions
occurring in the oil would be as realistic as possible. Standard ASTM D1934-95 (2005)
“Standard Test Method for Oxidative Aging of Electrical Insulating Petroleum Oils by
Open-Beaker Method” [121] was selected as the ageing method because the oils would
153
be heated in air, realistic for a free breathing transformer since oxygen is sourced from
the air.
Metals used in the construction of a transformer were selected as catalysts. Copper and
iron are usually chosen as the catalysts; however the target transformers are
manufactured from steel rather than iron. The steel can be painted or varnished. One
part of the transformer which is constructed from steel is the core. In this case, the steel
is in the form of thin layers which are glass coated although the edges are bare and thus
in contact with the oil. Therefore oils were aged with samples of core steel to
investigate whether there was a noticeable effect on the dielectric capabilities of the
oils.
The strips of metal were cut to approximately 4cm x 10cm, giving a total surface area
around 80cm2. Since the core steel is glass coated, only the edges, which were 1mm
thick and provide a much smaller surface area, were exposed to the oil.
The copper strips were cleaned with a fine glass-paper to remove any oxide layer. Strips
were then cleaned with methanol and dried in the air circulating oven to remove any
impurities residing on their surface.
Samples of mineral oil and ester were held at 115°C for up to 28 days in an air
circulating oven. Steffens points out that there can be two errors caused by such an oven
[122]. One is that the temperature within the oven may not be uniform. The other is that
the ventilation rate of the oven may not be sufficient to ensure that there is a constant
concentration of oxygen around the test specimen. In order to reduce variation in the
results the same oven was used to age all three oils.
After ageing the bottles were immediately sealed and left to cool naturally. Bottles were
removed after 7, 14 and 28 days and then discarded after the measurements were
performed. Samples were discarded after measurements to prevent the possibility of
contamination, resulting from the measurement, affecting the outcome of this
investigation.
A range of dielectric and chemical properties were selected for measurement. These
154
were: AC breakdown voltage, lightning impulse breakdown voltage, dielectric
dissipation factor, permittivity, acidity and water content.
7.6 Analysis of Chemical Transformation
The acidity, dielectric dissipation factor, relative permittivity and sludge content were
used to examine chemical reactions occurring within the oils.
7.6.1 Acidity
The acidity of the samples was measured using a Metrohm AG 686 Titroprocessor and
665 Dosimat, operated by TJH2b Analytical Services, according to standard IEC 62021
[58]. The acidity of one sample was analysed.
The inclusion of copper affected the results for the FR3 and mineral oil, as shown in
figures 72 and 73, but did not affect the results for Midel 7131. The inclusion of copper
increased acid production in the mineral oil, in contrast the acidity of the FR3 is did not
rise in the presence of the copper.
Since copper is catalytic it is understandable that it increased the rate of acid production
in the mineral oil. Cooper Power Systems were contacted and believe that in the case of
FR3, the copper changes its reaction path.
Without copper, hydrolysis was the preferred reaction path. When FR3 hydrolyses long
chain fatty acids are directly created, and so the acidity of the oil increases. In contrast
when FR3 is oxidised ketones, aldehydes and alcohols are produced, which have little
or no acidity. In order for a hydrocarbon to oxidise, as shown in figure 71, a radical
must be produced. Copper may be acting as a pre-oxidant catalyst increasing the rate of
radical production, and these radicals further react to form the other products of
oxidation.
Cooper Power believe if the ageing test were run for longer some of these compounds
would eventually oxidise to form acids.
The anti-oxidant in the FR3 would have certainly retarded oxidation in both cases,
however, when copper is present the anti-oxidant was perhaps insufficient to prevent the
155
by-products from forming.
0.4
Acidity (mg KOH/gram) 0.3
0.2
0.1
0
0 5 10 15 20 25 30
Ageing time (days)
Mineral FR3 Midel 7131
Figure 72: Change in the acidities of the oils after thermal ageing without using a
copper catalyst
0.4
Acidity (mg KOH/gram)
0.3
0.2
0.1
0
0 5 10 15 20 25 30
Ageing time (days)
Mineral FR3 Midel 7131
Figure 73: Change in the acidities of the oils after thermal ageing using a copper
catalyst
7.6.2 Dielectric Dissipation Factor
The tan δ (dielectric dissipation factor) of an oil is dependent on the quantity and
strength of polar compounds in the oil. Oil molecules become more polar as oxygen is
incorporated into the molecular structure of the oil during ageing. These polars can be
alcohols and ketones which have little or no acidity although they can react further
forming acids. Esters are inherently more polar than mineral oil due to the oxygen
atoms held in their molecular structure.
156
The main drawback to the tan δ is that this only provides an indication of the overall
quantity of polars in a sample, it does not indicate their structure. Consequently the
dielectric dissipation factor should not be directly compared across different oils, it is
the rate of change which is significant rather than the level.
All measurements were performed at 25°C ± 1°C, as per standard IEC 60247 [53], and
are given in figure 74. When the oil was poured into the test vessel a five minute stand
time was given for the air bubbles to escape. The sample was visually checked to be
free of bubbles prior to the measurement.
The most pronounced trend in tan δ was for FR3 aged with copper. Since FR3 is likely
to be oxidising due to the copper, the increase in tan δ is most likely due to the alcohols,
ketones and aldehydes; the previous acidity measurement indicated little change in the
acid values of the oils. The tan δ of the FR3 aged without copper did not significantly
change compared to when copper is present. Since the acid value of this sample
increases, but the tan δ does not change, this implies that the change in acidity is due to
the less polar long chain fatty acids created by hydrolysis of the ester.
The tan δ of the mineral oil increased slightly, from 0.05% when new to nearly 0.15%
after 28 days. As mineral oil is non-polar, the polar by-products of oxidation will have
been precipitated as sludge and may not have been sampled.
There is little change in the tan δ of the Midel 7131. When aged without copper its tan δ
increased from 0.10% to 0.14% while when aged with copper its tan δ increased to
0.2%. The initial increase may have been due to impurities oxidising.
Steel did not noticeably increase the dissipation factors. This is explicable since the
steel was glass coated, so only the edges were exposed, and steel is not as strong
catalytically as copper.
157
0.7
0.6
Dielectric Dissipation Factor (%)
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30
Ageing time (days)
Mineral Oil Mineral + copper Mineral + Steel Min + catalysts
FR3 FR3 + copper FR3 + Steel FR3 + catalysts
Midel 7131 Midel + copper Midel + Steel Midel + catalysts
Figure 74: Change in the dielectric dissipation factors of the oils during thermal ageing
7.6.3 Relative Permittivity
The measurements were performed at 25°C at the same time as the dielectric dissipation
factor test.
The relative permittivity of Midel 7131 and FR3 is 3.2, higher than that of the mineral
oil which is 2.2. The permittivities of the oils did not change during ageing, as shown in
figure 75.
It is noted in the test standard for measuring the relative permittivity of oil, IEC 60247,
that “only gross contamination is likely to affect permittivity” [53]. Consequently it is
likely that insufficient quantities of ageing products were created during this
investigation to have affected the relative permittivity of the oil.
158
4
Relative permittivity
2
0
0 5 10 15 20 25 30
Ageing time (days)
Mineral Oil Mineral + copper Mineral + Steel Min + catalysts
FR3 FR3 + copper FR3 + Steel FR3 + catalysts
Midel 7131 Midel + copper Midel + Steel Midel + catalysts
Figure 75: Change in the relative permittivities of the oils during thermal ageing
7.6.4 Oil Ageing Leading to Sludge
Sludge can block oil ducts and insoluble particles can affect the dielectric strength of oil
gaps. The appearance of the new oils is shown in figure 76. No sludge or solid matter is
observable in any of the oils. Sludge could be seen in the mineral oil but could not be
seen in either ester as shown in figures 77 - 79. The sample of FR3 aged with copper
turned brown, whereas the sample aged without copper remained green. The Midel
7131 did not change visibly regardless of whether copper was present. The inclusion of
steel did not visibly affect the appearance of any of the oils.
There are clear signs of chemical transformation in both mineral oil and FR3. However,
whereas mineral oil tended to form precipitate sludge FR3 did not. This observation is
shared by McShane who noted that when a natural ester oxidises although it
polymerises it does not sludge [123].
Whether or not sludge was formed during oxidation would have affected the dielectric
dissipation factors of the oils. Since mineral oil is non-polar, the polar by-products
would have been precipitated so would not have been detected by the dielectric
dissipation factor measurement. As FR3 is polar, and no sludge was precipitated, the
159
polar by-products would have stayed in solution and so would been detected by the
dielectric dissipation factor test. This may explain why the tan δ has increased in the
FR3 at a higher rate than the mineral oil despite clear signs of oxidation.
Mineral oil Midel 7131 FR3
Figure 76: Appearance of new oils, showing mineral oil, Midel 7131 and FR3
Figure 77: Appearance of mineral oil aged for 28 days without copper (left) and with
copper (right)
Oil
Copper
strip
Figure 78: Appearance of FR3 aged for 28 days without copper (left) and with copper
(right)
160
Oil
Copper
strip
Figure 79: Appearance of Midel 7131 aged without copper (left) and with copper (right)
7.7 Comparison of the Effect of Ageing on the Dielectric Strength of

Oil
This section investigates whether ageing has affected the dielectric strengths of the oils.
Since water is known to affect the dielectric strength of oil, the water content of each oil
was measured to assist with the explanation of the results. The levels of water for each
sample of oil are given in table 35.
The hygroscopy of the oils will change during ageing so the percentage saturation of the
oils will not be precisely known. Franklin observes that during chemical degradation
water may be chemically attached to the aldehydes, alcohols and acid groups which are
created and this attached water cannot be readily removed by temperature and vacuum
[106].
The moisture content of the FR3 aged with copper could not be found because the
ketones that were produced by oxidation interfered with the reagent, Hydranal AG-H,
used by the Karl Fischer coulometer. A suitable reagent, compatible with this
coulometer, was not available.
161
Table 35: Water content of oils after ageing
Sample Water content (ppm) of oil after ageing for:
7 days 14 days 28 days
Mineral oil 12 20 20
Mineral oil and copper 16 24 24
Mineral oil and steel 11 11 6
Mineral oil with copper and steel 13 9 12
FR3 64 58 33
FR3 and copper * - - -
FR3 and steel 66 59 31
FR3 with copper and steel * - - -
Midel 7131 38 42 45
Midel 7131 and copper 45 47 43
Midel 7131 and steel 43 46 43
Midel 7131 with copper and steel 26 18 37
* Could not be found due to ketone interference
7.7.1 Comparison of the Effect of Ageing on the Mean AC Breakdown Voltages
The AC breakdown voltage was measured according to standard ASTM D1816 using
the Baur DPA75 test set. The mean of twenty breakdowns was recorded.
The dielectric strengths of the mineral oil decreased with ageing as shown in figure 80.
Both water and particles are known to reduce the breakdown voltage of an oil.
Consequently the reduction in breakdown voltage is likely to have been caused by
increases in water and insoluble ageing products.
162
50
40
Mean Breakdown voltage 1mm gap (kV)
30
20
10
0
0 5 10 15 20 25 30
Ageing time (days)
Mineral Oil Min + copper Min + Steel Min + catalysts
FR3 FR3 + copper FR3 + steel FR3 + catalysts
Midel 7131 Mid + copper Mid + steel Mid + catalysts
Figure 80: Mean AC breakdown voltages of the oils after ageing with various catalysts
Despite signs of ageing in the FR3 the dielectric strength of this oil remains high. This
can be explained by the following observations: The measured water content of the
samples, in terms of percentage saturation, was low and is therefore unlikely to have
affected the breakdown voltage. Particles are also known to reduce the dielectric
strength of an oil. However, no insoluble ageing products were observed in this oil.
The dielectric strength of Midel 7131 does not appear to have been affected by ageing.
IEEE have published a guide, 62-1995, for field testing oil filled power transformers,
regulators and reactors [124]. This standard recommends that the dielectric strength of
the insulating oil should be, measured according to ASTM D1816, at least 26kV/mm
for equipment rated at voltages over 345kV. The dielectric strengths of the esters
remained above this level whereas, after 28 days of ageing, those of three of the four
samples of mineral oil had fallen below this voltage.
163
7.7.2 Comparison of the Effect of Ageing on the Distributions of AC Breakdown
Voltages
This section investigates the overall AC dielectric performances of the esters compared
to those of mineral oil. The distributions for the breakdown voltages of new oils have
been sourced from chapter four of this thesis. The distributions of new oil breakdown
voltages are at the higher end of the samples. This may be because the samples of new
oil were degassed whereas the aged oil was not.
Mineral oil
The samples which have the lowest overall distributions of breakdown voltages, shown
in figure 81, were mainly those which had been aged for 28 days.
1
0.9
0.8
0.7
0.6
New oil
No Catalyst 7 days
0.5 No Catalyst 14 days
No Catalyst 28 Days
0.4 Copper 7 Days

