Kou K 435
Kou K 435
Kou K 435
著者 Jang Kyunghoon
その他のタイトル ナノコンポジットコーティングを効果を考慮した油
/プレスボード界面における沿面放電挙動及び数値
モデル解析
学位授与年度 平成28年度
学位授与番号 17104甲工第435号
URL http://hdl.handle.net/10228/00006311
Doctoral Dissertation
ナノコンポジットコーティングの
ナノコンポジットコーティングの効果を考慮した油/プレス
効果を考慮した油 プレス
ボ―ド界面における沿面放電挙動及び数値モデル解析
February 2017
Department of Engineering
Graduate School of Engineering
Kyushu Institute of Technology
Jang Kyunghoon
ABSTRACT
DEPARTMENT OF ENGINEERING
Doctor of Philosophy
by Kyunghoon Jang
Abstract iv
Contents iiv
List of Figures iv
List of Tables iv
Acknowledgements iv
Symbols & Abbreviations iv
Chapter 1
1.1 OIL FILLED TRANSFORMER................................................................... 1
1.2 RESEARCH MOTIVATION AND PROBLEM ......................................... 3
1.3 RESEARCH OBJECTIVES AND CONTRIBUTIONS .............................. 4
1.4 THESIS STRUCTURE ................................................................................. 5
CHAPTER 2
2.1 MINERAL OIL ............................................................................................. 8
2.1.1 The effect of moisture on mineral oil ............................................................. 10
2.2 CELLULOSE-BASED PRESSBOARD .................................................... 11
2.2.1 The effect of moisture on cellulose-based pressboard ....................................... 14
2.3 CREEPAGE DISCHARGE PHENOMENA AT THE OIL/
PRESSBOARD INTERFACE .................................................................. 15
2.3.1 The influence of solid insulation in mineral oil ................................................ 15
2.3.2 Discharge propagation modes ....................................................................... 18
2.3.3 Effect of relative permittivity in composite insulation system ............................ 23
2.3.4 Permittivity and polarization ......................................................................... 25
CHAPTER 3
3.1 BASIC ELECTRODYNAMIC EQUATIONS ........................................... 28
3.2 CHARGE CARRIER GENERATION ....................................................... 29
CHAPTER 4
4.1 INTRODUCTION....................................................................................... 44
4.2 EXPERIMENT SETUP .............................................................................. 45
4.3 EXPERIMENTAL PROCEDURE………………………………………..47
4.3.1 Creepage discharge observation .................................................................... 47
4.3.2 Sample preparation&dielectric property measurement ...................................... 52
4.3.3 Surface roughness and nano silica distribution state ......................................... 55
4.3.4 Partial discharge inception............................................................................ 58
4.4 RESULTS (ROD-PALNE ELECTRODE)................................................. 61
4.4.1 Dielectric properties .................................................................................... 61
4.4.2 Discharge patterns and PDIV ................................................................................... 63
4.4.3 Discharge propagation length........................................................................ 68
4.5 RESULTS (NEEDLE-BAR ELECTRODE) .............................................. 69
4.5.1 Discharge patterns and PDIV ........................................................................ 69
4.5.2 Discahrge propagation length........................................................................ 74
4.6 DISCUSSION (EFFECT OF SOLID LAYER COATING) ...................... 76
4.6.1 Dry effect and permittivity effect ................................................................... 77
4.6.2 Surface modification effect ........................................................................... 79
4.6.3 Electron suppression effect ........................................................................... 81
4.7 SUMMARY ................................................................................................ 82
CHAPTER 5
5.1 EXPERIMENT METHOD ......................................................................... 85
5.1.1 Electrode setup ........................................................................................... 85
5.1.2 Sample preparation ..................................................................................... 87
5.1.3 Dielectric property measurement ................................................................... 91
5.2 RESULTS ................................................................................................... 92
CHAPTER 6
6.1 INTRODUCTION..................................................................................... 111
6.2 GOVERNING EQUATIONS IN OIL ...................................................... 112
6.2.1 Hydrodynamic diffusion-drift model ............................................................ 112
6.2.2 Charge emission from electrode and solid insulation surface ........................... 113
6.2.3 Lightning impulse voltage .......................................................................... 117
6.3 NEEDLE-BAR GEOMETRY .................................................................. 118
6.4 SIMULATION RESULTS ....................................................................... 120
6.4.1 Creepage discharge under high electric field ................................................. 120
6.4.2 Poole-Frenkel model for solid insulation dependent on effective barrier
height ...................................................................................................... 125
6.4.3 creepage discharge velocity and bdv dependent on permittivity effect ............... 126
6.5 SUMMARY .............................................................................................. 127
CHAPTER 7
7.1 CONCLUSIONS ....................................................................................... 130
7.2 FURTHER WORK ................................................................................... 131
APPENDIX A
APPENDIX B
APPENDIX C
I also wish to thank my thesis committee members, Prof. Mitani, Prof. Komori
and Prof. Toyoda for their valuable suggestions, guidance and encouragement that
have substantially helped in my thesis.
Next, I would like to thank the Nissan Chemical Industry., LTD for their
technical support of all the nano silica samples. I am thankful to all the members
of the Nissan chemical research team.
A big thank you to my colleagues and friends who are Rajab during Ph.D.
study, Impulse PD team Akahoshi and Kurachi for 3 years. And I would like to
thank to convey my friends in Korea.
I would like to thank my family, Jang doosoo, Lee Suil and Jang Kyungtak,
they have always been there to encourage and support me in what I have done,
and they have made many sacrifices to give me the opportunities. And welcome
back to Seoul, Korea for my cousin Minji Chang and her husband Jaisun Ihm :).
Abbreviations in thesis
AC Alternating current
DC Direct current
PD Partial discharge
BDV Breakdown voltage
PDIV Partial discharge inception voltage
HV High voltage
GND Ground
IEEE Institute of Electrical and Electronics Engineers
PMT Photomultiplier tube
wt% Weight percent
PB Pressboard
NP Neat pressboard or/and Neat epoxy
DP Dry pressboard
EP Epoxy coated pressboard
SP Silica/epoxy composite coated pressboard or/and Silica/epoxy
composite plate
TP Teflon coated pressboard
I.I Image Intensifier
𝑃d Discharge occurrence probability
𝑙d Discharge propagation length
𝑅z 10 point surface roughness
𝑅a Average surface roughness
CHAPTER 1
weak point giving rise to failure modes in the oil/pressboard composite insulation
system, it is because creepage discharge tend to propagate along the interface
between oil and pressboard and then leading to flashover and breakdown.
Cellulose paper or pressboard and mineral oil are the main insulation materials
used in oil filled transformer as a composite insulation system to protect the
equipment from lightning surge. However, partial discharge and breakdown
phenomenon by lightning surge has proved to be one of the major factors and
weak point at the oil/pressboard interface. Besides, aged equipment is increasing
rapidly. To enhance competitiveness and cost reduction of oil filled transformer,
there is need for alternative conventional insulation, miniaturization, and
simplification of insulation structure and improvement of design electric field. For
above needs, the distance between insulation is narrowed, meaning that electric
field and probability of discharge at oil/PB interface increases than designing
condition. Thus, it is necessary to improve the dielectric property of conventional
pressboard [1-9].
Figures 1.2 (a) and (b) show flashover failure along the mineral oil and
pressboard interface. The creepage discharges tend to propagate along the
interface between mineral oil and pressboard due to different permittivity. Despite
advances in manufacturing and monitoring technologies, some unexpected faults
and failures still occur. These are usually dielectric in nature, and often without
any obvious cause [10].
Lightning impulse withstanding property is one of important characteristics in
power apparatus to design of oil filled transformer; it is because the lightning
impulse is a pure natural phenomenon. On the other hand, it is very difficult to
predict the actual wave shape of a lightning disturbance. In addition, engineers
want to predict the discharge initiation, development process in composite
insulation system for upgrading the insulation design of power apparatus under
lightning surge. Indeed, the conditions of the occurrence of discharges and the
parameters influencing discharge development up to flashover are very useful for
the design and dimensioning of high voltage components and systems such as
insulators, spacers, bushings and circuit breakers envelopes. For these reasons, a
lot of works have recently been devoted to improve the dielectric properties of
insulating oil by adding specific functional additives into the oil [11, 12].
However, few studies have been focused on modifications of the insulating paper
using various specific functional additives to improve dielectric and mechanical
properties [13-16], it is because creepage discharge phenomena has been reported
in many literatures that streamer propagation in oil is greatly affected by the
presence of pressboard and other solid insulation [1, 17, 18-22]. Thus there is a
growing interest in suppression of creepage discharge in oil filled transformer.
(a) (b)
(c)
Figure 1.2 Flashover failure of insulation (a) to (c) [1, 2]
The main objective of this research is to study the behavior and characteristics
of creepage discharge at the oil/pressboard composite insulation system depending
on solid layer coating materials on PB surface such as epoxy resin and
epoxy/silica nanocomposite under standard lightning impulse voltage. Second
objective is to investigate the effect of nano size silica on suppression of creepage
discharge inception and discharge propagation process by silica/epoxy
nanocomposite coating method.
The research has involved two kinds of approach such as experimental results
and computer simulation studies. The experiments for creepage discharge
observation at the oil/pressboard interface have been conducted in an oil chamber
experiment setup. The creepage discharge characteristics of conventional
pressboard are compared with solid layer coated pressboard. A numerical analysis
method in composite insulation system has been developed in the COMSOL
Multiphysics 2D Model, a finite element analysis (FEA) software package to
understand the creepage discharge behavior and mechanism. With respect to all
these, contributions are followings:
Chapter 1 discusses the problems and weak point in terms of partial discharge
within large transformers associated with the oil/pressboard interface that
motivates this research. The research objectives have been outlined.
Chapter 2 presents a review of the literature that is directly relevant to both the
experimental work and numerical simulation model development that has been
undertaken as part of this thesis.
CHAPTER 2
A petroleum-based mineral oil has been most often employed in the electrical
insulation inside power transformers for more than a century for electrical
equipment including transformers, circuit breakers and power cables. Mineral oil
has an excellent performance as electrical insulation (electrical breakdown
strength and thermal conductivity than gaseous insulators) and cooling medium
[22, 23]. Unfortunately, as with all insulation, the failure of the liquid insulation
can cause catastrophic damage to not only the power equipment, but also the
surrounding environment. And also some problems such as scarcity and high price
of mineral oil, sulfide-induced corrosion of copper lead to be conductive in liquid
insulation, environmental pollution due to oil leakage, atmospheric pollution have
been pointed out for practical use [22].
Mineral oils are obtained from crude petroleum extracted from the earth.
Mineral insulating oil is a mix of hydrocarbons in the form of chain and ring
molecules with small amounts of sulphur, nitrogen, oxygen and trace metallic
elements [1, 23, 24]. Mineral oil is classified by the percentage content of the
following three hydrocarbon groups, which are paraffinic (C2n H2n+2 ), naphthenic
(C2n H2n ) and aromatic (Cn Hn ) as shown in Fig. 2.1 [23-26]:
Insulation oil is hydrophobic and oil and water do not readily mix but the real
problem with moisture in oil is that, even in small amounts, it has a marked effect
on the dielectric strength of the oil as shown in Fig. 2.2 [26]. The breakdown
voltages for each oil sample were normalized with the corresponding dry oil value
to account for the variation between different oil samples (60-88 kV). It is
observed that the breakdown voltage remains almost unchanged when the relative
moisture saturation is below 20%. Above that it decreases rapidly [27]. Guidelines
are given for acceptable levels of moisture according to transformer category in
the standard for insulating oils in electrical equipment which defines a minimum
breakdown of 55 kV/mm and a maximum water content of 10 ppm for
transformers rated at a minimum system voltage of 170 kV [1, 26].
Cellulose based insulation has been the preferred choice for the solid insulation
in power transformers, In 1939, G. T. Kohan of Bell Telephone Laboratories in
New York wrote an article in AIEE Transactions on cellulose as an insulating
material for various electrical application: paper capacitors, paper-insulated power
cables, oil filled cable [9]. Cellulosic insulation is used primarily in oil filled
transformers from distribution to large power units covering a wide range from 10
kVA to 1500 MVA and from line voltage to 1000 kV. In terms of physical size, it
ranges from the pole and pad mounted units on our streets to large substation units
that can have several tons of cellulosic insulation immersed in 40,000 to 100,000
L (~10,000 to 30,000 gallons) of oil [9]. The insulation structure consists of not
only the HV and LV insulation but also support structures, winding tubes, spacer
blocks and formed items for end closing. These are illustrated in Fig. 2.3.
Electrical grade paper and pressboard are mostly made from wood pulp
processed by the Kraft chemical process. The starting material is wood, both soft
wood and hard wood. Wood is a natural composite material that is made up of
flexible tubes of cellulose bound together by lignin, a brownish aromatic polymer
that is mostly removed during the pulping process. A schematic representation of
the fine structure of wood pulp is shown in Fig. 2.4 [9].
In general, fibres may consist of approximately 50-90% of carbohydrate group,
i.e. cellulose (40-80%) and hemicelluloses (10-40%). Fibres may also consist of
5-25% of lignin [28, 29]. Specially, Hemicellulose molecules are the second
major components that facilitate the hydrogen bonding process, but the
mechanical strength is reduced if their quantity exceeds about 10% [17]. Another
disadvantage of hemicelluloses is their ability to “hold on” to water which makes
the paper/pressboard more difficult to dry out and thus, this signifies its dominant
role in the hydrophilic behavior of the cellulose based solid insulation. Besides the
significant hygroscopic nature of cellulose paper is obvious from the moisture
sorption curves. Meanwhile, lignin is a component of wood that binds to cellulose
fibres to strengthen the cell walls of plants and add further to their matrix rigidity
[1, 17, 29].
For regular Kraft paper the life would be lowered by half for every doubling of
moisture content, though for upgraded paper the loss of life is not so drastic. From
a temperature perspective, the temperature increases above 75 ℃ for the
mechanical strength to decrease to half depending on the moisture content of the
paper [29, 34].
Table 2.1 shows the creepage discharge on different pressboard condition in 30
mm gap distance [35]. The results can be deduced that the moisture content in
pressboard plays a more critical role in creepage discharge at the oil-pressboard
interface. On the other hand, moisture in pressboard bulk has been said to play
important role in surface discharges [1]. Therefore, transformer insulation paper
requires rigorous dry out before oil impregnation. Drying of the cellulose is
required to reduce the moisture content, which if not completed can decrease the
dielectric strength and accelerate aging [22].
Creepage Discharge phenomena has been reported in the literature that streamer
propagation in mineral oil is greatly affected by the presence of pressboard and
other kinds of solid insulation [1, 22, 36-37, 41, 42]. Especially, different
insulation components or characteristics of oil-solid systems have been shown to
have serious impact on discharge inception and propagation. They are the
orientation of the oil-solid interface with respect to the dominant electric field
direction and the permittivity difference between oil and pressboard as shown in
Fig. 2.7 [22, 42]. And some researchers consider the electric filed distribution
with/without presence of the solid insulation [42]. Figure 2.8 (a) shows the
electric field distribution in the system without the presence of the insulating
surface. The electric field magnitude has a maximum in the direction of the axis of
the streamer. However, as seen in Figure 2.8 (b), when an insulating surface
(relative permittivity 𝜀𝑟 = 3.5) is placed in the gap parallel and close to the axis of
the streamer, the maximum field is no longer along the streamer axis, but points
towards the insulating surface. The maximum field is also larger with the presence
of the insulating surface. The streamer velocity in the presence of the insulator is
also increased moderately compared to no presence of solid insulator [43].
(a) Transformer oil-pressboard system where the (b) Transformer oil-pressboard system where
Interface is oriented parallel to the dominant the interface is oriented perpendicular to the
direction of the electric field. dominant direction of the electric field.
Figure 2.7 General orientations of oil-pressboard interface with respect to
dominant direction of electric field [1, 22]
(b) On Perspex
Figure 2.9 Discharge propagation lengths in FR3 at 43 kV [42].
Figure 2.10 shows the breakdown process at the oil-pressboard interface in four
distinct stages. The experiment was conducted by increasing the AC voltage
gradually [1, 28, 44]. As seen in Fig. 2.10, the first event occurs at PDIV level.
During this first stage, no visual activity has been observed but the occurrence of
PD activity is known based on the monitoring data from the PD measurement
system. As the voltage increases, the second stage occurs when a corona like
event is visible at the needle tip. This stage is observed to occur at a voltage level
that is above the PDIV level and lower than the flashover voltage, which is also
called the sustained PD voltage range. Surface discharges can be sustained for
long periods without surface flashover or breakdown as long as the voltage is
within this range. Next, as the voltage is increased closer to the flashover voltage,
the third stage occurs when streamers are observed from the ground bar electrode
and distinct crackling is heard. Finally, as the voltage is increased further, a
surface flashover occurs and causes electrical breakdown [1].
Figure. 2.10 Creepage discharge stages from discharge inception to breakdown [1,
26]
O. Kesaint and G. Massala [48] have reported the streamer average velocity
with respect to the applied voltage in the transformer oil with and without
pressboard as shown in Fig. 2.13. However, Lundgaard et al., [49] has also
reported that slow velocity streamer propagation could change to a fast mode. The
slow velocity streamer was found to cause weak darkening path on the pressboard
surface, whilst the fast velocity has led to a burnt track on the pressboard surface,
as shown in Fig. 2.14 [1].
Figure 2.13 Average streamer velocity versus voltage in the liquid alone and with
a solid parallel to the field (d=10 cm) [48]
Figure 2.14 Positive streamer propagation along solid interface; Upper: the
positive streamer model, Lower: actual tracks observed on pressboard surface [1]
The polarity effect in insulating oil in inhomogeneous electric fields manifests
differences in discharge initiation, structure and propagation velocity of streamers.
The physicochemical processes implicated in the development of streamers in
each polarity can be succinctly explained as follows [47, 49]:
(1) In the vicinity of the positive electrode, either free electrons or electrons
detached by field emission are accelerated towards the anode. Whereas the
electrons rapidly drift to the anode, the positive ions essentially stand still. The
liquid increases its temperature due to the interaction between the electrons and
the fluid molecules. This local heating causes a low-density region, which
becomes the origin of positive streamer branches. Inside this region, ionization of
fluid molecules generates more free electrons which arrive at the anode. The
remaining positive ions build a space charge representing the new, virtual tip. This
pulsed process repeats periodically and the positive pre discharge propagates in
the direction of the electric field until the inception conditions for subsequent
stages are attained.
(2) The initiation process for negative streamers differs from the positive one.
At sufficiently high fields, electrons are injected into the liquid and due to the
interaction between the electrons and fluid molecules and the associated energy
release, a low density region is formed. Whereas the positive streamer appears as
a three stage process, only two propagation stages of the negative pre discharge
could be observed whereby secondary modes can only be detected at large
electrodes gap. Depending on the growth rate of electric field, different structures
can occur (leafless tree-top, frequently ramified or filamentary structure). Each
mode has a typical minimum propagation velocity.
Figure 2.15 Streamer inception probability distribution function for point cathode
in transformer oil with and without solid interface [51]
Figure 2.16 shows the liquid/solid interface with the protrusions and troughs on
the solid surface that can be modelled in the figure as liquid and solid parts in
series. The interface breakdown should be induced by a partial breakdown of the
liquid part due to its lower dielectric strength, and factor K was introduced to
describe the reduction of the creepage breakdown strength ∆𝑈𝑠 to the breakdown
strength of open gap ∆𝑈𝑂 [42, 59].
∆𝑈𝑠 ∆𝑥𝑠 𝜀𝑜
K= = 1− ∙ (1 − ) (2.1)
∆𝑈𝑂 ∆𝑥0 𝜀𝑠
𝜀𝑜
lim∆𝑥𝑠 →0 𝐾 = 1 and lim∆𝑥𝑠 →∆𝑥 𝐾 = 𝜀𝑠
𝜀𝑜
Therefore K should be larger than and less than 1 assuming that the liquid
𝜀𝑠
permittivity is smaller than that of solid materials, and it should vary with the
combination of liquid and solid. The larger the permittivity mismatch between
liquid and solid insulation, the more reduction in creepage discharge and
breakdown strength [42, 59]. The supporting experimental evidences can be found
in references [50- 52, 60, 61].