Copper 14 Days
0.3 Copper 28 Days

Steel 7 Days
Steel 14 Days
0.2
Steel 28 Days
Copper + Steel 7 Days
0.1
0
0 10 20 30 40 50
Figure 81: Effect of ageing on the distribution of AC breakdown voltages of mineral oil
The sample which was aged with steel for 28 days has a higher mean breakdown
164
voltage than the other samples aged for 28 days. However, it has a low water content of
6ppm. In certain instances the effect of ageing is apparent in samples aged for different
lengths of time which have the same content of water. The effects of ageing can be seen
in the following distributions:
The samples of mineral oil aged without catalysts for 14 and 28 days have the same
content of water however the median breakdown voltage of the sample aged for 28 days
is 7kV, or 23%, lower than that of the sample aged for 14 days.
The samples of mineral oil aged with copper for 14 and 28 days have the same content
of water however the median breakdown voltage of the sample aged for 28 days is
11kV, or 32%, lower than that of the sample aged for 14 days.
The samples of mineral oil aged with copper and steel for 7 and 28 days have
approximately the same content of water however the median breakdown voltage of the
sample aged for 28 days is 7kV, or 22%, lower than that of the sample aged for 7 days.
When analysing the breakdown voltages of the 28 day samples it would appear that the
effect of water is more predominate on the results than whether or not a catalyst has
been used.
FR3
As shown in figure 82 ageing does not appear to have affected the distributions of
breakdown voltages. Unlike the breakdown voltages of mineral oil, those of the samples
aged for 28 days are not lower than those aged for shorter durations.
165
1
0.9
0.8
0.7
New oil
0.6
No Catalyst 7 days
No Catalyst 14 days
0.5
No Catalyst 28 Days
Copper 7 Days
0.4
Copper 14 Days
Copper 28 Days
0.3 Steel 7 Days
Steel 14 Days
0.2 Steel 28 Days
0.1 Copper + Steel 14 Days
0
0 10 20 30 40 50 60
Figure 82: Effect of ageing on the distribution of AC breakdown voltages of FR3
Water would not have affected the breakdown voltages of FR3 to the same extent as
those of mineral oil because FR3 is more hygroscopic. Although the oil aged with
copper visibly changed colour no sludge was seen after ageing. Neither hydrolysis nor
oxidation appears to have affected the breakdown voltage of FR3.
The lowest breakdown voltages of the samples of FR3 are greater than that of the
mineral oil, which was 12kV.
Midel 7131
As shown in figure 83 the breakdown voltages of Midel 7131 aged for 28 days are not
lower than those of Midel 7131 aged for less time.
As for FR3, water would not have affected the breakdown voltages of Midel 7131 to the
same extent as those of mineral oil because Midel 7131 is more hygroscopic.
166
The lowest breakdown voltages of this ester are higher than those of the mineral oil.
0.9
0.8 New oil

No Catalyst 7 days
No Catalyst 14 days
0.7
No Catalyst 28 Days
Copper 7 Days
0.6 Copper 14 Days
Copper 28 Days
0.5 Steel 7 Days
Steel 14 Days
Steel 28 Days
0.4
0.3 Copper + Steel 28 Days
0.2
0.1
0
0 10 20 30 40 50 60
Figure 83: Effect of ageing on the distribution of AC breakdown voltages of Midel 7131
7.7.3 Comparison of the Effect of Ageing on the Lightning Impulse Dielectric

Strength of Oil
The lightning impulse breakdown voltage was measured according to standard ASTM
D3300-94. A Haefely 10 stage impulse generator was used to provide a 1.2µs/50µs
negative voltage waveshape. The test cell was fitted with 12.7mm diameter spherical to
spherical brass electrodes set to a gap of 3.8mm. A low voltage transient was applied
and raised in steps of -10kV until 5 flashovers were observed. It is noted that the
lightning impulse voltage was raised in steps of -10kV, so the true breakdown voltage
may be up to 10kV lower than measured. The mean lightning impulse breakdown
voltages are given in table 36.
167
Table 36: Mean lightning impulse breakdown voltages of the oils before and after
ageing for 28 days

Mean breakdown voltage of new oil
-196 -181 -165
(kV)
Mean breakdown voltage of oil aged
without catalysts -168 -178 -170
(kV)
Mean breakdown voltage of oil aged
with copper -161 -168 -162
(kV)
The lightning impulse dielectric strengths of aged mineral oil are lower than those of
new mineral oil, shown in figure 84. The samples had relatively high levels of water and
the lightning impulse dielectric strengths are similar to those expected for mineral oil
with these levels of water, shown in figure 47. Although Linhjell notes that non-
conductive particles do not affect the lightning impulse dielectric strength of an oil to a
large extent, it may be that the insoluble sludge adsorbs water and becomes more
conductive and thus can affect the lightning impulse dielectric strength of oil.
0.9 20ppm 5ppm

Unaged
0.8 Aged No Catalyst 24ppm
Aged with copper
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
100 120 140 160 180 200
Breakdown voltage (-kV)
of mineral oil
The lightning impulse dielectric strength of FR3 does not appear to have been
168
substantially affected by ageing, shown in figure 85. There was a general trend that the
breakdown voltages of the FR3 were more dispersed when aged than when new,
although this may be due to the higher scatter of the lightning impulse dielectric
strength of this oil seen in figure 48.
1
0.9 Unaged
26ppm 33ppm
0.8 Aged No Catalyst
Aged with copper
0.7
Water content not

0.6 found due to ketone
interference
0.5
0.4
0.3
0.2
0.1
0
100 120 140 160 180 200
Figure 85: Effect of ageing on the distribution of lightning breakdown voltages of FR3
There appears to be no difference in the lightning impulse dielectric strengths of Midel

7131, shown in figure 86.
169
1
0.9 Unaged
0.8 Aged No Catalyst
Aged with copper
0.7
0.6
0.5
0.4
0.3
0.2
43ppm 77ppm 45ppm
0.1
0
100 120 140 160 180 200
of Midel 7131
7.8 Conclusions
The mineral oil showed clear signs of ageing and its breakdown voltage decreased. Its
levels of acidity and tan δ both increased indicating that oxidation products were
present. The appearance of this oil changed, it darkened and insoluble sludge was
observed.
At 28 days of ageing the AC breakdown voltages of three of the four samples of mineral
oil were below the 26kV/mm set by IEEE 62-1995. The water levels of these samples
were high, however, since in some cases the water levels were similar to the samples
after 14 days of ageing, water cannot solely explain the drop in breakdown voltage.
Particles of insoluble sludge may cause dielectric failure. To cause breakdown a particle
must be within the electrically stressed volume of oil, however, dielectrophoretic forces
will attract these particles into this region. It is therefore likely that the breakdown
voltage of mineral oil has been affected by both water and insoluble sludge.
The mean lightning impulse breakdown voltage of mineral oil fell by around 30kV after
28 days of ageing. This may have been caused by the insoluble sludge particles and
170
water in conjunction. The water would have been adsorbed by the particles and thus
they would become more conductive, perhaps conductive enough to reduce the
lightning impulse breakdown strength.
The molecular nature of the compounds within an oil can affect its lightning impulse
breakdown voltage. Pahlavanpour and Eklund observed that as the aromatic content of
mineral oil increases, its lightning impulse dielectric strength is reduced [47]. During
oxidation the aromatic content of mineral oil will decrease because aromatics form
asphaltenes which are precipitated as sludge. However, the decrease in the aromatic
content of mineral oil due to oxidation did not result in an increase in its lightning
impulse dielectric strength as the reaction products have the opposite effect.
The FR3 shows signs of chemical degradation. It can either hydrolyse or oxidise,
depending on whether copper is present. The water content of this oil was low and from
the results shown in chapter five is unlikely to have affected its AC or lightning impulse
breakdown voltages. Insoluble sludge was not visible in this ester. Neither the by-
products of oxidative and hydrolytic reactions appear to have affected the AC or
lightning impulse breakdown voltages of the FR3.
The Midel 7131 is the most chemically stable oil used in this investigation. The acidity
of this oil did not change during this investigation indicating that little or no hydrolysis
has occurred. The water content of this oil was low and from the results presented in
chapter five is unlikely to have affected its AC or lightning impulse breakdown voltage.
No insoluble sludge was visible after ageing for 28 days. Therefore it is unsurprising
that the breakdown voltages of Midel 7131 have not been affected.
171
Chapter 8: Effect of Large Oil Gaps on the Dielectric
Strength of Oil
8.1 Introduction
Blume reported that the dielectric strength of mineral oil (in kV/mm) decreases as the
distance between the electrodes rises [61]. The previous chapters of this thesis have
only considered the AC dielectric strengths of oils using small electrode gaps of 1mm or
2mm. In power transformers the geometries between conductors are larger than this,
therefore it is necessary to investigate the dielectric strengths of the esters using larger
electrode gaps.
Kawaguchi et al investigated the dielectric strength of mineral oil using large oil gaps
up to 250mm and determined that both the area of the electrodes and the distance
between them influence the dielectric strength of the oil [125].
Trinh et al studied the dielectric strength of large oil gaps up to the order of tens of
centimetres [126]. They found that particles were instrumental in decreasing the
dielectric strength of mineral oil as the distance between the electrodes, and therefore
the oil volume, increases. Figure 87 shows the reduction in dielectric strength with
increasing gap (mm) and volume of stressed oil (cm3) as the particle count (δp) is
increased.
No effect was seen when the particle count was less than 14 but at higher particle
counts, of 17 and 18 shown in figure 87, the reduction in dielectric strength was steep.
The Weidmann Reference Curve (WRC) is also shown in the figure. This is a design
curve showing the minimum permissible dielectric strength of an oil as a function of
electrode gap.
The size and quantity of the particles were described with the parameter δp which is
given by equation 8.1. The number of particles in 10ml of oil having a diameter greater
than 1µm is given by n0 and d1 is the largest size of particle expected in the sample of
oil.
@6 = ln(D #& ) (8.1)

172
Figure 87: Effect of particles on the dielectric strength of oil [126]
The practical difficulty of using equation 8.1 is that it assumes the largest size of
particle is known. However, there is always the possibility of particles contaminating a
test vessel within any laboratory and the sizes of these particles cannot be known.
The particle content of an oil is highly variable because some of the particles will settle
at the bottom of the container and not be sampled. Furthermore when an AC field is
applied to the test cell the particles will experience a force and be attracted towards
regions of high electric stress. Consequently the particle distribution inside a test cell is
not uniform. The force on a particle is given by equation 8.2, where r is the radius of the
particle, εOil is the relative permittivity of the oil, εparticle is the relative permittivity of the
particle and grad E2 is the gradient, in three dimensional space, of the square of the
electric field.
& ( 01. )
% = ' ( ) '*+,-./

2(3# ' (8.2)
1. *+,-./
The aim of this investigation was to compare the breakdown voltages of the esters to
those of mineral oil using electrode gaps of 5mm and 10mm. However, since particles
affect the dielectric strength of oil, it is necessary to ensure that a difference in
173
breakdown voltages of two oils is actually due to the oil itself and not contamination.
Although the exact particle content of the oils was not determined, it is expected to be
low because the oils are in a new condition, as supplied by the manufacturer.
A test cell was developed, detailed in the next section, which was capable of operating
at the high voltages required to break down an oil gap of up to 10mm.
8.2 Development of Large Electrode Gap Cell
A test cell, shown in figure 88, was developed to operate at high voltages. In practice
the maximum voltage reached before external flashover was 300kV. At this voltage the
connection to the test cell, rather than the test cell itself, was the cause of the flashover.
The test cell stands at around 90cm high and has a capacity of 25 litres of oil. A valve is
located at the base of the vessel to allow the removal of the oil. The distance between
the electrodes is set by the aluminium spacers.
Perspex end plates

Aluminium toroids
PVC collars
Aluminium electrode
spacers
Brass 5cm diameter
electrodes
Corning glass vessel

Nylon bolts
Figure 88: Test cell used in this investigation for large electrode gap experiments
174
8.2.1 Insulation Design
Appropriate insulating materials were selected to allow the cell to operate at high
voltages, these were:
• A QVF Corning glass cylinder which was chosen for the test cell. Glass was
selected to allow full optical access.
• Nylon screws, washers and nuts. Plastic items were chosen because these are
non-conductive.
• Flanges and stands manufactured from PVC, which was chosen because it is
non-conductive and is not prone to cracking.
• Perspex end plates. Perspex was selected because it is transparent and non-
conductive.
The main challenge was to prevent air flashover around the cell. Sharp radii or
protrusions around the conductors can raise the electric field to a level which will cause
corona. Corona is detrimental as it can lead to the air arcing around the outside of the
cell. Aluminium toroids were used to enlarge the radii of the conductors in areas of high
electric stress, such as around the high voltage connection of the cell, thus reducing the
magnitude of the electric field in these regions.
AREVA T & D suggested placing toroids at both ends of the test cell because since the
AC changes in polarity, for half of the AC cycle the earthed side of the test cell will be
at a higher voltage than the high voltage connection at the top. However, since the floor
under the test cell was earthed by a metal grid, no problems were encountered which
were caused by the bottom connection. In practice the bottom toroid was removed so as
not to impede the flow of oil out of the cell.
Finite element analysis was performed on the design of the test cell by AREVA T & D,
shown in figure 89. It can be seen that the radii of the top toroids help to maintain a low
magnitude of electric field around the connection between the test cell and high voltage
supply. In this analysis 100 volts were applied to the high voltage connection at the top
of the test cell. Equipotential lines are drawn at 5 volt intervals.
175
V/m
Figure 89: Finite element analysis showing the distribution of the electric field around
the test cell
8.2.2 Development of the Electrodes
Brass spheres of 5cm diameter were used as the electrodes. The distance between the
electrodes was set precisely by a series of 25mm diameter aluminium rods which were
screwed between the electrode and top end plate. Aluminium disc spacers cut to 5mm,
10mm and 15mm were used to verify the distance between the electrodes.
8.2.3 Schematic of Circuit
The schematic of the circuit is given in figure 90. An AC resonance test set was used to
provide the high voltages required to measure the dielectric strengths of the oils. The
advantage of using a resonance test set is that as soon as the oil breaks down the supply
falls out of resonance, the output voltage decreases and therefore the arc is extinguished.
A 700kΩ water resistor was used to limit the short circuit current during dielectric
failure and so minimise degradation to the oil.
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High voltage connection
Water resistor
AC
resonance Test cell
test set
Haefely
system
control
Earth connection
Figure 90: Schematic of test circuit used to provide up to 300kV to the test cell
The AC resonance test set was controlled by a computer and software supplied by
Haefely test AG.
8.2.4 Other Items Used in the Test
The following items, which are not shown in the circuit schematic, were used:
• The connections between the components used 54mm diameter copper pipe.
Toroids were added in regions of high electric stress around the connections to
the water resistor and near to the elbows to reduce the levels of corona.
• A Yukon Ranger 5x42 digital image intensifier was used to observe the corona
• The water resistor and copper pipe was supported by ceramic insulating stands
• An oil containment tray was used to safeguard against leaks or spills
A photograph of the circuit including the test cell is given in figure 91.
177
Figure 91: Laboratory setup showing the AC resonance test set, water resistor and test
cell
8.2.5 Capability of System
No corona could be detected visually using the image intensifier below 250kV. Air
discharges were seen to emanate above this voltage from the 90° copper elbows on the
ends of the water resistor. At 300kV there was an air flashover between the 54mm
copper pipe and the electrically floating tops of the ceramic insulators supporting the
water resistor.
8.3 Comparison of the AC Breakdown Voltages of the Oils Using

Electrode Gaps of 5mm and 10mm
8.3.1 Introduction
The investigation to compare the breakdown voltages of the oils using electrode gaps of
5mm and 10mm was performed in two parts. The first part used a small sample size of
ten measurements and electrode gaps of 5mm and 10mm. A twenty minute stand time
was given between breakdowns for the breakdown products to disperse. The second part
used a large sample size of thirty measurements and an electrode gap of 5mm. A five
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minute stand time was given between breakdowns.
Before the test cell was used, and between different oils, it was disassembled and
cleaned with petroleum ether. The individual components were cleaned with the oil to
be used for the next test before the test cell was re-assembled. Once assembled, oil was
passed through the test cell to remove any particulates.
As it is known that particles reduce the breakdown voltage of oil, it was important to
reduce the risk of contaminating the oil during handling. The oil is delivered by the
manufacturer in 20 litre or 25 litre containers, which are then stored outside the
laboratory in a shed. The tops and sides of these containers were cleaned with petroleum
ether, using fibreless wipes manufactured by Kimtech, before the oil was poured into
the test cell to remove any particles residing on the container. If the containers were not
clean, then particulate matter could be swept into the test cell by the flow of oil.
The test cell was sealed after it was filled with oil and left to stand overnight. This
precaution was taken to give particulate matter time to settle to the bottom of the test
cell and so reduce their impact on the breakdown voltage. The cell was sealed to
prevent atmospheric moisture from dissolving into the oil. The test cell was opened
immediately before and after testing for the water content of the oil to be measured.
The voltage was controlled automatically by the Haefely software and was applied in a
step by step format rising at 2kV per second. The rms voltage was recorded when the oil
failed. Once failure had occurred the oil was left to stand for either five or twenty
minutes before the next measurement was performed to give the products of breakdown
time to disperse.
8.3.2 Results of the Small Sample of Breakdown Voltages
Restating the test conditions, ten breakdowns were found with a twenty minute stand
time between them.
The water content of a sample taken from the oil at the top of the test cell was measured
immediately before the voltage was applied. The water contents of the oils are given in
table 37. The relative humidity is calculated for room temperature, around 20°C.
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Table 37: Water content of the oils used in the large electrode gap investigation
Gap Mineral oil FR3 Midel 7131
Size (ppm) (%RH) (ppm) (%RH) (ppm) (%RH)
5mm 15 27 132 12 175 6
10mm 18 32 113 10 224 8
The individual breakdown voltages of the oils using electrode gaps of 5mm and 10mm
are shown in figures 92 - 94. Figures 92 and 93 show the raw data that was obtained.
Only five breakdowns were recorded for the Midel 7131 and mineral oil at an electrode
spacing of 10mm because in the other five instances the oil did not break down below
250kV. Figure 94 shows the cumulative probability of the oils failing as a function of
the breakdown voltage. The mean breakdown voltages of the oils are given in table 38
and the lowest breakdown voltages are given in table 39.
250
200
150
100
Mineral oil 5mm
50 FR3 5mm
Midel 7131 5mm

0
0 1 2 3 4 5 6 7 8 9 10
Breakdown number
Figure 92: Distribution of AC breakdown voltages using an electrode gap of 5mm
180
300
250

200
150
Mineral oil 10mm

100
FR3 10mm
50
Midel 7131 10mm
0
0 1 2 3 4 5 6 7 8 9 10
Breakdown number
Figure 93: Distribution of AC breakdown voltages using an electrode gap of 10mm
1
Mineral oil 5mm
0.9 Mineral oil 10mm
0.8 FR3 5mm
FR3 10mm
Cumulaive probability
0.7
Midel 7131 5mm
0.6 Midel 7131 10mm
0.5
0.4
0.3
0.2
0.1
0
50 100 150 200 250
Figure 94: Probability of breakdown with changing voltage using 5mm and 10mm
electrode gaps
181
Table 38: Mean AC breakdown voltages of the oils
Gap Property Mineral oil FR3 Midel 7131

Size (kV) (kV) (kV)
5mm Mean
Breakdown 164 141 134
Voltage
Standard
28 11 13
Deviation
10mm Mean
* *
Breakdown 228
Voltage
Standard * *
26
Deviation
*
Sample size of 10 breakdowns unavailable
Table 39: Lowest AC breakdown voltage of the oils
Gap Property Mineral oil FR3 Midel 7131

Size (kV) (kV) (kV)
5mm Breakdown
95 114 116
Voltage
10mm Breakdown
150 161 195
Voltage
Actual failure of the oil was characterised by continual arcing. The test set would fall
out of resonance, the oil would re-establish itself as an insulator, the transformer moves
back into resonance, the output voltage increases although the oil fails again. Therefore
the test set continually oscillated in and out of resonance.
Occasional breakdown events were noted in the oils, particularly at 10mm distances, at
voltages below those which would cause continual arcing of the oil gap. In some cases,
at the 10mm gap, a few breakdowns occurred at 100kV although the oil did not fail until
over 200kV.
It is thought that these occasional breakdowns were caused at least in part by particles
suspended in the oil in the vicinity of the electrodes. Once breakdown had occurred the
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causal particle was displaced away from the electrode by the expanding gas generated
by the arc. The voltage output of the AC test set falls until the arc is extinguished and
then rises. After the particle has been removed, since dielectric failure is initiated by a
weak link, the oil fails on the next weakest link, at a higher voltage.
For the breakdown voltages using a 5mm gap it is notable that even though the mean
breakdown voltage of mineral oil is 20kV to 30kV higher than that of the esters, the
lowest breakdown voltage of mineral oil is around 20kV lower than that of the esters.
The mean breakdown voltages could not be found for either mineral oil or Midel 7131
with the 10mm gap as both oils withstood the highest voltage that could be delivered by
the test cell, 250kV, in five instances. However, the implication of this is clearly that the
mean breakdown voltages for these two oils were higher than that of FR3, although it is
impossible to say by how much. As for the 5mm gap the lowest breakdown voltage of
the mineral oil was less than that of the esters, by between 11kV and 45kV.
8.3.3 Investigation of the AC Dielectric Strengths of the Oils Using a Larger