⃗⃗ = 𝜀0 𝐸⃗⃗ + 𝑃⃗⃗
𝐷 (2.3)
= 𝜀𝑟 𝜀0 𝐸⃗⃗ ,
Results in the displacement field, which is a true measure of the total field from
both free and polarization charges that can act upon free charge. Thus, the greater
a material’s relative permittivity 𝜀𝑟 , the greater the total force that acts upon free
charge in a system [17].
(a) (b)
Figure 2.17 (a) The net charge enclosed within a differential sized volume of
dipoles has contributions only from dipoles that are cut by the surfaces. All totally
enclosed dipoles contribute no net charge. (b) Only those dipoles within a distance
𝑑⃗ ∙ 𝑛⃗⃗ of the surface are cut by the volume. [17]
CHAPTER 3
Electrohydrodynamics
∂𝜌+
+ ∇ ∙ 𝐽⃗+ = 𝐺𝐶+ + 𝑅𝐶+ (3.2)
∂t
∂𝜌−
+ ∇ ∙ 𝐽⃗− = 𝐺𝐶− + 𝑅𝐶− (3.3)
∂t
of significant electrical stress, and then the next step in the process is the
identification of sources and sinks of free charge carriers. The sources and sinks
of free charge carriers can be broadly categorized as either being bulk effects or
boundary effects. The injection of electrons from an electrode into the liquid via
Fowler-Nordheim tunneling is an example of a boundary effect and such a source
of charge would be accounted for by the setting of boundary and initial conditions
for the charge continuity equations. The electric field dependent dissociation of
weakly bonded neutral ion pairs in transformer oil under high electric field
stresses is an example of a bulk charge generation effect and is accounted for by
the generation terms of the charge continuity equations. The recombination of
positive and negative ions to form neutral species is accounted for by the
recombination terms of Eqn. 3.2 and 3.3.
In generally, electrons are released from the metal electrode surface due to
high electrostatic fields over 1~10× 108 V/m as shown in Fig. 3.1. A theory to
describe field emission was first developed by Fowler and Nordheim in 1928,
hence the process of field emission is often referred to as Fowler-Nordheim field
emission, of Fowler-Nordheim charge injection [62, 63]. Fowler and Nordheim’s
work involved the development of an equation to describe the electric field
dependent current density in a vacuum, due to the quantum-mechanical tunneling
of electrons from the metal through the potential barrier at the metal/vacuum
interface. The level of electron tunneling, which takes place increases
exponentially with the electric field level. This is due to the fact that as the field
level increases the potential barrier at the metal/vacuum interface narrows, leading
to an exponential increase in the probability of electrons tunneling through the
barrier. The electron current was measured by Fowler and Nordheim. Electrons in
the proximity of the Fermi level may have the probability of passing through the
barrier – a phenomenon known as the “tunnel effect”. The basic equation for the
emission current by the influence of electric field can be expressed as follows:
3
⃗⃗⃗⃗⃗⃗2
𝑒 3 |𝐸| 8𝜋√2𝑚∅2
𝐽FE = exp (− ) (3.4)
8𝜋ℎ∅ ⃗⃗⃗⃗⃗⃗
3ℎ𝑒|𝐸|
Where, 𝐽FE is the emitted current density, e is the magnitude of electron charge,
⃗⃗⃗⃗⃗⃗ is the electric field, h is Planck’s constant and ∅ is 4.5 eV. This equation is
|𝐸|
based on the potential energy distribution at the metal/vacuum interface. Figure
3.2 shows the mechanism of field emission from the metal surface, W(x) is
potential barrier with applied field: 𝑊(𝑥) = −𝑒|𝐸⃗⃗ |𝑥, 𝑥 > 0. This potential
energy distribution is known as the “Triangular Barrier Approximation”, which
overestimates the potential barrier height at the metal/vacuum interface. This
overestimation arises from the fact that the “Triangular Barrier Approximation”
does not take into account the effects of image force barrier lowering caused by
the presence of emitted charge in the vacuum. The one dimensional potential
energy distribution, W(x), external to the metal/vacuum interface taking into
account the image force barrier lowering effects has the following form: 𝑊(𝑥) =
𝑒2
−𝑒|𝐸⃗⃗ |𝑥 − (16𝜋𝜀𝑥) , x > 0. The shape of the potential energy distribution near the
metal/vacuum interface, when image force effects are taken into account is
illustrated by the lower trance in Fig. 3.2.
Figure 3.1 Free electron emission from ground electrode under high electric field
1~10× 108 V/m
Figure 3.2 Mechanism of field emission from the metal surface [64].
−𝑒 2 −𝑒 2
𝐹(𝑥) = = (3.5)
4𝜋𝜀0 (2𝑥)2 16𝜋𝜀0 𝑥 2
−𝑒 2
𝑊𝑒1 = (3.6)
16𝜋𝜀0 𝑥
which gives a parabola shown by curve 1 of Fig. 3.2. The effect of the
accelerating external field when applied at right angles to the cathode surface
gives the electron a potential energy
𝑊E = −𝑒𝐸𝑥 (3.7)
which is a straight line shown by Fig. 3.1 (red line). The total energy is then
−𝑒 2
W = 𝑊a + 𝑊E = − ( ) − 𝑒𝐸𝑥 (3.8)
16𝜋𝜀0 𝑥
which shown the resultant blue line (Fig. 3.2). Thus a marked reduction ∆𝑊 in the
potential barrier is obtained. The maximum reduction at 𝑥𝑚 is obtained by
differentiating equation (3.8) or
𝑑𝑊 𝑒2
= 2
− 𝑒𝐸 = 0
𝑑𝑥 16𝜋𝜀0 𝑥m
𝑒
𝑥𝑚 = √
16𝜋𝜀0 𝐸
Inserting this value into Eqn. (3.8) the lowering in the work function becomes
𝑒𝐸
∆W = −e√ (3.9)
4𝜋𝜀0
𝑒𝐸
𝑊𝑒𝑓𝑓 = 𝑊a − √ (3.10)
4𝜋𝜀0
and the saturation current due to electron emission using Eqn. (3.14) in the
presence of field E becomes
𝑒 𝑒𝐸
𝐽s = 𝐴𝑇 2 𝑒𝑥𝑝 [− (𝑊a − √ )] (3.11)
𝑘𝑇 4𝜋𝜀0
which is known as the Schottky’s equation. If the current density in the absence of
external field is 𝐽0 (Eqn. (3.14)) then rearranging (3.11)
𝑒 𝑒𝐸
𝐽𝑠 = 𝐽0 𝑒𝑥𝑝 [ (−√ )] (3.12)
𝑘𝑇 4𝜋𝜀0
In metals at room temperature the conduction electrons will not have sufficient
thermal energy to leave the surface. The emission current is related to the
temperature of the emitter by the Richardson relation for thermionically emitted
saturation current density:
4𝜋𝑚𝑒𝑘 2 2 𝑊𝑎
𝐽TH = 3
𝑇 𝑒𝑥𝑝 [− ] (3.13)
ℎ 𝑘𝑇
where e and m are the electronic charge and mass respectively, h is Planck’s
constant, k Boltzmann’s constant, T the absolute temperature and Wa the surface
4𝜋𝑚𝑒𝑘 2
work function. A is Richardson constant (𝐴 = ).
ℎ3
𝑊𝑎
𝐽TH = A𝑇 2 𝑒𝑥𝑝 [− ] (3.14)
𝑘𝑇
Figure 3.3 Schematic diagram of thermionic emission from the metal surface [64]
(a) Case of low electric field (b) Case of high electric field
Figure 3.4 Molecular ionization by electric field [64].
In the case of low external electric field (Fig. 3.4 (a)), when the combined
force between electron and positive ion is stronger than that of external applied
force, the charges are chemically bonded stably in the insulating oil. Therefore,
there are a lot of neutral molecules.
Whereas, in high external electric field (Fig. 3.4 (b)) where collisions occur
between neutral molecules and free electrons accelerated in the high electric field.
The collisions energize a valence electron in the neutral molecule promoting it to
the conduction band and generating a positive ion and another free electron [17]
The development of a model that describes the process of field ionization in
dielectric liquids, such as transformer oil, is challenging due to the lack of a
comprehensive liquid-state theory. Consequently, the literature contains very few
publications that propose liquid phase field ionization models. The models that do
exist are based on Zener’s theory of electron tunneling in solids [17, 65-69].
In their ground breaking work, Devins, Rzad and Schwabe [68] applied the
Zener model to dielectric liquids to explain discharge propagation. In this work,
the field ionization charge density generation rate source term is
𝑞 2 𝑛0 𝑎|𝐸⃗⃗ | 𝜋 2 𝑚∗ 𝑎∆2
𝐺𝐹 (|𝐸⃗⃗ |) = 𝑒𝑥𝑝 (− ) (3.15)
ℎ 𝑞ℎ2 |𝐸⃗⃗ |
according to the purity and chemical composition of insulating oil, and the
material information of pure transformer oil used in this paper has been proved by
J. G. Hwang [17, 38, 40]. To apply the ionization ratio by the external electric
field to the insulation oil, it is expressed as Eqn. (3.15) by multiplying the
ionizable density of electrons and molecules.
𝑒 2 𝑛0 𝑎|𝐸⃗⃗ | 𝜋 2 𝑚∗ 𝑎∆2
𝐺𝐼 (|𝐸⃗⃗ |) = 𝑒 2 𝑛0 𝛾(|𝐸⃗⃗ |) = 𝑒𝑥𝑝 (− ) (3.16)
ℎ 𝑒ℎ2 |𝐸⃗⃗ |
Table. 3.1 Characteristic values of pure transformer oil [1, 17, 38, 67-84]
Parameter Symbol Value Reference
Permittivity of transformer oil 𝜀oil 2.2
Positive ion mobility 𝜇p 5 × 10 𝑚2 𝑠 −1 𝑉 −1
−9 [79]
Negative ion mobility 𝜇n 5 × 10−9 𝑚2 𝑠 −1 𝑉 −1 [79]
Electron mobility 𝜇e 1 × 10−3 𝑚2 𝑠 −1 𝑉 −1 [67, 71, 72]
Ion-ion recombination 𝑅pn 9.908× [73, 83, 84]
10 𝑚3 𝑠 −1 𝑚𝑜𝑙 −1
6
(3.17)
The rate at which neutral ion-pairs dissociate to form free ions and the rate at
which free ions recombine to form neutral ion-pairs is controlled by two kinetic
rate constants, KD for dissociation and KR for recombination. According to
Onsager’s theory, the value of the dissociation constant KD, is dependent upon the
applied electric field, while the recombination constant KR, is electric field
invariant. The electric field dependence of the dissociation constant results in an
increase in the concentration of free ions, and thus the conductivity of the liquid
increases as the electric field increases [62].