Sample Size
This part of the investigation compares the breakdown voltages of the oils using an
electrode gap of 5mm and a sample size of thirty measurements. Increasing the number
of measurement reduces the confidence interval (error) of the mean breakdown voltage
and provides more observations at the lower end of the distribution. Thus this will give
a better comparison between the dielectric strengths of the oils.
The cell was filled with oil and left to stand overnight. The water content of the oils,
given in table 40, was measured immediately before and after the test from the oil at the
top of the test cell. The relative humidity is calculated for room temperature, around
20°C.
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Table 40: Water content of oils before and after investigation
(ppm) (%RH) (ppm) (%RH) (ppm) (%RH)
Before
20 36 165 15 31 1
measurement
After
17 31 83 8 124 5
measurement
The water content of the FR3 was shown to decrease by 82ppm during the course of the
experiment. The higher initial value may have been due to water condensing on the
surface of the FR3 overnight. Du reports, “Even though water is heavier than the oil,
small water bubbles can still exist near the upper body of the oil by surface tension”
[91]. Once an electric field is applied to the oil, dielectrophoretic forces exerted on the
water move the water into regions of high electric stress and away from the top of the
body of oil. Therefore the concentration of water near the top of the test cell decreases
as the water becomes more uniformly spread throughout the oil volume.
The water content of the Midel 7131 increased by 93ppm between measurements.
However, as this oil is extremely hygroscopic this only represents an increase in relative
humidity of 4%. This may be due to the oil absorbing water from the air in the
headspace of the test cell or from the atmosphere of the laboratory as the oil was
sampled for measurement.
A five minute stand time was given between breakdowns. During the previous
investigation, when a twenty minute stand time was given, the oil was periodically
inspected after breakdown. The visible gas bubbles produced by breakdown were found
to quickly disperse, therefore it was concluded that a shorter stand time could be used.
The voltage was applied in steps rising at 2kV per second. The results are given in
figures 95 and 96. Breakdown was defined as when there was continual arcing between
the electrodes for at least three seconds.
Figure 95 shows the raw data and figure 96 displays the cumulative probability of
failure. The results are similar to the first experiment using an electrode gap of 5mm,
shown in figure 92. However, the breakdown voltages shown in figure 95, with the
exception of the first few, tend to lie between 150kV and 200kV whereas in figure 92
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they tend to lie between 100kV and 200kV.
Table 41 gives the mean and lowest breakdown voltages of the oils. Similarly to the
mean and lowest breakdown voltages from the first experiment, shown in tables 38 and
39, the mean breakdown voltage of the mineral oil is higher than that of the esters while
the lowest breakdown voltage of the mineral oil is lower.
250
200
150
100
Mineral oil
50 FR3
Midel 7131
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Breakdown number (n)
Figure 95: Breakdown voltages of oils using an electrode gap of 5mm and a sample size
of 30 measurements
1
Mineral oil
0.9
FR3
0.8
Midel 7131
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
50 100 150 200 250
Figure 96: Cumulative distribution function of the data obtained from the 30
measurement sample size
185
Table 41: Mean and lowest breakdown voltages of the oils using a 5mm electrode gap
Property Mineral oil FR3 Midel 7131

(kV) (kV) (kV)
Mean
Breakdown 181 159 164
Voltage
Lowest
breakdown 114 149 125
voltage
The breakdown voltages appear to be grouped around certain values, as shown by the
red lines in figure 97. These groups are spaced around 7kV – 9kV apart.
1
Mineral oil
0.9
FR3
0.8
Midel 7131
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
50 100 150 200 250
Figure 97: Grouping of breakdowns around certain voltages
Since the grouping of data appears across the three oils, this may be caused by the test
setup rather than the impurities within an oil. In practice two observations were noted
that may explain the data grouping, which are:
i. The AC test set did not precisely raise the voltage in steps of 2kV/s.
Occasionally the voltage would step by 5kV to 10 kV then remain constant for
several seconds. It may be that the output of the test set is stepping between the
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voltages of the data groups rather than rising at 2kV/s.
ii. Spikes were shown to exist on the voltage supply by the test software. This is
believed to have been caused by air discharges around the high voltage
connection to the test cell. Spikes may have triggered dielectric breakdown of
the oil gap.
The test circuit requires modification to prevent corona from appearing around areas of
high electrical stress. Once these air discharges have been removed, a more
representative distribution of breakdown voltages may be obtained.
8.4 Influence of Large Electrode Gap on the Mean Dielectric Strength

of the Oils
Blume [61], Kawaguchi [125] and Trinh [126] have observed that the dielectric strength
of oil is affected by the distance between the electrodes. This section analyses whether
the dielectric strengths of the oils using a 1mm gap (in chapter four) are different from
those when the electrode gap is 5mm.
The conditions of both tests must be discussed in order to ensure that the comparison is
valid.
The breakdown voltages in chapter four were measured according to ASTM D1816.
ASTM D1816 specifies 36mm diameter spherically capped electrodes of the VDE
specification 0370 type.
The breakdown voltages obtained using the 5mm electrode gap were not measured to a
standard. The electrodes used in the large gap test cell were spherical and have a radius
of 25mm. This is the same radius as the electrically active area of the VDE electrodes.
Therefore it is unlikely that there will be differences in breakdown voltage caused by
the geometries in the electrodes.
There may still be differences between the breakdown voltages according to whether
the oil is stirred or not, as this influences the motion of particles within the oil.
Table 42 compares the mean dielectric strengths of the oils according to the electrode
187
gaps of 1mm and 5mm. Figure 96 shows the overall distributions of dielectric strength
according to these electrode gaps.
In chapter four the oils were degassed and dried before their breakdown voltages were
measured whereas they were not conditioned before testing using an electrode gap of
5mm. The water content of the oils was measured before and after test; however, their
gas content was unknown. Facilities were not available to condition the quantities of oil,
25 litres, required to fill the test cell.
Consequently it is difficult to determine how much of the drop in dielectric strength of

the oils is due to them being unconditioned and how much is actually due to the large
volume effect.
Table 42: Comparison of the mean dielectric strengths of the oils and effect of electrode
gap
Gap Mineral oil FR3 Midel 7131

Size kV/mm kV/mm kV/mm
1mm
ASTM D1816 39 41 47
distribution
5mm
10 sample 33 28 27
distribution
5mm
30 sample 36 32 33
distribution
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1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 10 20 30 40 50 60
Dielectric strength (kV/mm)
Mineral oil 1mm ASTM D1816 FR3 1mm ASTM D1816 Midel 7131 1mm ASTM D1816
Mineral oil 5mm FR3 5mm Midel 7131 5mm
Figure 98: Effect of electrode gap on the dielectric strength of oil
8.5 Withstand Voltage of a 20mm Electrode Gap

It has been noted that two types of breakdown can occur. One is occasional, momentary,
breakdown as have been observed and the other is continual arcing.
When an oil is used in a transformer, there must not be any momentary breakdowns of
the oil gap. Therefore the next test investigates applying a realistic level of electrical
stress for a transformer to an oil for a certain duration to ascertain whether there are any
flashovers.
A voltage of 200kV was applied to an electrode gap of 20mm for one hour. The electric
stress equates to 10kV/mm, comparable to the highest levels of stress encountered in a
power transformer.
None of the oils failed during this investigation. Further research is required to analyse
the effect of other levels of stress and electrode gap on the withstand voltage of oil.
189
8.6 Conclusions
When the electrode gap was set to 5 mm the mean of the AC breakdown voltages for
both esters are lower than that of the mineral oil. This was consistent in both the first
investigation, based on ten measurements, and in the second investigation, based on
thirty measurements.
In the first experiment the mean AC breakdown voltage for mineral oil was 164kV and
the mean breakdown voltages for FR3 and Midel 7131 were 85% and 82% of this
respectively. In the second experiment the mean AC breakdown voltage of mineral oil
was 181kV and the mean breakdown voltages for FR3 and Midel 7131 were 88% and
91% of this respectively.
It was not possible to measure the breakdown voltages of the mineral oil and Midel
7131 using an electrode gap of 10mm because these oils frequently withstood the
maximum operating voltage of the system. The connections between the test cell and
AC test set will require modification to operate at voltages higher than 250kV.
Despite the mean breakdown voltages of the esters being less than that of the mineral
oil, the lowest breakdown voltages of the mineral oil are less than those of the esters.
This was shown consistently in the three experiments, using a 5mm electrode gap and
ten breakdowns, using a 5 mm gap and 30 breakdowns, and using a 10mm gap and ten
breakdowns.
In the first of the two investigations using an electrode gap of 5mm, based on ten
measurements, the lowest AC breakdown voltages for mineral oil was 95kV, 83% of
that of both FR3 and Midel 7131. In the second investigation, based on thirty
measurements, the lowest AC breakdown voltage of mineral oil was 114kV, 77% of
that of FR3 and 90% of that of Midel 7131. The lowest breakdown voltage for mineral
oil when using a 10mm gap was 150kV, 93% of that of FR3 and 77% of that of Midel
7131.
The dielectric strengths of the oils are lower when a 5mm electrode gap is used as
compared to a 1mm gap. Further analysis is required to determine whether the
differences are due to contamination or the molecular nature of the oil.
190
It is difficult to conclude how particles have affected the breakdown voltages of each oil
because their particle content was not measured. A future study could investigate the
effect of using filtered oil.
191
Chapter 9: Summary, Conclusions and Further Work
9.1 Summary of the Work Presented in this Thesis

The work presented in this thesis has focussed on the effectiveness of esters as electrical
insulation, compared to that of mineral oil. This study has analysed the AC and
lightning impulse breakdown voltages of the oils under a variety of conditions which
are representative of the operating environment inside the transformer. The breakdown
voltages of the oils were analysed under the following situations:
• When the oils were new and had little contamination
• When the oils were contaminated with water
• When the oils were subjected to temperature, between 30°C and 70°C
• When wet oil was subjected to temperature, between 30°C and 70°C
• When the oils were thermally aged using an air atmosphere and potential metal
catalysts
• When the electrode spacings are larger than 1mm, up to 5mm and 10mm
9.2 Conclusions, Implications and Future Work

This section reviews three scenarios, drawing conclusions, considering the implications
for transformer insulation design and suggesting what future work could be done to
further ascertain the compatibility of ester oils with power transformers, in each case.
These scenarios are as follows:
i. Application of an AC voltage across a 1mm or 2mm electrode gap according to

standard ASTM D1816
ii. Application of an AC voltage across a 5mm electrode gap
iii. Application of a lightning impulse across an electrode gap of 3.8mm according
to standard ASTM D3300
9.2.1 AC Breakdown Voltages of Oils Using 1mm and 2mm Electrode Gaps
It can be concluded that the AC breakdown voltages of the esters, measured according
to ASTM D1816, were at least equal to those of the mineral oil throughout the
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investigations performed in this study.
The distribution of one hundred breakdown voltages for each oil as new was analysed.
This showed that not only was the mean breakdown voltage of the esters at least equal
to that of the mineral oil, the lowest breakdown voltage of the esters was also similar.
Dielectric failure of oil is initiated by some weak link. Although the oils were new, they
were not filtered before use. Consequently it is very likely that breakdown was initiated
by particulate contamination. Therefore in order to observe a significant difference in
the AC breakdown voltages of the oils due to their differing chemistries, it may be
necessary to remove this particulate contamination from the oil. Not only must the oil
be filtered, but the test system must be set up to prevent the oil becoming contaminated
once filtered.
A transformer is filled with filtered oil. The implication is that, although esters were
found to perform similarly to mineral oil in these experiments, there might be a
significant difference in their breakdown voltages once the oils are filtered to a level
comparable to that expected for oil being used within a transformer.
The suitability of using the Gaussian and Weibull distributions to model the distribution
of breakdown voltages and estimate a withstand voltage was investigated. The results
provided by the Weibull distribution were more accurate than those given by the
Gaussian distribution. The distributions of breakdown voltages failed the Shapiro Wilk
test for normality, meaning that the Gaussian distribution is not an appropriate model.
The reason for this is that the Gaussian distribution makes the, essentially flawed,
assumption that the distribution has no skewness while the Weibull distribution does not
make this assumption. The Weibull distribution provided a reasonable approximation
across much of the spread of data but broke down at low probability.
The AC breakdown voltages of the esters were affected less by water than those of
mineral oil. The reason for this is that esters are far more hygroscopic than mineral oil,
so can dissolve more water. The effect of water on breakdown voltage is related to the
relative humidity of the oil. If an ester is exposed to atmospheric moisture then its
relative humidity will equilibrate with that of the air. Therefore if the ester is not kept
dry within the transformer a higher amount of water will dissolve in it and possibly
193
reduce its dielectric strength.
Although in this investigation the esters were found to have higher breakdown voltages
than mineral oil at the same relative humidity and ambient temperature, which might
seem to imply that the effect of relative saturation on an ester should not be of greater
concern than for mineral oil, the significance of the effect of particles on the breakdown
voltage of an oil is such that this is not assured. Therefore further work using filtered
oils must be undertaken to satisfy the industry of the effect of particles and water.
The effect of water on the breakdown voltage of esters was found to not only be related
to its relative humidity. Chadband believes that water causes breakdown by changing
the conductivity of hygroscopic insulating particles suspended within the oil [32]. Since
esters are more hygroscopic than mineral oil they absorb a greater proportion of the
water, hence keeping the particles drier. When the particles are dry they remain non-
conductive and therefore, according to Chadband’s theory, there is less of an effect on
the breakdown voltage of the oil.
In a transformer, the implication of Chadband’s hypothesis is that the reduction of oil