With the presence of external electric field, the dissociation rate constant 𝐾𝐷
has the following form:
Where 𝐾𝑑0 is the zero field dissociation constant (𝑠 −1 ) and 𝑓(|𝐸⃗⃗ |) is the electric
field dependent function, which relates the increase in the dissociation rate to the
electric field level. The electric field dependent function is defined as:
𝐼1 (4𝑏)
𝑓(|𝐸⃗⃗ |) = (3.19)
2𝑏
Where,
𝑞 3 |𝐸⃗⃗ |
b=√ (3.20)
16𝜋𝜀0 𝜀𝑟 𝑘 2 𝑇 2
c𝐾𝐷0 = 𝑛±0
2
𝐾𝑅 (3.21)
where c is the density of neutral ion pairs, 𝑛± 0 is the equilibrium free ion
concentration in the absence of the electric field in the transformer oil. The
recombination rate constant, 𝐾𝑟 is related to the permittivity and mobility by the
Langevin relation as the following [83]:
𝑒0
𝐾𝑅 = (𝜇 + 𝜇− ) (3.22)
𝜀 +
where 𝜇+ and 𝜇− are the mobility of free positive ion and negative ion in
transformer oil, respectively. In order to develop insight into whether or not
electric field enhanced ionic dissociation plays a significant role in the initiation
and growth of streamers in transformer oil, it is necessary to characterize the
parameter cKD, as this term represents the free charge carrier source term in the
transformer oil. This characterization can be accomplished by using the low field
conductivity value of transformer oil. The conductivity of transformer oil is
measured to verify the effect of ion dissociation during discharge inception and
propagation in insulation oil. The initial concentration of ionic species can be
obtained from the medium’s conductivity using the following expression [83]:
σ = e(𝜇+ 𝑛+ 0 − 𝜇− 𝑛− 0 ) (3.23)
𝜎
𝑛± 0 = (3.24)
𝑒(𝜇+ + 𝜇− )
The concentration of the free ions in the absence of the electric field is substituted
into the Eqn. (3.18) as following:
𝜎 2
c𝐾𝐷0 = ( ) 𝐾𝑅 (3.25)
𝑒(𝜇+ + 𝜇− )
𝜎 2
c𝐾𝐷 = ( ) 𝐾𝑅 × 𝑓(|𝐸⃗⃗ |, 𝑇) (3.26)
𝑒(𝜇+ + 𝜇− )
The electric field dependent ionic dissociation process, which is described above
is a bulk charge generation mechanism, meaning that when modeling the process,
the term cKD represents the generation term in the charge continuity equations for
both the positive and negative ions. This is contrast to the case of field emission or
Fowler-Nordheim charge injection. Forwler-Nordheim charge injection is a
boundary process and so no bulk generation term exists in the continuity equation
for the injected electron.
(a) Without external electric field (a) With external electric field
Figure 3.5 Ionic dissociation by electric field [amended from 64]
When there is no external electric field (Fig. 3.5 (a)), the positive ion and the
negative ion are in a stable state; there are many neutral ion pairs. Whereas, when
the external energy becomes larger than the bonding energy of neutral ion pairs,
they are detached from each other as shown in Fig. 3.5 (b). On the other hand, the
increase of free ions caused by dissociation increases the conductivity of the fluid
[64].
During the formation and growth of a streamer there will exist concentrations
of free positive ions and electrons in the dielectric liquid. These free charge
carriers are produced due to molecular ionization as discussed in the previous
section. The interaction of these free charge carriers with each other and the
surrounding media can be assumed to open up the possibility of electron-ion
recombination, electron attachment to neutral species, forming negative ions and
ion-ion recombination as shown in Fig. 3.6. When developing an electrodynamic
model for streamer initiation and growth in dielectric liquids it is important to
include, when relevant such processes [62].
By transferring the electron, recombination occurs between positively and
negatively charged particles. A photon may be released from this process [83].
The Langevin-Debye relationship is used to model positive ion-negative ion 𝑅𝑝𝑛
and positive ion-free electron 𝑅𝑝𝑒 recombination rates in the transformer oil (thus
reducing the number of electrons and increasing the number of negative ions in
the liquid dielectric) [1, 17 38, 84-86]. According to the Langevin-Debye
relationship, the recombination rates can be expressed as
𝑞(𝜇𝑝 + 𝜇𝑛 )
𝑅𝑝𝑛 = (3.27)
𝜀
𝑞(𝜇𝑝 + 𝜇𝑒 )
𝑅𝑝𝑒 = (3.28)
𝜀
𝜆𝑎 1 × 10−3
𝜏𝑎 = = 3
= 2 × 10−7 (s) (3.29)
⃗⃗
𝜇𝑒 |𝐸 | 5 × 10
This value for 𝜏𝑎 corresponds well with the attachment time constants used by
other authors in the literature [17, 84-87]. Although attachment undoubtedly takes
place during streamer growth in dielectric liquids, its impact on the overall
streamer propagation process is reasonably small due to the fact that attachment
processes take place on a longer time scale than important dynamics such as the
separation of positive ions and electrons in the ionization zone at a streamer’s tip
[87].
During the course of the research being presented in this thesis, the ion and
electron mobility values in transformer oil 𝜇± and 𝜇𝑒 , respectively, are used as
input parameters for all electrodynamic simulations. A mobility values of
1 × 10−9 m2 /V ∙ s is used for the positive and negative ions in all simulations.
This value has been verified experimentally for transformer oil in [82]. It is also in
agreement with the theoretical analysis presented in [88]. A mobility value of
1 × 10−4 m2 /V ∙ s is used electrons in all simulations. This value corresponds
with the data presented in [86] and the electron mobility model described in [89].
3.6 SUMMARY
CHAPTER 4
4.1 INTRODUCTION
Figures 4.1 (a) and (b) show experimental setup as type 1 side view and top
view of electrode system, respectively. The diameter of the rod electrode and
plane electrode was 6 and 70 mm, respectively. The rod electrode is placed so that
the tip touches the pressboard surface. The position of pressboard and electrode
configuration in the experimental system determines the electric field distribution
at the oil/pressboard interface. On the other hand, a more directional and intense
electric field is created towards the solid surface from localized and
inhomogeneous electric field at the edge of the rod electrode compared to other
methods. But, the creepage discharge do not always propagate radially in this
electrode configuration. For this reason, it is difficult to evaluate the discharge
propagation length.
In the case of needle-bar electrode configuration as type 2 (Figs. 4.2 (a) and
(b)), the tip radius of the needle electrode was 10 μm and gap distance 50 mm to
the bar electrode. To generate the creepage discharge in one direction, we used
guide electrode beneath a PB. The needle electrode was placed at an angle of 30
degree from the surface of a specimen with the needle tip touching the pressboard
surface. These above two methods have been widely used to study surface
discharge phenomena.
Figures 4.3 (a) to (c) show microscope image of needle electrode before and
after impulse experiment and after breakdown. As can be seen in Fig. 4.3 (b), the
needle electrode tip is not changed after 400 times impulse voltage, whereas
scratches appear nearby needle tip, and the number of scratches and size increased
with increasing the number of the applied voltage voltages (average scratch size:
20 μm). But the results revealed that these kinds of scratches nearby the needle tip
didn’t affect the discharge inception voltage. On the other hand, in Fig. 4.3 (c), the
needle tip is mutated after breakdown. The radius of curvature expanded by times
3, affecting the discharge inception voltage. Thus, when the experiment used the
needle electrode, it is very important to check the needle electrode tip after
experiment. In this work, the needle electrode was checked after every experiment
using a microscope to acquire reliable data.
Figure 4.3 Needle electrode (a) before experiment, (b) after experiment and (c)
after breakdown
Figures 4.4 and 4.5 (a) to (d) show schematic diagram and photograph of the
experimental measuring system. Vacuuming was made in the chamber after the
test sample was immersed in the insulating oil for three hours to remove moisture
and gasses from the insulating oil and fill oil molecules into the PB structure.
Discharge image was observed using a digital camera (Fujifilm Finepix S100fs)
and usual digital camera equipped with an image intensifier (Hamamatsu C9016-
2x series-23). Discharge light emission was also detected with a photomultiplier
tube (PMT, Hamamatsu Photonics, H6780-20) to determine PDIV. A 50 Ω
resistor was used to obtain the discharge current signal.
A positive standard lightning impulse voltage was applied to the electrode
varied from 60 to 100 kV by a step with increment of 20 kV (type 1) and from 20
to 45 kV by a step with increment of 5 kV. The interval time between each
voltage level was one minute. The impulse voltage application was repeated 10
times (type 1) and 5 times (type 2) at each voltage level, respectively.
Figure 4.4 Schematic diagram of the experimental setup and measuring system
(d) CCD camera, two image intensifier, streak camera, two PMT and three optical
lenses
Figure 4.5 Photograph of the experimental system
(b) C9016-2X
Figure 4.6 FINEPIX S100FS and image intensifier (I.I)
Five kinds of PB samples were used; namely, neat pressboard (NP), dry
pressboard (DP), epoxy resin coated pressboard (EP-A and EP-F), Teflon coated
pressboard (TP) and pressboard coated by silica/epoxy nanocomposite (SP). Three
samples of each specimen were prepared for reproducibility on experiment results.
Figure 4.10 shows the schematic diagram to prepare for surface coating on the
pressboard surface. In preparing nano silica/epoxy composite, nanoparticles were
dispersed in the base epoxy bisphenol A of F type at the proportion of each weight
percent using a vacuum mixer. The mass ration of epoxy resin to curing agent is
30:10. EP-A, EP-F and SP specimens were prepared by thinly coating PB surface
with bisphenol A type epoxy resin (EP-A), bisphenol F type epoxy resin (EP-F),
silica/bisphenol F type epoxy resin SP, respectively, and then put in a vacuum
oven for 30 minute and then being dried using a dry oven for 3 hours at each 70
and 150℃. DP specimen was also dried under the same condition as EP, TP and
SP specimen. DP is a reference specimen in this research work. SP specimens
with different SiO2 nano filler contents (0, 0.2, 0.5, 1, 3, 5 and 50wt%) were
prepared as shown in Table 4.2. Figures 4.11 (a) and (b) show pressboard samples
used in experiment before and after epoxy coating on the one side surface of PB.
Figure 4.10 Schematic diagrams to prepare for nano silica and epoxy/silica
coating on surface of pressboard
Figure 4.12 shows the weight and thickness variation of each sample before
and after drying process. We confirmed that the average decreasing rate of dried
specimen as DP, EP-A, EP-F and SP of weight, thickness and of each specimen
decreased by 5.3% and 3%, respectively.
Dielectric properties of each specimen were measured with an impedance
analyzer (IWATSU Impedance Analysis PSM3750) at room temperature and
frequency from 50 Hz to 2 MHz after the drying process. The number of test
samples of each specimen was two. The size and thickness of a sample was 70
mm by 70 mm and 850 μm, respectively. Prior to measurement, gold electrodes
with diameter of 50 mm were deposited onto both sides of a sample by Magnetron
sputter (MSP-1S) with a thickness of 3 Å for 3 minute to ensure the
reproducibility of measurement and improve the contact area between the
electrode and the surface of PB. The gold sputtering thickness on the PB surface is
54 nm. The dielectric properties were measured after oil immersion process for 3
hours. Note that measurements of dielectric properties were conducted two times
each for two samples with error of 3 %.
Figure 4.12 Weight and thickness variation of each sample before and after drying
process
Figure 4.13 shows the surface roughness before and after epoxy resin coating.
The result represents an assembly of surface irregularities and constitutes main
Figure 4.13 Surface roughness before and after epoxy resin coating (a) DP and (b)
EP-A
Figure 4.14 Surface roughness of each type of sample measured using a surface
roughness tester (bottom: Ra, top: Rz)
Figure 4.16 SEM image of SiO2 nanoparticles surrounded by red circle dispersion
in base epoxy matrix (Cross section view) (a) 0.2wt%, (b) 0.5wt%, (c) 1wt%, (d)
3wt%, (e) 5wt% and (f) 50wt%
Figures 4.17 (a) and (b) show examples of discharge images and typical
waveforms of positive standard lightning impulse voltage and those detected with
PMT without and with creepage discharge, respectively. We determined the
partial discharge inception using PMT, image intensifier and discharge current
waveform. In general, the luminous sensitivity of PMT (500 [μA/lm]) is higher
than that of the image intensifier (230 [μA/lm]) as shown in Table. 4.3. Besides
we found that the image intensifier can’t catch the light intensity from creepage
discharge below 50 pC as shown in Figure 4.18. For this reason, we found that
sometime the image intensifier did not perceive the discharge light in spite of
PMTs perceived at low apply voltage. Thus, PMT is more reliable tool to decide
PDIV that is determined when a waveform is detected from PMT instead of the
image intensified camera.
Figures 4.13 (a) and (b) shows general waveforms with/without creepage
discharge. In the case of no PD in Fig. 4.17 (a), there is no signal PMT, discharge
current and image intensifier image. On the other hand, when the creepage
discharge occurred, discharge light emission can be detected clearly by PMTs,
current waveform and image intensifier as shown in Fig. 4.17(b).
(a) (b)
Figure 4.17 Determination of creepage discharge inception voltage (a) without
creepage discharge inception at 25 kV and (b) with creepage discharge inception
at 55 kV
Figure 4.18 Relation between the output of image intensified camera and charge
amount in pC as a function of lightning impulse voltage
Figures 4.19 (a) and (b) show the real frequency dependence of real part 𝜀r′ and
imaginary part 𝜀r′′ of the complex relative permittivity for different nano silica
filler loading 𝑆l at room temperature. It can be seen in Figures 4.19 (a) that 𝜀r′
decreases stably with increasing frequency from 50 Hz to 2 MHz, whereas the
relative dielectric loss 𝜀r′′ increases with increasing as a function of frequency in
Fig. 4.19 (b). As can be seen in Fig. 4.20, 𝜀r′ of silica/epoxy nanocomposite coated
samples at 100 kHz decreases at 100 kHz corresponding to dominant frequency
component that the standard lightning impulse voltage contains.
It is also found that 𝜀r′ of presents firstly decreases and increases with the
increase of the 𝑆l , and reaches a minimum at 1wt%. The increase of 𝜀r′ with
decrease in frequency is generally known as caused by interfacial polarization at
occuring the interface between epoxy and nanoparticles [53-58]. Q. Wang and G.
Chen et al., [92] has reported same results on decrease 𝜀r′ for silica/epoxy
nanocomposite. When fillers are loaded into the epoxy resin, the changes of
dielectric properties with the presence of the nano size filler and their loading
concentration may be caused by the following reason from Nelson and Forthergill
[93]: decrease in the permittivity 𝜀r′ of nano particle/epoxy resin composites is
related to the restriction of dipole movement at the interaction zone. For example,
the measured real part of the permittivity at 393 K using high permittivity TiO2
filler (≈ 99) is: 9.99 (base resin), 13.8 (micro-composite, size: 1.5 μm), and 8.49
(nanocomposite, size: 23 nm) at 1 kHz. The nanocomposite has a lower
permittivity than the base resin and micro composite. The electrical properties of
nanocomposites are mainly determined by the dispersion and nanoparticle filler
loading characteristics. The physical and chemical characteristics of the interface
can be influenced by these factors, leading to changes in micro scale features such
as traps, carrier mobility and free volume [93, 94]. On the other hand, free volume
in nano size particle/epoxy composite systems will decrease when nanostructured,
and will increase when micro structured. Free volume is demonstrated in
experiment and in theory by Nelson and Forthergill. Obviously, free volume plays
an important role in the reduction of the permittivity 𝜀r′ [93-97].
Prior to study discharge patterns under 60, 80 and 100 kV of impulse voltage
application, PDIV of each sample was measured first to compare with modified
other samples. Figures 4.21 (a) to (f) show discharge image of each sample at 100
kV. White lines and circles in the figures depict the high voltage electrode and
ground electrode, respectively. Here, let the discharge propagation length (𝑙d ) be
defined as the length from the high voltage electrode to a site of the longest
discharge edge part. It should be noted that creepage discharges under a positive
lightning impulse voltage do not always propagate radially in this electrode
configuration. Such orientation and distribution of branches on the surface of
insulator is considered to be due to distortion of the electric field resulting from
surface charge accumulated on the insulator [98]. The creepage discharge trend
such as discharge light intensity, the number of discharge branches and discharge
length is changed according to dry process and surface coated material on the
surface of PB. The discharges are composed of ramified branches of streamer
propagating on the surface of NP, DP and TP samples, while emitting intense
luminous area. Whereas the discharge image in EP-A and EP-F show weak light
spots at all the voltage levels and propagating discharge shows filamentary
branches. On the other hand, the discharge pattern of SP-0.2 wt% and SP-5 wt%
shows more intense white luminous part at their streamer and branch than that of
EP-F samples and propagating discharge shows filamentary branches. Thus, we
confirmed that the surface conditions and materials on PB influence creepage
discharge properties and tendency.
The total number of discharge branches observed on the surface of each sample
was counted using a binary image analysis program (AZO V2.30) as shown in Fig.
4.22. It is seen in these figures that the The discharges are composed of ramified
branches of streamer propagating on the surface of NP, DP and TP samples. Note
that NP, DP and TP samples have more divided discharge branches from main
streamer than EP-F sample as shown in Fig 4.23.
Figure 4.22 Discharge binary images of each sample using image analysis
program at 80 kV
Figure 4.23 The number of discharge branches of each sample at 80 kV and 100
kV
Figure 4.24 shows discharge occurrence probability (𝑃d ) at each voltage level
for different kinds of specimen. In NP, the probability (𝑃d ) of 100% of discharge
occurrence is observed at each voltage level from 60 to 100 kV. On the other hand,
it is seen that 𝑃d at 60, 70 and 100 kV is 33.3, 96.6 and 100 % (DP), 13.3, 66.6
and 100% (EP-A), 10, 33.3 and 80% (EP-F) and 36.6, 56.6 and 100% (TP),
respectively. The discharge occurrence probability of DP decreased at only 60 kV.
These results indicate that the drying process and the moisture level in PB should
affect the discharge inception as well as development process. On the other hand,
it should be noticed that 𝑃d of SP (0.2, 0.5, 3 and 5 wt%) are less than 63.5 and
73.3% from 60 to 100 kV, and that 𝑃d of SP with 50 wt% was higher than that of
EP-F at all the voltage levels. These results will be discussed in Section 4.6.
Next, let PDIV ratio 𝑘1 can be defined as the ratio of PD occurrence
probability of SP to that of EP-F. The ratio 𝑘1 of SP specimen was defined as the
voltage of 10% discharge occurrence probability of SP divided by that of EP-F.
Figure 4.25 shows the 10% PD occurrence probability ratio 𝑘1 dependent on filler
loading of SiO2 nano fillers under the impulse voltage. As can be seen in Fig. 4.25,
the ratio 𝑘1 is larger than one, meaning that discharge occurrence suppression
property can be improved with appropriate 𝑆𝑙 compared to that of EP-F. The ratio
𝑘1 presents the highest values at SiO2 filler loading of SP-0.2wt%, while further
increasing 𝑆l results in decrease of 𝑘1 .