dielectric strength caused by water will be influenced by its particle content. Generally,
as a transformer ages its particle content increases. Consequently water may affect the
dielectric strength of oil more when the transformer is old than when new.
Temperature does not appear to affect the breakdown voltage of dry oil, therefore,
physical properties such as density and viscosity have had little or no effect over the
studied temperature range.
Temperature appeared to increase the breakdown voltage of oil by decreasing its

relative humidity, as when oil is heated, it becomes more hygroscopic. However, the
breakdown voltages of Midel 7131 did not appear to be a simple function of relative
humidity. Chadband proposed that water reduces the dielectric strength of an oil by
affecting the conductivity of hygroscopic particles. Therefore it is plausible that as the
more hygroscopic ester is heated it dries the particles, which become less conductive,
reducing their effect on the breakdown voltage.
194
Future work will be necessary to investigate the effect of particles on the breakdown
voltages of oil, especially when the oil is wet and hot.
The breakdown voltage of wet oil did not change immediately as it was heated and
cooled. The implication of this is that if the temperature of a transformer oil suddenly
changes, its breakdown voltage does not also change suddenly.
The mean breakdown voltages of the esters were not reduced by thermal ageing, even
when there were signs of ageing in the FR3. The mean breakdown voltage of mineral
oil was found to have been reduced. It is thought that both water and insoluble
particulate matter was the cause of this reduction. The breakdown voltage of the FR3
may have not been reduced because this ester had neither high water content nor
observable sludge.
The by-products of ageing are polar, therefore, they do not dissolve well into non-polar
mineral oil. Since FR3 is more polar, the ageing by-products are more soluble in this
oil. As particles are known to initiate dielectric failure, it may be that the breakdown
voltage of FR3 did not fall during ageing because this oil prevented the formation of
solid matter.
The overall effect of the by-products of oil ageing on its breakdown voltage is also
dependent on how the by-products interact with the cellulosic insulation. It is proposed
that the acids formed by hydrolysis of an ester are benign when compared to those
created by oxidation of mineral oil, and as such, they do not degrade the cellulose to the
same extent [112].
When cellulose degrades water is produced, which may affect the breakdown voltage of
the oil [127]. Water itself increases the rate of cellulose degradation. An advantage of
the hydrolysis reaction is that this removes water, and therefore helps to limit the rate of
cellulose degradation. When the rate of cellulose degradation is suppressed, less water
is created and therefore the reduction in breakdown voltage of the oil is less.
9.2.2 AC Breakdown Voltages of Oils Using an Electrode Gap of 5mm
Further studies are required before a conclusion can be reached. The breakdown
voltages of the esters were comparable to those of the mineral oil. The results showed
195
the breakdowns to be bunched around certain voltages. Therefore it may be that failure
is being initiated by either contaminates within the test cell or a characteristic of the test
circuit, for instance voltage spikes.
The mean dielectric strength of the oils using a 5mm electrode gap was lower than when
a 1mm was used. However, it is unknown whether this decrease was caused by the
nature of the oil, contamination in the oil or the construction of the test circuit.
The oils will require filtering and the system must be changed to prevent the oils
becoming contaminated once filtered.
9.2.3 Lightning Impulse Breakdown Voltages of Oils Using an Electrode Gap of

3.8mm
The lightning impulse breakdown voltages of the esters, when new, were found to be
between 10% and 20% less than those of the mineral oil. The mean breakdown voltages
were -196kV for mineral oil, -181kV for FR3 and -165kV for Midel 7131. The
difference between the mean breakdown voltages for mineral oil and FR3 may not be
significant because the measurement error may be up to 10kV.
Both particles and the molecular nature of the oil affect the lightning impulse dielectric
strength of an oil. Since the duration of the lightning impulse is very short, particles do
not have time to be moved around by the electric field [77]. Conductive particles affect
the lightning impulse breakdown of oil more than non conductive ones because they
polarize instantly causing breakdown, whereas non-conductive ones do not have
sufficient time [43].
It is unclear whether the lower mean lightning impulse breakdown voltage of Midel
7131 is caused by its molecular nature or whether the particles suspended within it are
more conductive than the other two oils.
It was noted that water reduced the lightning impulse breakdown voltage of mineral oil.
This may have been caused by suspended particles adsorbing water and becoming more
conductive, hence polarizing faster and initiating breakdown. The mean lightning
196
impulse breakdown voltage of mineral oil was also reduced by ageing. Water and
particles of insoluble sludge were observed to exist in the sample of aged mineral oil.
The lightning impulse breakdown voltages of the esters did not appear to have been
affected by water or ageing. It may have been that the esters were not sufficiently wet to
observe an affect on their breakdown voltage. As esters are more hygroscopic than
mineral oil they absorb a greater proportion of the water present in the sample keeping
the particles dryer. The lightning impulse breakdown voltages of the aged samples of
ester were not reduced being visibly free from insoluble sludge.
9.3 Final Conclusions
Particles and water are instrumental in reducing the breakdown voltages of oil.
Therefore a study of the dielectric strengths of esters should not just investigate the
performance of these oils when new, but it must also consider the effect of
contamination on their breakdown voltages.
The AC dielectric performance of esters was at least comparable to that of mineral oil.
The lightning impulse breakdown voltage of the esters was slightly less than that of
mineral oil when new but was not reduced by water and ageing, as was that of mineral
oil. Hence the performance in service may actually be better.
9.4 Future Work
The studies presented in this thesis have focussed on actual breakdown of oil and have
not studied the actual mechanisms leading to dielectric failure. In order to analyse how
the molecular structure of an ester influences its dielectric strength the processes
occurring just before breakdown must be analysed.
This project has only studied the dielectric performance of oils using simple
configurations of electrode. In reality the geometries of the conductors inside a
transformer are more complex than this, and may include cellulose. Therefore in order
to investigate the suitability of esters for replacing mineral oil in a transformer, the
197
dielectric strength of an oil gap using geometries realistic of an actual transformer must
be studied.
198
Appendix A: Tabulated Data of the Breakdown Voltages of
New Oil
Table 43: AC Breakdown voltages of new oil
Observation Mineral Oil FR3 Midel 7131 Observation Mineral Oil FR3 Midel 7131
(n) (kV) (kV) (kV) (n)
1 37.3 38.4 40.2 62 39.7 47.6 47.1
2 36.3 40.3 36.6 63 32.4 43.0 53.3
3 33.2 33.4 25.9 64 41.5 44.3 57.5
4 41.2 42.5 43.3 65 45.3 44.1 44.8
5 40.3 31.5 40.7 66 40.9 46.9 50.9
6 35.5 32.6 42.9 67 47.0 30.0 54.4
7 37.7 33.5 24.2 68 36.1 47.7 51.5
8 40.1 43.5 49.1 69 37.3 42.9 51.8
9 25.2 38.6 54.8 70 38.0 37.2 49.1
10 40.1 34.9 46.4 71 40.5 46.0 48.9
11 37.7 29.6 29.3 72 44.5 43.8 52.2
12 39.3 41.4 50.4 73 43.0 42.7 43.9
13 30.0 42.9 45.4 74 41.5 48.1 42.5
14 35.8 39.7 38.0 75 42.3 44.6 49.5
15 33.9 37.1 54.0 76 40.3 34.0 35.8
16 38.6 42.5 32.7 77 38.5 48.0 48.9
17 36.5 40.6 47.6 78 42.2 34.9 51.5
18 36.5 38.9 53.7 79 42.6 40.5 54.5
19 30.8 29.1 49.2 80 40.5 43.8 41.5
20 37.5 30.3 49.6 81 45.1 40.6 58.9
21 39.5 38.3 47.8 82 39.8 45.2 45.5
22 40.2 37.3 40.4 83 44.8 45.1 51.2
23 40.2 38.7 44.8 84 44.0 44.6 45.5
24 35.8 40.9 48.9 85 39.3 46.4 37.6
25 41.5 33.7 43.1 86 40.6 47.0 50.4
26 37.4 45.0 51.9 87 45.5 46.6 49.1
27 36.4 40.6 42.5 88 44.2 410 36.8
28 37.9 37.1 47.1 89 40.4 42.8 46.1
29 38.7 41.6 48.6 90 44.5 41.1 48.0
30 35.4 40.7 42.1 91 40.6 44.7 55.4
31 38.0 36.1 41.4 92 43.3 46.0 42.0
32 31.5 35.6 47.3 93 44.3 49.2 37.5
33 34.8 44.9 47.7 94 42.2 45.1 39.2
34 37.1 40.3 50.4 95 45.1 48.0 46.7
35 33.8 33.7 49.1 96 40.0 48.2 48.3
36 39.6 37.0 50.3 97 40.8 37.5 48.1
37 40.1 36.9 49.7 98 42.7 33.7 49.6
38 41.1 48.4 45.7 99 44.6 37.7 42.9
39 41.3 43.9 44.6 100 41.2 34.7 38.1
40 39.8 42.2 42.7 101 49.5
41 38.0 45.3 44.7 102 56.1
42 41.9 23.8 45.1 103 52.4
43 35.5 39.2 45.2 104 40.6
44 37.6 46.3 53.9 105 37.1
45 37.6 29.9 36.9
46 41.9 34.0 53.9
47 39.3 39.8 47.8
48 38.0 42.9 39.8
49 44.3 41.0 50.0
50 34.4 41.2 49.6
51 40.9 38.9 51.4
52 40.1 50.2 50.0
53 37.1 43.6 33.8
54 36.6 39.7 51.7
55 40.3 39.3 51.8
56 38.2 45.8 49.6
57 39.0 43.3 40.0
58 41.3 42.9 51.0
59 44.9 41.1 43.0
60 40.5 40.2 56.2
61 41.2 48.4 45.7
199
Table 44: Breakdown voltages for repeat of Midel 7131
Observation Breakdown Observation Breakdown Observation Breakdown Observation Breakdown
voltage voltage voltage voltage
(n) (kV) (n) (kV) (n) (kV) (n) (kV)
1 25.0 26 34.6 51 32.1 76 38.8
2 36.3 27 44.1 52 31.8 77 43.8
3 30.8 28 46.1 53 37.1 78 40.8
4 39.0 29 39.9 54 40.4 79 40.7
5 30.4 30 44.4 55 37.5 80 34.8
6 38.2 31 48.6 56 26.0 81 34.8
7 33.7 32 41.1 57 37.5 82 37.6
8 40.9 33 25.5 58 43.3 83 41.3
9 39.0 34 33.8 59 39.7 84 43.5
10 34.1 35 36.2 60 44.4 85 39.5
11 25.4 36 30.4 61 42.4 86 41.5
12 29.7 37 41.4 62 41.6 87 45.6
13 29.8 38 33.4 63 36.8 88 37.4
14 44.3 39 31.6 64 43.5 89 41.5
15 42.5 40 43.6 65 37.5 90 39.8
16 43.5 41 34.0 66 43.0 91 42.1
17 42.3 42 45.1 67 39.3 92 37.0
18 23.8 43 39.3 68 43.6 93 41.1
19 28.2 44 35.6 69 41.5 94 36.6
20 32.8 45 42.5 70 36.2 95 38.0
21 33.6 46 37.9 71 34.9 96 39.0
22 41.1 47 44.6 72 42.4 97 46.7
23 15.2 48 46.7 73 43.8 98 42.0
24 34.1 49 43.1 74 39.8 99 39.0
25 43.7 50 35.3 75 40.1 100 34.8
Table 45: Lightning impulse breakdown voltages of new oil
Observation Mineral oil FR3 Midel 7131