Figures 4.26 and 4.27 show the discharge propagation length ld of each type of
specimen with different SiO2 nano filler loading, respectively, at all the voltage
levels. It is evident from the two figures that ld for each sample increases as the
applied impulse voltage increases from 60 to 100 kV. Note that the average
discharge propagation length ldave of the solid layer coating samples EP-A, EP-F,
TP and DP is shorter than that of NP sample at all the voltage levels. On the other
hand, it should be noticed that ldave of PS-0.2, 0.5 and 5 wt% is shorter than that of
the other samples at all the voltage levels. These results indicate that the solid
layer coating of epoxy, Teflon and nano silica/epoxy composites on PB should
affect not only the discharge inception but also the development process as well.
That might be influenced by dry process and surface modification. These detailed
results will be discussed in Section 4.6 together with the results of the needle-bar
electrode system.
Figures 4.28 (a) to (e) show creepage discharge image of each sample NP, DP,
EP-A, SP-0.2 wt% and SP-3 wt% at 45 kV using the needle-bar electrode system,
respectively. White triangles in the figures depict the high voltage electrode. The
measuring method of discharge propagation length (ld) is the same with Section
4.3.2. The discharges are composed of ramified branches of streamer propagating
on the surface of NP and DP samples, while emitting intense luminous area
appears at the end part of their branch tip and streamer. Note that NP and DP
samples have more discharge branches than EP-A, EP-F and SP specimens and
this phenomenon is similar with the results obtained by the rod-plane electrode
system. Figure 4.29 shows discharge light intensity as a function of the applied
impulse voltage Vi of each kind of sample. The discharge light intensity of EP-A,
EP-F and SP specimen shows weak discharge light intensity at all the voltage
levels than that of NP and DP. Propagating discharge of EP-A, EP-F and SP
samples shows filamentary branches.
Figure 4.30 shows discharge occurrence probability (𝑃d ) at each voltage level
Vi for different kinds of specimen. Each specimen was tested 3 times at least
under the same test conditions. In NP, the probability (𝑃d ) of 100% of discharge
occurrence is observed at each voltage level from 25 to 45 kV. On the other hand,
it is seen that 𝑃d at 20, 25 and 30 kV is 66.6, 86.6 and 100% for DP, 53.3, 73.3
and 86.6% for EP-A and 26.6, 53.3 and 73.3% for EP-F, respectively. These
results indicate that the drying process and moisture level in PB affect both the
discharge inception and development processes. On the other hand, it should be
noticed that 𝑃d of 0.2 and 3 wt% at Vi 40 and 45 kV is 100%. These results
indicate that the SiO2/epoxy composite on the surface of PB should improve the
discharge inception voltage.
Figure 4.28 Discharge patterns of (a) NP, (b) DP, (c) EP-F, (d) SP-0.2wt% and (e)
SP-3wt% at Vi 45 kV
Figure 4.30 Discharge occurrence probability at each voltage level for different
kinds of specimen
Figure 4.31 shows 𝜀𝑟′ and 30% discharge occurrence probability ratio k2, which
is defined as Vi giving 30% 𝑃d of EP-F divided by that giving 30% 𝑃d of nano
silica/epoxy composite coated PB. The ratio k2 dependent on the filler loading of
silica nano fillers under the Vi. As seen in Figure 4.31 the ratio k2 is larger than
one. Meaning that insulation performance against the creepage discharge
generation can be improved with appropriate filler loadings compared to that of
NP. Note that k2 presents the highest value 1.4 at silica filler loading of 3 wt%,
while decreases with further increasing nano silica filler loading above 5 wt%.
High filler loading sample with 50 wt% of the filler shows still a high ratio k2 than
that of EP-F. Moreover, 𝜀𝑟′ firstly decreases and increases with the increase of the
filler loading, and reaches a minimum at 3 wt%. It can be concluded that the
reduction of 𝜀𝑟′ corresponds to the improved Pd of SP specimens.
Many researchers conveyed the similar conclusions on the effect of nano filler
loading on the performance of vacuum surface flashover and breakdown
properties, and proposed a variety of models and interpretations. Yu Chen et al.
investigated the vacuum surface flashover characteristic of nano size Al2O3/epoxy
nanocomposite. The flashover voltage shows the highest values at Al2O3 filler
loading of 3 wt%. The experimental results were explained in terms of the effects
of different roles of shallow and deep traps introduced by the nano filler loading
[56]. Shengtao Li et al. also investigated the surface flashover and breakdown
voltages of TiO2/epoxy nanocomposite in SF6 gas. The optimal filler loading of
TiO2 for the normalized flashover voltage k1 was 1 wt% [53-55]. On the other
hand, the present study reveals that the PD occurrence probability of SP-0.2 wt%
SiO2 added epoxy composite insulation (SP) is improved to be 1.3 times as much
as that of EP-F. The decreasing PD occurrence probability with the nano filler
loading can be explained in two ways as follows; 1) SiO2/epoxy nano composites
coating on PB suppresses emission of trapped electron from the surface of PB in
the discharge inception process, and 2) the discharge inception voltage possibly
depends on the surface roughness as well as the filler loadings. More detailed
discussion will be made in Section 4.6
Figures 4.32 and 4.33 show the discharge propagation length ld of each sample
at all the voltage levels. It is evident from the figure that ld for each sample
increases as the applied Vi increases from 20 to 45 kV. Note that the average
propagation length ldave of DP, EP-A, EP-F and SP samples at all Vi is shorter than
that of NP samples by 42%, 64% and 70%, respectively. Figure 4.34 shows
relation between discharge propagation length and relative permittivity. Discharge
propagation length ratio k3 be defined as 45 kV giving ld of neat EP divided by
that giving ld of silica/epoxy nanocomposite. As seen in Fig. 4.34, discharge
propagation length ratio k3 is larger than one, meaning that the insulation
performance against the creepage discharge propagation can be improved with
appropriate 𝑆𝑙 compared to that of EP. Note that k3 presents increases and
decreases with the increase of the 𝑆𝑙 above 3 wt%, respectively. It can be
concluded that the low 𝑆𝑙 improved ld. But note that once discharge occurred, ld of
each sample is becomes the same at each voltage level, besides scattering of the
data overlaps each other, meaning no appreciable effect of the filler loading on ld
in oil condition. These results will be discussed in Section 4.6.
Figure 4.32 Discharge propagation length ld of NP, DP, EP-A and EP-F as a
function of Vi
Figure 4.34 The relationship between average discharge propagation length ldave
ratio k3 and permittivity 𝜀r′ of SP with different silica filler loading at 45 kV
The effect of the solid layer coating on Pd and ld is discussed. The following
three factors are possibly considered to explain the experimental results on Pd and
ld, respectively:
Note that cellulose paper placed on a factory floor is said to be able to hold 4-8%
moisture in the relative humidity of 30 to 70% in winter and summer, respectively
as shown in Fig. 4.35 [9]. Besides, PB cellulose fibres form microcapillaries,
which contain insulation oil, gaseous residues and water molecules.
creepage discharge is more likely to occur and then propagate along the surface of
PB with increase in the C [pF/mm2] of solid insulation, because the electrostatic
energy stored in the C increases [99, 101]. We confirmed that the weight,
thickness after dry process and C after epoxy/silica nanocomposite coating
decreased by 5.3%, 3% and 14%, respectively. Equation 4.1 and figure 4.36 show
relation between capacitance and estimated discharge inception voltage.
𝑉 = K𝐶 −𝑛 (4.1)
Estimated discharge inception voltage after dried process and surface coating
on PB from Eqn. 4.1 increases with decreasing specific capacitance as shown in
Fig. 4.32. Besides, in rod-plane electrode results, Pd of DP decreased by 66.7% at
only 60 kV and ld also decreased by and 12.1, 4.2 and 10.2% at each Vi as shown
in Fig. 4.24, 4.26, 4.30 and 4.32. It is because the capacitance decreases, resulting
in less discharge development according to Eqn 4.1. Thus, it can be said that the
moisture level in PB affects the discharge inception and development as well.
Figure 4.36 Relation between estimated discharge inception voltage and the
specific capacitance before and after dry process of pressboard at 70 and 150℃
for 3 hours, respectively
The second possible reason for Pd and ld is a surface modification effect by the
solid layer coating on PB. The surface of NP and DP exhibits numerous
protrusions of cellulose fibrous as shown in Fig. 4.37 [98, 101], whereas the
surface protrusions of EP-A, F and SP samples were covered with epoxy resin.
For that reason, there are no protrusions on the surface of coated PB using a
microscope as shown in Fig. 4.37. We estimated the electric field distribution with
presence of protrusions around the high voltage electrode using COMSOL
Multiphysics 2D MODEL as well as surface roughness measurement results as
shown in Fig. 4.38.
The generalized hydrodynamic drift-diffusion equations combined with
Poisson’s equation were employed in dielectric liquids. The detailed analysis
method using COMSOL MULTIPHYSICS will be dealt in Chapter 6.
Figure 4.39 shows the simulation results, the electric field is disturbed with the
presence of protrusions around the needle electrode simultaneously with discharge
inception over 1 × 108 V/m , and then the creepage discharge is likely to
propagate toward protrusion tip along the pressboard surface. Concentrated
electric field in protrusion tip is more likely to increase with increasing time than
in protrusion pole part as shown in Fig. 4.40. Thus, in the case of NP and DP, it
might be possible that the electric field concentration occurs at the protrusion tip
and it could be starting point of a creepage discharge inception.
Figure 4.40 The electric field results of protrusion tip parts and pole parts
The third possible reason for Pd and ld is that epoxy/silica nano composites
coating may suppress initial electron emission contributing to creepage discharge
inception and propagation from the surface of PB, resulting in the decrease of the
Pd at all the Vi as well as the decrease in ld as well.
Let us propose a surface flashover model in the nanocomposite coating PB as
illustrated in Fig. 4.41. In general, oil immersed PB form microcapillaries which
contain insulation oil. Porosity of PB causes oil to penetrate into the PB bulk. The
free charges such as positive ion, negative ion and electron are generated from oil
immersed PB bulk due to molecular ionization and ionic dissociation under a high
electric field [32]. During creepage discharge process, charge carriers emitted
from electron avalanches could excite the electron from the surface of PB, and
newly generated electrons can play a role as the seed of new electron avalanches
and some of these secondary electrons will again strike the surface of PB,
producing tertiary electron [103]. Then, the creepage discharge is more likely to
incept and then can more readily creep along the surface of PB. Deep electron
4.7 SUMMARY
1. 𝜀r′ decreases with the increase of the 𝑆𝑙 , while further increasing 𝑆l results in
increase 𝜀r′ .
CHAPTER 5
5.1 EXPERIMENT
Figures 5.1 (a) and (b) show side view and top views of electrode system,
respectively. The tip radius of the needle electrode was 10 μm and gap distance
was 50 mm to the bar electrode. The needle electrode was touched at an angle of
30 degree from the surface of silica/epoxy nanocomposite. There is no back
electrode at the bottom place of the specimen to consider only the surface effect of
specimens on creepage discharge.
The whole electrode system was placed in a mineral oil immersed chamber as
shown in Fig. 5.2. Vacuuming was made in the chamber for 2 hours to reduce
gasses that influence to PDIV of the oil/solid composite insulation system.
Discharge image was observed using a digital camera (Fujifilm Finepix S100fs)
and a digital camera equipped with an image intensifier (Hamamatsu C9016-2x).
Discharge light emission was also detected with a photomultiplier tube (PMT,
Hamamatsu Photonics, H6780~4) to determine PDIV. A 50 Ω resistor was used to
obtain the discharge current signal.
A positive standard lightning impulse voltage was applied to the needle
electrode varied from 25 kV (PDIV of neat epoxy) to 75 kV by a step with
increment of 5 kV. The interval time between each voltage level was one minute.
The impulse voltage application was repeated 5 times at each voltage level.
Figure 5.2 Diagram of experimental setup to measure and observe PDIV and
creepage discharge properties in oil and SiO2 /epoxy composite insulation system
Table 5.1 lists prepared silica/epoxy nanocomposite with different filler loading
(0.1, 0.5, 1, 3, 5, 10, 20, 45 wt%) of 45 nm and particle size (12, 22, 45, 80, 130,
500 nm and 13 μm) as shown in Table 5.1.
Figures 5.3 and 5.4 show photos and SEM images of prepared with different
nano 𝑆𝑙 . All samples were supplied from Nissan chemical industries., LTD. The
size of each sample for creepage discharge measurement and dielectric property is
70 mm by 100 mm and 3 mm, 70 mm by 70 mm and 1 mm, respectively. Figures
5.3 and 5.4 shows SEM image of both surface layer and middle layer of 12, 22, 45
and 80 nm silica fillers to investigate the nano silica state of dispersion in the base
epoxy matrix. To observe nano silica state of dispersion, samples with pretreated
by Platinum vapor deposition and protective film laminated using focused ion
beam (FIB) with accelerating voltage 1.0 kV. The observation of the particle
dispersion state was investigated by Nissan Chemical Co. Ltd. As can be seen in
Figs. 5.3 and 5.4, white circles in the figures show nano silica particles dispersed
in base epoxy. All the silica/epoxy nanocomposite specimens seem to exhibit
good dispersion of nanoparticles in both surface layer and middle layer.
Figure 5.3 Photos of samples with different nano silica filler loading and neat
epoxy (a) neat epoxy (b) 0.1wt%, (c) 0.5wt%, (d) 1wt%, (e) 3wt%, (f) 5wt%, (g)
10wt%, (h) 20wt% and (i) 45wt%
Figure 5.4 SEM images of surface and middle layer of nano silica/EP
composites with different nano silica
Figure 5.5 SEM images of surface and middle layer of nano silica/EP
composites with different nano silica
Before dielectric property measurement, all the samples were dried for 1 hour at
100℃ to remove the moisture effect. Figures 5.6 (a) and (b) show the weight and
thickness before and after the drying process of silica/epoxy nanocomposite. As
you can see in the figures, the weight decreases after the dry process and then
increases after 24 hours at room temperature. But there is no variation of thickness
before and after the dry process.
Figures 5.8 (a) to (b) show frequency dependence of real part (permittivity 𝜀r′ )
and imaginary part (dielectric loss 𝜀r′′ ) of the complex dielectric constant 𝜀r∗ for
EP with different nano silica filler loadings at room temperature. It can be seen in
Figure that 𝜀r′ decreases stably with increasing frequency from 50 Hz to 2 MHz.
As can be seen in Fig. 5.9, 𝜀r′ increases with increase in the filler loading at 100
kHz corresponding to dominant frequency component that standard lightning
impulse voltage contains. It is also obvious from Fig. 5.9 that 𝜀r′ decreases with
decreasing the filler loading below 1 wt%, and reaches a minimum at 0.1 and 0.5
wt%, while further increasing nano 𝑆l results in increased 𝜀r′ above 3 wt%. This
reduction in 𝜀r′ was discussed in Chapter 4. As can be seen in Fig. 5.8 (b), 𝜀r′′
decreases with increasing frequency from 50 Hz to 2 MHz, while no significant
difference appears in 𝜀r′′ under 20 wt% loading at 100 kHz.
Figure 5.9 Relative permittivity at 100 kHz with different nano silica filler loading
Figures 5.10 (a) to (b) and 5.11 (a) to (b) show frequency dependence of real
part (permittivity 𝜀r′ ) and imaginary part (dielectric loss 𝜀r′′ ) of the complex
dielectric constant 𝜀r∗ for EP with different nano silica size of 3 wt% and 10 wt%,
respectively at room temperature. It can be seen in Figure that 𝜀𝑟′ decreases stably
with increasing frequency. As can be seen in Fig. 5.11 (a) and 5.12 (a), 𝜀r′
increases with increase in the filler size at 100 kHz corresponding to dominant
frequency component that standard lightning impulse voltage contains. It is also
obvious from Fig. 5.11 (a) and 5.12 (a) that 𝜀r′ decreases with decreasing the filler
size below 22 nm, while further increasing nano silica filler size results in
increased 𝜀r′ above 22 nm with keeping the filler loading constant. As can be seen
in Fig. 5.10 (b) and 5.11 (b), 𝜀r′′ increases with increasing frequency, while no
significant difference appears in 𝜀𝑟′′ under 20 wt% loading at 100 kHz.
Santanu Singha and M. Joy Thomas et al., [104] have reported dielectric
property with different particle size. Micro size particle/epoxy composites show a
higher permittivity value than the nanocomposites. They suggest the reason on the
high permittivity value in micro composites probably due to the fact that there is
no restriction in the mobility of epoxy chains with micro fillers [104]. Toshikatsu
Tanaka et al., [105-107] have reported electron traps existing inside core quantum
dots (QDs), shell and interface in a core-shell structure embedded in polymer
matrix. The QDs model has formed polymer matrix, shell insulator and core
quantum dot. Following Eqn. 5.1 shows polarizability in core-shell system [105-
107].
where core with permittivity and shell radius is 𝜀1 and r1, shell with
permittivity , fraction of the total particle volume occupied by the core and
thickness is 𝜀2 , 𝜌 = (r1 /r2 )3 and (r2-r1), respectively.
Eqn 5.1 can be explained in terms of increase in 𝜀r′ with filler loading and size.
On the other hand, α and 𝜀r′ are proportional to each other. The α increase with
increase nano filler size, relation between polarizability and 𝜀r′ shows follows:
𝜀r′ = 𝜀0 + 𝜒
𝜌 = (r1/r2)3 is the fraction of the total particle volume occupied by the core.
A core-shell nanoparticle can be approximated as an effective homogeneous
sphere with an equivalent permittivity given by the Eqn. 5.2. The 𝜀𝑐 increase with
increase nanoparticle size from Eqn. 5.2.
𝜀1 (1 + 2𝜌) + 2𝜀2 (1 − 𝜌)
𝜀𝑐 = 𝜀2 (5.2)
𝜀1 (1 − 𝜌) + 𝜀2 (2 + 𝜌)
Figure 5.12 Relative permittivity at 100 kHz as a function of nano silica size for
different filler loading
Figures 5.13 (a) and (b) show creepage discharge image of EP and EP 45-1 wt%
at 75 kV as well as waveforms of two PMT signals, current and impulse voltage.
The decision way of PDIV is same with that given in Chapter 4. Note that white
triangles in the figures depict the high voltage electrode. Here, let the discharge
final length ld be defined as the length from the high voltage electrode to a site of
a longest discharge edge part. Discharge streamer in neat EP exhibits more intense
luminous from the needle tip and higher peak current than that of EP 45-1 wt% at
all the voltage levels as observed from PMT signal and current waveform.
Prior to study creepage discharge pattern under 25-75 kV of impulse voltage
application, PDIV of neat EP was measured to be 30 kV. Three specimens were
used to confirm reproducibility at least under the same conditions. Creepage
discharges of all the samples were found to occur intermittently and randomly at a
given Va. Figure 5.14 shows discharge occurrence probability (Pd) as a function of
Vi with different 𝑆l . As can be seen in the Figure, Pd of 100% is observed over 45
kV for neat EP, while EP 45-45 wt% exhibits higher Pd than neat EP at 30 kV.
Next, let 50% creepage discharge occurrence ratio k4 be defined as Vi giving 50%
Pd of neat EP divided by that giving 50% Pd of silica/epoxy nanocomposite.
Figure 5.14 Discharge occurrence probability at each voltage level with different
nano silica filler loading
Figure 5.15 shows the relationship between 𝜀𝑟′ and 50% discharge occurrence
probability ratio k4. As seen in figure, the ratio k4 is larger than one, meaning that
the insulation performance against the creepage discharge generation can be
improved with appropriate 𝑆l compared to that of neat EP. Note that k4 presents
the highest value 1.33 at 𝑆l of 1 wt%, while further decreases with increasing nano
𝑆l above 3 wt%. 𝜀𝑟′ presents firstly decreases and increases with the increase of the
𝑆l , and reaches a minimum at 0.5 wt%. It can be concluded that the appropriate
low 𝑆l improved Pd of silica/epoxy nanocomposite specimens.
Figure 5.16 shows Pd as a function of Vi for different nano silica size with
keeping the filler loading constant. As can be seen in Figure, EP with big size
nano particles (130, 500 nm and 13 μm) exhibits higher Pd than neat EP and EP
with small size particles at all the Vi, whereas EP with small size particles as low
as 80 nm and 3 wt% show that creepage discharge occurrence can be improved.