(n) (kV) (kV) (kV)
1 -200 -184 -164
2 -198 -184 -170
3 -199 -174 -164
4 -195 -183 -164
5 -190 -181 -164
200
Appendix B: Tabulated data of the Effect of Water on the
Breakdown Voltage of Oil
Table 46: AC Breakdown voltages of mineral oil as a function of water content
Water content of mineral oil in ppm and breakdown voltage in kV using 1mm
electrode gap
5ppm 7ppm 14ppm 17ppm 19ppm 20ppm 28ppm
36.4 16.8 18.1 10.6 13.0 11.9 5.9
29.7 22.3 15.9 13.1 14.5 13.8 6.5
22.6 23.2 15.6 15.2 19.2 12.7 4.5
25.6 22.1 14.0 12.2 14.1 12.6 5.1
30.3 16.8 15.8 11.4 14.1 15.3 6.8
32.9 28.1 17.7 9.6 15.0 16.0 5.4
32.0 20.6 21.7 16.9 9.6 17.6 6.0
35.5 18.8 16.8 8.8 18.1 14.2 7.9
29.1 19.8 19.2 15.8 14.5 16.9 6.7
25.3 17.2 19.9 15.6 10.4 11.2 5.5
30.6 17.4 23.0 18.1 18.0 19.5 7.5
29.0 24.1 19.5 17.5 17.5 17.3 7.6
28.2 18.2 22.3 21.7 17.1 17.9 8.1
32.3 17.7 19.4 22.3 17.4 19.9 7.3
25.9 25.7 24.7 14.8 19.4 15.6 6.5
30.1 22.3 26.9 14.3 24.2 15.2 7.2
20.3 30.0 18.2 10.9 18.1 14.0 6.4
31.6 27.9 26.0 11.5 18.1 16.8 6.5
37.2 24.2 27.5 18.1 23.6 15.8 7.6
24.3 20.1 26.0 15.1 25.7 - 7.0
Table 47: AC Breakdown voltages of FR3 as a function of water content
Water content of FR3 in ppm and breakdown voltage in kV using 1mm electrode gap
31ppm 70ppm 117ppm 146ppm 272ppm 339ppm 420ppm 532ppm 881ppm 1500ppm
28.1 32.0 38.7 46.5 28.8 33.5 20.7 14.1 7.4 13.9
32.9 33.3 31.3 45.7 38.3 34.4 17.7 22.7 7.8 9.0
38.7 39.3 41.8 43.8 39.9 46.6 27.0 18.6 8.3 6.9
30.9 42.1 39.4 34.7 43.1 38.7 33.0 30.2 7.9 8.7
33.3 39.7 43.0 34.5 37.0 21.2 23.4 21.3 9.2 12.8
37.8 33.0 42.6 29.5 44.0 43.5 17.5 21.7 9.1 6.6
32.7 34.2 43.5 31.7 39.4 38.8 26.2 28.0 8.3 8.7
30.0 39.1 40.9 33.0 37.6 37.8 23.7 24.7 9.6 10.7
29.2 37.7 24.5 32.6 35.3 36.4 32.4 30.2 6.8 9.3
31.2 42.1 41.3 31.3 32.5 41.1 31.2 29.6 8.3 9.8
34.9 44.9 34.1 30.4 44.7 23.7 7.2
34.9 42.7 39.9 24.5 34.6 24.1 7.6
37.7 45.2 44.8 38.6 42.4 33.3 8.0
31.8 43.5 37.8 45.8 47.2 25.8 7.4
28.4 45.1 39.8 41.3 43.5 18.0 7.4
37.9 40.3 37.5 36.6 45.1 16.2 6.7
37.2 44.9 42.2 39.6 41.3 23.6 8.6
37.0 42.2 47.3 45.4 41.5 22.0 8.8
35.5 34.1 34.4 32.7 18.7 27.7 8.0
40.3 36.8 42.3 44.5 37.0 21.5 7.5
201
Table 48: AC Breakdown voltages of Midel 7131 as a function of water content
Water content of Midel 7131 in ppm and breakdown voltage in kV using 1mm electrode gap
76ppm 168ppm 312ppm 539ppm 644ppm 799ppm 1188ppm 1569ppm 1921ppm

42.0 32.2 18.3 42.5 52.9 19.4 13.5 10.1 11.1
42.2 16.8 27.9 39.2 33.9 27.5 14.8 8.7 9.1
43.2 34.0 36.0 30.6 19.9 15.1 15.0 10.1 9.0
44.4 43.3 40.5 21.7 38.7 38.8 9.8 10.0 13.1
41.2 35.1 42.9 51.2 42.3 25.9 15.3 9.2 9.7
47.6 44.4 43.8 47.2 27.5 32.5 11.9 5.6 9.6
46.5 47.3 46.6 51.3 47.2 20.6 11.3 6.5 8.8
50.0 42.8 49.3 52.9 50.3 31.9 14.7 12.4 9.0
47.8 47.5 20.8 25.6 52.2 23.1 18.8 11.8 11.3
45.2 47.0 27.4 27.7 41.5 18.5 18.9 10.9 11.1
52.5 42.7 30.1 50.9 36.6 32.2 11.0
36.9 41.6 37.6 47.9 45.6 44.3 10.1
46.7 23.2 45.0 55.9 33.3 22.1 12.1
31.8 40.0 52.2 35.6 36.1 40.9 12.3
47.8 46.1 44.7 46.1 28.5 30.2 12.3
38.8 19.9 53.7 41.2 55.8 35.8 11.3
50.6 39.5 37.2 54.3 26.0 33.5 10.1
35.3 44.8 52.5 48.4 22.6 43.1 13.6
44.2 37.5 52.7 39.8 27.6 31.3 11.9
46.4 42.1 46.1 24.3 34.6 27.2 13.3
Table 49: Lightning Impulse Breakdown voltages of mineral oil as a function of water
content
Water content of mineral oil in ppm and

breakdown voltage in kV
5ppm 7ppm 14ppm 17ppm

-202 -190 -190 -164
-205 -195 -190 -170
-205 -198 -190 -170
-205 -199 -191 -170
-208 -200 -191 -172
Table 50: Lightning Impulse Breakdown voltages of FR3 as a function of water content
Water content of FR3 in ppm and breakdown voltage

in kV
26ppm 70ppm 117ppm 273ppm 339ppm

-174 -160 -175 -170 -179
-181 -161 -188 -170 -179
-183 -170 -188 -176 -179
-184 -170 -190 -176 -181
-184 -171 -192 -176 -181
202
Table 51: Lightning Impulse Breakdown voltages of Midel 7131 as a function of water
content
Water content of Midel 7131 in ppm and breakdown

voltage in kV
77ppm 168ppm 312ppm 539ppm 644ppm

-164 -170 -167 -169 -160
-164 -170 -167 -169 -170
-164 -170 -167 -169 -171
-164 -171 -170 -170 -177
-170 -179 -173 -170 -177
203
Appendix C: Tabulated Data of the Effect of Temperature on
the Breakdown Voltage of Oil
Table 52: AC Breakdown voltages of dry oil as a function of temperature

Temperature Breakdown Temperature Breakdown Temperature Breakdown
voltage voltage voltage
(°C) (kV) (°C) (kV) (°C) (kV)
1 64.0 28.2 61.2 37.0 70.2 38.0
2 62.8 32.6 59.7 39.9 68.6 32.9
3 61.7 30.7 58.1 34.9 67.1 37.4
4 60.5 33.5 56.6 36.6 65.5 35.3
5 59.4 31.9 55.0 36.7 64.0 37.1
6 58.2 35.5 53.5 39.2 62.4 39.2
7 57.2 29.2 52.9 38.0 61.3 38.8
8 56.2 33.4 52.3 38.1 60.1 38.0
9 55.2 35.6 51.7 38.1 59.0 40.0
10 54.2 34.2 51.1 40.3 57.8 35.6
11 53.2 40.5 53.5 37.7 56.7 35.4
12 52.5 33.4 49.6 32.6 55.8 39.2
13 51.8 33.3 48.7 37.5 55.1 35.2
14 51.0 32.6 47.9 34.3 54.2 27.7
15 50.3 32.2 47.1 33.0 53.4 42.6
16 49.6 34.2 46.1 30.3 52.6 34.0
17 49.0 37.9 45.4 31.2 51.8 32.3
18 48.4 32.2 44.8 33.6 51.0 38.8
19 47.8 29.2 44.1 37.5 50.1 36.6
20 47.2 38.0 43.5 35.0 49.3 37.1
21 46.7 32.1 42.8 34.0 48.5 31.9
22 46.1 36.8 42.3 36.2 47.9 36.5
23 45.5 32.1 41.7 34.5 47.3 36.1
24 44.9 35.9 41.2 34.7 46.6 34.3
25 44.3 22.7 40.6 37.1 46.0 33.8
26 43.7 34.9 40.1 34.9 45.4 31.3
27 43.2 32.5 39.7 29.6 45.4 35.8
28 42.7 32.7 39.3 33.5 45.4 35.8
29 42.3 34.4 38.4 28.3 45.4 34.4
30 41.8 31.6 38.4 33.5 45.4 34.9
31 41.3 28.1 38.0 37.6 42.6 37.5
32 41.0 30.6 37.7 34.0 42.0 33.5
33 40.6 33.6 37.4 30.9 41.5 34.7
34 40.3 29.9 37.1 33.2 40.9 35.4
35 39.9 32.3 36.8 34.9 40.4 39.3
36 39.6 26.7 36.5 30.9 40.5 34.9
37 39.3 31.8 36.3 33.3 40.1 34.7
38 39.0 30.2 36.1 25.1 39.7 37.6
39 38.6 33.6 35.9 34.7 39.4 38.6
40 38.3 28.3 35.7 32.3 39.0 36.8
41 38.0 24.1 35.6 37.3 38.6 34.6
42 37.8 33.1 35.4 35.1 38.3 35.8
204
43 37.5 31.3 35.2 37.5 38.0 30.1
44 37.3 30.8 35.0 37.4 37.8 37.5
45 37.0 28.7 34.8 36.6 37.5 33.6
46 36.8 28.7 34.6 34.8 37.2 37.1
47 36.6 31.4 34.4 36.0 36.9 35.9
48 36.3 26.0 34.2 39.2 36.6 36.3
49 36.1 28.2 34.1 33.2 36.4 32.2
50 35.8 32.2 33.9 32.7 35.8 33.3
51 35.6 32.6 33.7 36.7 35.6 36.8
52 35.4 25.8 33.6 38.0 35.3 37.8
53 35.3 32.0 33.5 33.8 35.1 35.7
54 35.1 28.2 33.3 37.2 34.8 33.7
55 34.9 26.6 33.2 39.2 34.6 37.0
56 34.8 31.3 33.1 30.3 34.3 35.6
57 34.6 32.9 33.1 37.0 34.0 35.9
58 34.4 29.8 32.8 38.2 33.8 38.2
59 34.2 25.7 32.7 35.0 33.7 37.5
60 34.1 35.3 32.6 40.2 33.5 36.8
61 33.9 26.7 32.5 31.9 33.4 39.3
62 33.8 28.1 32.3 34.5 33.2 32.3
63 33.7 32.9 32.2 38.7 33.1 37.1
64 33.6 23.7 32.1 32.3 32.9 36.9
65 33.5 31.3 31.9 37.1 32.8 33.0
66 33.4 31.5 31.8 35.7 32.6 34.5
67 33.2 31.2 31.7 33.1 32.5 32.3
68 33.1 27.3 31.6 40.6 32.3 23.9
69 33.0 31.3 31.6 37.3 32.1 33.7
70 32.9 35.1 31.5 40.3 32.0 38.1
71 32.8 34.2 31.4 34.4 31.8 34.0
72 32.7 33.3 31.4 34.8 31.7 31.6
73 32.6 34.4 31.4 35.1 31.5 35.3
74 32.5 32.6 31.3 36.1 31.3 29.5
75 32.4 34.4 31.3 38.3 31.2 37.4
76 32.3 32.6
77 32.2 32.2
78 32.1 30.4
79 32.1 28.8
80 32.0 29.2
81 31.9 31.8
82 31.8 27.7
83 31.7 34.6
84 31.7 29.0
85 31.6 30.4
Table 53: AC Breakdown voltages of wet oil as a function of temperature

Temperature Breakdown Dielectric Temperature Breakdown Dielectric Temperature Breakdown Dielectric
voltage Strength voltage strength voltage Strength
(°C) (kV) (kV/mm) (°C) (kV) (kV/mm) (°C) (kV) (kV/mm)
68.1 20.3 10.2 66.8 34.7 17.4 72.2 18.8 9.4
66.7 32.8 16.4 65.5 41.5 20.8 70.4 19.9 10.0
65.2 27.4 13.7 64.1 47.5 23.8 68.7 22.9 11.5
205
63.8 19.8 9.9 62.8 49.0 24.5 66.9 24.5 12.3
62.4 34.0 17.0 61.5 50.9 25.5 65.1 20.5 10.3
61.0 31.4 15.7 60.2 51.1 25.6 63.4 29.8 14.9
59.5 32.1 16.1 58.8 40.1 20.1 61.6 24.2 12.1
58.1 31.3 15.7 57.5 29.7 14.9 59.8 22.5 11.3
56.7 35.7 17.9 56.2 31.6 15.8 58.0 24.6 12.3
55.2 34.4 17.2 54.8 48.2 24.1 56.3 20.6 10.3
53.8 28.7 14.4 53.5 44.3 22.2 54.5 25.2 12.6
53.0 25.5 12.8 52.5 46.9 23.5 53.7 28.7 14.4
52.2 25.8 12.9 51.5 49.1 24.6 53.0 21.7 10.9
51.4 35.5 17.8 50.6 53.9 27.0 52.2 28.2 14.1
50.6 36.0 18.0 49.6 48.6 24.3 51.4 26.0 13.0
49.9 40.2 20.1 48.6 45.1 22.6 50.7 27.9 14.0
49.1 25.7 12.9 47.8 43.6 21.8 49.9 31.6 15.8
48.3 33.1 16.6 47.0 39.2 19.6 49.1 28.3 14.2
47.5 28.9 14.5 46.2 40.3 20.2 48.3 29.5 14.8
46.7 31.2 15.6 45.4 43.6 21.8 47.6 29.3 14.7
45.9 43.3 21.7 44.6 35.9 18.0 46.8 30.8 15.4
45.4 24.2 12.1 44.1 37.2 18.6 46.3 18.1 9.1
44.9 33.9 17.0 43.7 26.9 13.5 45.7 29.3 14.7
44.4 29.0 14.5 43.2 36.0 18.0 45.2 27.3 13.7
43.9 35.5 17.8 42.7 28.5 14.3 44.7 26.9 13.5
43.4 34.3 17.2 42.3 38.4 19.2 44.2 31.0 15.5
42.8 20.0 10.0 41.8 33.0 16.5 43.6 30.1 15.1
42.3 32.6 16.3 41.3 34.0 17.0 43.1 27.8 13.9
41.8 30.3 15.2 40.8 35.6 17.8 42.6 34.4 17.2
41.3 22.9 11.5 40.4 43.1 21.6 42.0 29.4 14.7
40.8 32.6 16.3 39.9 40.6 20.3 41.5 26.9 13.5
40.5 32.2 16.1 39.6 31.4 15.7 41.0 22.9 11.5
40.1 42.9 21.5 39.2 40.6 20.3 40.5 29.5 14.8
39.8 23.2 11.6 38.9 35.2 17.6 40.0 32.6 16.3
39.4 28.2 14.1 38.5 41.5 20.8 39.5 34.7 17.4
39.1 26.4 13.2 38.2 31.9 16.0 39.1 28.6 14.3
38.7 25.4 12.7 37.9 38.0 19.0 38.6 30.2 15.1
38.4 24.5 12.3 37.5 37.1 18.6 38.1 29.1 14.6
38.0 27.0 13.5 37.2 35.8 17.9 37.6 25.5 12.8
37.7 30.6 15.3 36.8 34.0 17.0 37.1 31.1 15.6
37.3 26.7 13.4 36.5 37.7 18.9 36.6 27.8 13.9
37.0 20.7 10.4 36.2 42.2 21.1 36.4 34.0 17.0
36.8 24.6 12.3 36.0 39.1 19.6 36.1 28.6 14.3
36.5 19.8 9.9 35.7 33.1 16.6 35.9 37.8 18.9
36.3 19.5 9.8 35.4 38.0 19.0 35.7 35.3 17.7
36.0 25.1 12.6 35.2 35.8 17.9 35.5 30.0 15.0
35.7 22.9 11.5 34.9 43.0 21.5 35.2 30.6 15.3
35.5 23.8 11.9 34.6 38.0 19.0 35.0 24.2 12.1
35.2 22.1 11.1 34.4 36.6 18.3 34.8 38.2 19.1
35.0 23.2 11.6 34.1 42.2 21.1 34.5 34.6 17.3
34.7 25.4 12.7 33.8 25.5 12.8 34.3 28.6 14.3
34.5 22.6 11.3 33.7 32.7 16.4 34.1 22.4 11.2
34.4 27.1 13.6 33.5 33.5 16.8 33.8 28.7 14.4
34.2 31.4 15.7 33.4 35.6 17.8 33.6 33.8 16.9
34.1 32.5 16.3 33.2 40.1 20.1 33.3 32.1 16.1
33.9 17.9 9.0 33.1 39.0 19.5 33.1 34.4 17.2
33.7 20.1 10.1 32.9 40.3 20.2 32.8 34.0 17.0
206
33.6 23.5 11.8 32.8 39.7 19.9 32.6 43.1 21.6
33.4 19.8 9.9 32.6 39.4 19.7 32.3 20.6 10.3
33.3 26.5 13.3 32.5 36.5 18.3 32.1 36.6 18.3
33.1 30.4 15.2 32.3 35.0 17.5 31.8 22.0 11.0
33.0 28.9 14.5 32.1 38.9 19.5 31.6 23.4 11.7
32.8 30.9 15.5 31.9 40.1 20.1 31.3 31.7 15.9
32.7 30.7 15.4 31.7 32.3 16.2 31.1 32.5 16.3
32.6 37.3 18.7 31.5 33.2 16.6 30.8 24.0 12.0
32.5 33.7 16.9 31.3 30.7 15.4 30.6 26.2 13.1
32.3 33.5 16.8 31.1 34.0 17.0 30.3 31.3 15.7
32.2 28.0 14.0 30.9 35.7 17.9 30.1 40.5 20.3
32.1 23.5 11.8 30.7 34.6 17.3 29.8 29.9 15.0
31.9 28.3 14.2 30.5 38.1 19.1 29.6 37.6 18.8
31.8 26.9 13.5 58.9 37.2 18.6 70.3 41.0 20.5
31.7 26.0 13.0 57.8 35.8 17.9 68.9 32.0 16.0
31.5 28.0 14.0 56.7 37.4 18.7 67.5 24.2 12.1
31.4 26.7 13.4 55.7 39.7 19.9 66.1 25.3 12.7
31.3 37.0 18.5 54.6 14.7 7.4 64.7 34.5 17.3
31.2 28.6 14.3 53.5 26.6 13.3 63.3 34.2 17.1
31.0 24.0 12.0 52.4 26.9 13.5 61.8 35.3 17.7
30.9 24.1 12.1 51.3 44.2 22.1 60.4 23.9 12.0
30.8 32.5 16.3 50.3 41.2 20.6 59.0 34.1 17.1
30.6 27.9 14.0 49.2 42.6 21.3 57.6 27.3 13.7
65.6 43.6 21.8 48.1 44.2 22.1 56.2 38.8 19.4
63.9 41.0 20.5 47.4 39.3 19.7 55.1 33.5 16.8
62.2 38.5 19.3 46.6 40.0 20.0 53.9 40.7 20.4
60.4 37.1 18.6 45.9 46.5 23.3 52.8 37.7 18.9
58.2 41.4 20.7 45.1 29.4 14.7 51.6 34.3 17.2
57.0 39.2 19.6 44.4 45.1 22.6 50.5 40.9 20.5
56.0 45.2 22.6 43.7 41.1 20.6 49.9 33.1 16.6
55.1 44.6 22.3 42.9 37.6 18.8 49.2 33.8 16.9
54.1 33.5 16.8 42.2 37.8 18.9 48.6 30.9 15.5
53.1 28.9 14.6 41.4 44.7 22.4 47.9 30.6 15.3
52.2 41.5 20.8 40.7 44.1 22.1 47.3 32.8 16.4
51.2 39.9 20.0 40.3 37.5 18.8 46.6 34.9 17.5
50.2 38.2 19.1 39.9 38.2 19.1 46.0 29.3 14.7
49.2 36.7 18.4 39.6 34.0 17.0 45.3 41.2 20.6
48.3 39.3 19.7 39.2 36.1 18.1 44.7 34.1 17.1
47.3 36.9 18.5 38.8 44.8 22.4 44.0 37.9 19.0
46.5 48.4 24.2 38.5 43.9 22.0 43.5 34.6 17.3
45.7 41.4 20.7 38.1 42.4 21.2 42.9 35.3 17.7
44.9 38.6 19.3 37.8 35.9 18.0 42.4 32.8 16.4
44.1 40.5 20.3 37.4 41.5 20.8 41.8 33.5 16.8
43.4 49.1 24.6 41.3 33.6 16.8
42.6 50.7 25.4 40.7 40.0 20.0
41.8 44.4 22.2 40.1 34.1 17.1
41.0 44.8 22.4 39.6 32.6 16.3
40.2 45.5 22.8 39.0 38.4 19.2
38.4 25.5 12.8
37.9 37.2 18.6
37.4 34.7 17.4
36.9 34.2 17.1
36.4 34.2 17.1
36.0 38.1 19.1
207
35.5 38.0 19.0
35.0 28.5 14.3
34.5 35.1 17.6
34.0 24.6 12.3
208
Appendix D: Tabulated Data of the Effect of Ageing on the
Breakdown Voltage of Oil
Table 54: AC Breakdown voltages of mineral oil as a function of ageing duration and
catalyst
Breakdown voltage in kV
No Catalyst Copper Steel Copper + Steel
7 days 14 days 28 days 7 days 14 days 28 days 7 days 14 days 28 days 7 days 14 days 28 days
17.9 17.8 12.5 26.1 22.3 14.2 20.0 19.3 25.5 18.0 28.8 14.4
21.5 19.5 13.6 26.5 22.8 15.8 22.9 23.8 29.6 19.2 31.7 16.9
24.9 20.3 14.5 27.1 22.8 15.9 24.7 24.6 30.4 26.9 32.1 17.3
25.1 23.9 17.2 27.3 23.7 16.8 26.0 27.2 34.4 27.1 36.6 18.0
25.2 24.3 19.2 30.0 26.0 16.9 27.2 32.6 35.3 28.8 37.4 18.1
26.5 25.3 19.4 30.2 29.8 18.8 28.5 32.8 35.5 29.3 38.0 18.4
26.6 26.2 19.8 30.4 30.4 18.9 28.5 33.6 35.6 30.6 38.5 18.8
26.9 27.6 19.9 31.9 32.1 22.8 28.7 35.0 37.2 30.9 38.7 20.5
27.5 27.8 20.1 32.1 32.4 23.5 30.2 36.0 37.8 30.9 39.4 21.1
28.3 29.7 20.3 35.1 34.0 24.8 30.9 36.2 37.8 31.3 40.3 24.7
28.4 30.0 21.7 36.1 34.0 24.8 31.7 36.7 38.4 31.5 40.6 26.5
28.4 31.1 22.2 36.3 34.6 25.2 32.1 36.7 38.5 32.5 42.4 27.5
30.6 32.0 23.5 36.7 37.0 25.7 32.1 37.1 38.7 32.6 42.6 28.4
32.0 32.4 23.7 36.9 39.6 27.5 32.2 37.2 38.9 35.9 42.9 28.5
32.0 37.7 27.8 39.4 40.2 28.0 32.3 37.2 39.3 37.6 43.3 29.5
32.9 38.3 27.9 39.6 40.4 28.1 33.2 38.7 39.9 37.6 43.8 29.5
34.5 39.1 28.4 39.6 40.4 28.4 34.0 39.3 39.9 38.0 44.1 29.9
35.8 39.6 30.2 41.8 42.6 29.4 34.5 40.9 40.2 38.0 44.1 32.9
36.0 39.7 34.6 42.9 42.7 29.7 34.7 41.5 40.6 39.2 44.6 34.9
39.5 40.1 35.0 42.9 43.1 33.2 35.9 42.0 42.6 39.5 45.1 37.5
Table 55: AC Breakdown voltages of FR3 as a function of ageing duration and catalyst
25.2 30.4 23.6 21.1 23.6 28.8 27.0 29.7 24.9 24.5 16.1 19.4
26.5 30.7 23.9 24.5 27.8 32.0 27.5 32.4 25.3 25.7 16.7 25.3
27.5 30.8 32.1 24.9 31.5 32.8 28.0 32.6 28.8 25.8 17.0 27.5
30.2 30.9 35.1 27.0 32.0 35.7 28.8 33.8 31.8 28.7 19.8 28.9
32.8 31.1 35.2 29.4 35.5 36.1 29.2 34.2 32.0 31.4 19.9 29.3
33.8 31.2 36.2 30.4 36.7 37.4 30.1 35.3 33.1 31.6 23.1 29.7
34.2 31.4 37.3 31.1 36.9 40.5 30.4 35.7 35.1 32.0 23.8 30.2
34.8 31.8 37.9 31.2 37.3 41.3 30.7 36.5 37.3 32.8 23.8 30.6
36.0 34.6 40.0 31.7 38.3 41.9 30.9 38.5 37.4 32.9 23.8 32.2
36.5 36.1 41.3 31.8 38.8 42.1 31.3 39.0 37.7 34.2 27.3 32.9
209
36.8 36.5 41.3 32.9 39.7 43.9 31.3 40.1 39.7 34.2 28.6 34.6
37.3 36.8 41.6 33.6 40.1 44.0 31.3 40.6 41.3 34.7 29.6 35.8
38.0 37.1 42.4 33.9 40.5 45.7 32.3 41.0 42.0 34.8 32.6 38.1
39.1 39.1 43.1 34.4 41.3 46.2 32.5 41.3 42.2 35.3 33.5 39.4
39.3 40.4 44.1 36.0 41.6 47.0 32.9 41.3 42.6 35.6 33.8 41.7
39.9 42.5 44.8 36.7 41.8 47.2 33.3 41.6 43.1 35.9 33.9 41.7
40.0 43.9 45.0 36.8 42.2 48.2 34.6 42.2 43.2 36.0 34.3 42.2
40.0 44.1 45.4 36.9 43.8 48.5 34.9 42.6 44.9 36.6 34.9 44.1
41.1 45.4 45.4 38.3 43.8 48.9 35.9 43.7 45.1 37.2 38.9 44.2
41.8 46.4 47.3 38.7 43.9 50.7 37.8 46.4 46.6 38.3 38.9 44.3
Table 56: AC Breakdown voltages of Midel 7131 as a function of ageing duration and
catalyst
14.4 23.4 35.6 20.2 33.3 24.7 30.1 18.1 37.9 33.1 31.2 19.8
22.1 35.9 36.7 20.4 35.8 30.5 31.5 19.7 39.5 33.6 31.7 24.9
24.5 37.0 38.7 37.5 38.5 34.2 33.9 29.3 39.6 36.1 33.0 29.5
28.9 38.0 39.7 37.6 38.9 36.6 36.4 32.1 40.1 36.4 33.5 34.1
29.0 38.6 40.1 37.8 42.7 36.8 36.5 32.4 41.3 36.6 34.7 35.3
32.1 39.1 40.9 40.1 43.3 37.2 37.8 33.7 42.0 37.0 38.3 36.9
32.5 39.7 43.1 42.0 43.5 37.6 38.2 35.1 43.9 37.8 41.3 37.3
33.1 39.8 44.1 42.2 43.6 37.7 38.7 38.7 44.0 38.6 41.8 37.6
33.2 41.2 44.2 43.6 43.8 37.9 39.0 38.8 44.9 39.3 43.0 38.4
34.2 42.2 47.8 44.5 44.2 40.5 39.1 39.6 45.3 39.8 44.2 39.9
34.2 42.6 48.0 45.8 44.9 41.3 40.5 41.1 45.5 40.2 44.5 40.4
36.5 42.7 48.5 46.3 45.8 42.4 40.5 41.2 45.8 40.5 44.5 41.5
41.4 42.8 52.5 46.5 45.8 42.5 41.8 45.3 46.8 41.4 45.6 41.8
41.6 43.0 52.8 46.8 47.6 42.6 43.1 45.4 47.7 41.6 46.2 42.2
41.9 43.2 53.0 49.7 47.6 45.5 43.2 46.1 48.1 41.9 46.8 46.3
42.7 43.5 53.5 50.2 47.8 45.6 45.3 46.7 50.8 42.5 47.7 47.3
43.1 44.0 53.9 50.3 51.3 45.8 45.5 47.5 51.8 43.0 49.9 49.5
43.3 45.3 54.0 50.3 51.5 45.9 45.5 50.6 52.5 43.1 49.9 49.7
43.6 46.3 54.3 51.3 53.0 46.1 45.9 50.7 52.7 43.4 50.4 50.1
45.1 46.6 55.2 54.1 55.9 46.2 46.6 51.5 52.9 44.5 50.5 54.2
210
Table 57: Lightning impulse breakdown voltages of the oils as a function of ageing
duration and catalyst

(kV) (kV) (kV)
Unaged Aged no Aged Unaged Aged no Aged Unaged Aged no Aged
catalyst with catalyst with catalyst with
Copper Copper Copper
1 -190 -150 -149 -174 -160 -150 -164 -170 -160
2 -195 -153 -149 -181 -160 -170 -164 -170 -160
3 -198 -166 -150 -183 -160 -170 -164 -170 -160
4 -199 -177 -153 -184 -176 -170 -164 -170 -163
5 -200 -180 -170 -184 -190 -174 -170 -170 -165
6 -180 -170 -190 -176
7 -170 -190
8 -170 -190
9 -170 -190
211
Appendix E: Tabulated Data of the Breakdown Voltages of
Oil Using Electrode Gaps of 5mm and 10mm
Table 58: AC breakdown voltages of the oils using an electrode gap of 5mm and 10mm
(kV) (kV) (kV)
5mm gap 10mm gap 5mm gap 10mm gap 5mm gap 10mm gap
1 95 237 114 161 152 195

2 199 >250 134 218 119 248
3 174 214 142 249 140 250
4 173 150 158 243 116 247
5 182 >250 142 245 148 >250
6 165 >250 143 246 141 >250
7 166 233 144 232 133 >250
8 180 >250 144 230 133 >250
9 149 227 143 220 124 >250
10 160 >250 144 233 149 229
Table 59: AC breakdown voltages of the oils using an electrode gap of 5mm
(kV) (kV) (kV)
1 114 152 125
2 142 150 142
3 151 158 165
4 191 166 161
5 167 152 147
6 203 151 163
7 206 149 157
8 182 166 156
9 205 158 143
10 199 165 149
11 158 149 173
12 182 166 156
13 199 158 157
14 167 149 173
15 206 158 165
16 198 157 158
17 182 149 157
18 162 165 181
19 175 166 181
20 183 167 166
21 175 166 182
22 191 150 159
23 190 158 159
24 185 167 168
25 177 167 184
26 199 175 159
27 182 165 185
28 182 150 186
212
29 167 166 180
30 198 151 184
213
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Evaluation of the Dielectric Capability of Ester Based Oils for Power

Thesis · June 2008

The user has requested enhancement of the downloaded file.

BASED OILS FOR POWER TRANSFORMERS

A thesis submitted to The University of Manchester for the degree of

School of Electrical and Electronic Engineering

Word count: 54,000

Figure 1: Sharing of the electric field across a composite insulator ............................... 25

Aromatic Aromatics are constituents of mineral oil. An aromatic is “a class

1.1 Background to the Use of Oil as a Transformer Dielectric

Using esters as transformer dielectrics is by no means a recent innovation. Natural

Nytro 10GBN Envirotemp FR3 Midel 7131

Viscosity @ 40°C (cSt) 9 32-33 28

Specific heat (J/kg K) 1860 1880 1880

An insulating oil must remain liquid under ambient temperatures to be an effective

The electric stress in a composite system is distributed across the components as a

Figure 1: Sharing of the electric field across a composite insulator

It is common to monitor the condition of the insulating oil to determine when

1.2 Overview and Aims of this Thesis

The following research is presented in this thesis:

i) A comparative study of the AC and lightning impulse dielectric strengths of new

1.3 Overview of Chapters

Chapter 2: Literature review

Chapter 3: Methods Used to Measure the Properties of the Oils

Where possible, measurements have been performed in accordance with an appropriate

Chapter 4: Comparison of Breakdown Voltages of New Oil

The dielectric failure of an oil is a statistically distributed quantity. Therefore in order to

Chapter 5: Effect of Water on the Breakdown Voltages of New Oil

Chapter 6: Comparison of the Effect of Temperature on the Breakdown Voltages of

Chapter 7: Comparison of Effect of Ageing on the Breakdown Voltages of Oil

Chapter 8: Effect of Large Oil Gaps on the Dielectric Strength of Oil

Chapter 9: Conclusion and Further Work

2.2 The use of mineral oil in transformer insulation

Figure 2: Progression of the transmission voltages and power ratings of electricity

Manufacturing year Litres of insulating oil per

2.3 Introduction to the Oils Used in this Investigation

The oils investigated by this project were:

Nytro 10GBN which is an uninhibited mineral oil conforming to BS148

Envirotemp FR3 which is a vegetable oil based product supplied

2.3.1 Nytro 10GBN

Nytro 10GBN is an uninhibited naphthenic mineral oil. The basic hydrocarbon

Figure 3:: Basic hydrocarbon structures in mineral oil [25]

2.3.2 Envirotemp FR3

2.3.3 Midel 7131

2.4 Mechanism of the Dielectric

2.4.1 Introduction to the Dielectric Failure of Oil

2.4.2 Introduction to the Bubble Theory of Breakdown

i. Local discharge occurs at cathode

ii. Discharge vaporises surrounding oil creating bubble

iii. Electric field ionizes bubble creating streamer

iv. Streamer propagates across electrode gap

v. Streamer bridges electrodes forming arc

2.4.3 Particle Initiated Breakdown

The importance of water is that it increases the conductivity of hygroscopic insulating

4 = 550( ' 5 (67) (2.4)

2.5 Differences Between Failure Caused by Lightning Impulse and AC

The mechanism of dielectric failure of an oil caused by a lightning impulse is different

2.5.1 Effect of Polarity on the Lightning Impulse Breakdown Voltage of Oil

In the case of a transient of one polarity, such as a lightning impulse, a difference in

2.5.2 Effect of Particles on the Lightning Impulse Breakdown Voltage of Oil

2.5.3 Effect of the Molecular Structure on the Lightning Impulse Breakdown

Aromatic content Impulse breakdown ASTM Gassing tendency

2.6 Summary and Areas Identified for Investigation

H(H&) < 0<9 U )(H0&)