Figure 5.17 shows the relationship between 𝜀r′ and 50% 𝑃d . Note that 50% PD
occurrence probability ratio k4 presents the highest value 1.25 at nano silica size
of 22 nm, while ratio k4 decreases with increasing nano silica size.
Shengtao Li et al., [94] have reported surface flashover performance under
impulse voltage in vacuum with nanoparticles (NPs) and micro size particles
(MPs) in terms of shallow and deep traps. MPs show contrary behavior and MPs
causes a serious low flashover voltage, whereas small amounts (up to 3 wt%) of
NPs improve flashover performance by over 58% compared with neat polystyrene.
MPs can introduce shallow traps while NPs introduce deep traps. The deep traps
are crucial in improving flashover performance by trapping the charge carriers and
thereby weakening secondary electron multiplication processes. In Fig. 5.17, nano
size particle 22 nm can be improved Pd by over 28% and 43% compared with neat
EP and 13 um size particle, respectively. This result shows similar trend with
reference [94]. Thus, it might be possible that the nano size particle improve
creepage discharge inception process, meaning that charge carriers are suppressed
by deep trap from emitted secondary electron of the surface of epoxy/silica
nanocompsoites.
Figure 5.16 Discharge occurrence probability 3 wt% at each voltage level with
different nano silica size
Figures 5.18 to 5.22 show the discharge propagation length ld at Vi and ratio k5
of each kind of sample with different filler loading and size at 75 kV. It is evident
from Figs. 5.18 to 5.22 that ld for each kind of sample increases as the applied
voltage Vi increases from 30 to 75 kV. Note that the average discharge
propagation length ldave of nano silica/epoxy composite samples at all the voltage
levels is shorter than that of neat EP samples. Figs 5.19 and 5.21 show the ldave
ratio k5 at 75 kV. Ratio k5 be defined as 75 kV giving ld of neat EP divided by that
giving ld of silica/epoxy nanocomposite. As seen in figure, the ratio k5 is larger
than one, meaning that the insulation performance against the creepage discharge
propagation can be improved with appropriate 𝑆l and filler size compared to that
of neat EP. Note that k5 presents increases and decreases with the increase of the
𝑆l and filler size above 3 wt% and 80 nm, respectively. It can be concluded that
the low 𝑆l and EP with small size particles improved ld. But as mentioned in
chapter 4, once discharge occurred, 𝑙d of each sample is becoming the same at
each voltage levels, besides scattering of the data overlaps each other, meaning no
appreciable effect of the filler loading on 𝑙d appears under the present condition.
Figure 5.18 Discharge propagation length of EP with different silica filler loading
as a function of Vi with keeping the 45 nm filler size
Figure 5.19 The relationship between average discharge propagation length ldave
and permittivity 𝜀r′ of EP as a function of silica filler loading at 75 kV
Figure 5.20 Discharge propagation length ld of EP with different silica filler size
as a function of Vi with keeping the 3 wt% filler loading
Figure 5.21 The relationship between average discharge propagation length ldave
and permittivity 𝜀r′ of EP as a function of silica filler size at 75 kV with keeping
the 3 wt% filler loading
Figure 5.22 Discharge propagation length ld of EP with different silica filler size
as a function of lightning impulse voltage with keeping the 10 wt% filler loading
5.2.4 DISCUSSION
Next, the effect of nano silica on PDIV is discussed. The following two reasons
are possibly considered to explain the experimental results of the effect of nano
silica loading on the discharge occurrence probability of EP as shown in Figs.
5.15 and 5.16:
𝑉𝑝 𝑉𝑝
𝜀𝑎𝑘 = ( ) ∗ 𝜀𝑝𝑘 + (1 − 𝑘
) ∗ 𝜀𝑚 (5.1)
100 100
where core with permittivity and shell radius is 𝜀1 and r1, shell with permittivity
and fraction of the total particle volume occupied by the core is 𝜀1 and (r2-r1),
𝜌 = (𝑟1 /𝑟2 )3 and α is polarizability.
The effect of decrease in 𝜀r′ with filler loading and size can not be explained,
but, it can be explained in terms of increase in 𝜀r′ with filler loading and size. The
𝜀r′ reduction effect with low nano filler loading is discussed in Chapter 4. In the
case of Eqn. 5.2, the α increase with increase nano filler size, the relation between
polarizability and 𝜀r′ shows follows:
𝜀r′ = 𝜀0 + 𝜒
𝑉𝑝 𝑉𝑝
𝜀a𝑘 = ( ) ∗ 𝜀p𝑘 + (1 − 𝑘
) ∗ 𝜀m (5.3)
100 100
Figure 5.23 E-d characteristics of each sample with different nano silica filler
loading
5.3 SUMMARY
CHAPTER 6
6.1 INTRODUCTION
∂𝜌+ 𝜌+ 𝜌− 𝑅± 𝜌+ 𝜌− 𝑅+,𝑒
+ ∇ ∙ (𝜌+ 𝜇+ 𝐸⃗⃗ ) = 𝐺𝐼 (|𝐸|) + 𝐺𝐷 (|𝐸|, 𝑇) + + (6.2)
∂t 𝑞 𝑞
∂𝜌− 𝜌+ 𝜌− 𝑅± 𝜌𝑒
+ ∇ ∙ (𝜌− 𝜇− 𝐸⃗⃗ ) = −𝐺𝐷 (|𝐸|, 𝑇) − + (6.3)
∂t 𝑞 𝜏𝑎
∂𝜌𝑒 𝜌+ 𝜌− 𝑅+,𝑒 𝜌𝑒
+ ∇ ∙ (−𝐷𝑒 ∇𝜌𝑒 𝜌𝑒 𝜇𝑒 𝐸⃗⃗ ) = −𝐺𝐼 (|𝐸|) − − (6.4)
∂t 𝑞 𝜏𝑎
∂T 1
+ 𝐯 ∙ ∇𝑇 = (𝑘 ∇2 𝑇 + 𝐸⃗⃗ ∙ 𝐽⃗) (6.5)
∂t 𝜌𝑙 𝑐𝑣 𝑇
In also (6.1) - (6.5), the parameters 𝜇+ , 𝜇− and 𝜇𝑒 are the mobilities of the positive
ions (1 × 10−9 m2 . V ∙ s [17, 65]), negative ions (1 × 10−9 m2 . V ∙ s [17, 65]) and
electrons (1 × 10−4 m2 . V ∙ s [17, 66, 67]), respectively, 𝜌+ , 𝜌−, 𝜌e are positive
ions, negative ions and electrons, respectively; 𝜀r is the relative permittivity of a
material; E is the total electric field intensity due to the applied voltage and space
charge distributions; T is the temperature; q is the electronic charge; 𝑘T thermal
conductivity (0.13 W/m∙K); 𝑐v specific heat (1.7 × 103 J/kg ∙ K); 𝐽+ , 𝐽− , 𝐽e are
current density of positive ion, negative ion and electron, respectively; 𝐺I (|𝐸|) is
the molecular ionization; 𝐺D (|𝐸|, 𝑇) is the ionic dissociation source term; R is the
recombination rate; 𝜏a is the electron attachment time constant; v is oil’s velocity.
The governing equations for solid insulation are composed of Gauss’ law, the
conduction current equation for zero space charge.
∇ ∙ 𝐽⃗ = 0 (6.7)
where 𝜀r is relative permittivity of solid insulation; 𝐸⃗⃗ and 𝐽⃗ are electric field
within a solid insulation and current density of the solid insulation that is
following equation (6.8) using Ohm’s law.
𝐽⃗ = 𝜎𝐸⃗⃗ (6.8)
⃗⃗
𝜕𝐷
I = ∫ (𝐽⃗⃗⃗𝑐 + ) ∙ 𝑑𝑎⃗ (6.9)
𝑆 𝜕𝑡
⃗⃗
where 𝐷 is applied voltage and space charge distribution by total flux density and 𝑎⃗
is the surface integration on the electrode or discharge space.
To consider the electron emission for the surface of solid insulation and for
ground electrode and back electrode, the charge generation in PB bulk is assumed
to be given by a dominant process among candidates of Poole-Frenke (P-F)
emission from PB surface to dielectric liquid, and field emission from the metal
electrode to dielectric liquid expressed in equations as follows:
2 3
𝑒 3 |𝐸⃗⃗ | 8𝜋√2𝑚ΦD 2
𝐽𝐹𝐸 = exp (− ) (6.10)
8𝜋ℎΦD 3ℎ𝑒|𝐸⃗⃗ |
𝑒ΦD
𝐽𝑇𝐻 = 𝐴𝑇 2 𝑒𝑥𝑝 (− ) (6.11)
𝑘𝑇
𝛽𝑃𝐹 √𝐸 − ∅
𝐽𝑃𝐹 = 𝐴𝐸 2 𝑒𝑥𝑝 ( ) (6.12)
𝑘𝑇
4𝜋𝑞𝑘 2 𝑚∗
𝐴=
ℎ3
where 𝐽FE is emitted current density due to the influence of the applied electric
field; 𝐽TH is emitted current density due to the influence of thermal; 𝐽PF is emitted
current density from solid insulation bulk; 𝑒 is the magnitude of electronic charge
( 1.602 × 10−9 𝐶 ); |𝐸⃗⃗ | is the local electric field; h is Planck’s constant; k is
Boltzmann’s constant; m is free electron mass; A = 1.2 × 106 A/(m2 K 2 ) is
Richardson’s constant; ΦD is effective barrier height.
We confirmed that the relation between each current density (𝐽FE , 𝐽TH , 𝐽PF ) and
electric field. The result revealed that the 𝐽FE increases with increasing electric
field linearly. Whereas 𝐽PF shows non-linear relation and high current density than
that of 𝐽FE after 70 kV/mm as shown in Fig 6.1. On the other hand, current density
by temperature variation showed no significant change (about 1E-51 A/m2 ). Thus
we considered 𝐽FE and 𝐽PF from electrode and PB surface, respectively.
Figure 6.1 Relation between each current density (𝐽FE , 𝐽PF ) and electric field
where 𝑇f and 𝑇t are virtual front time, virtual time of half voltage
Figures 6.6 and 6.7 show needle-bar electrode system and needle-bar geometry
in COMSOL Multiphysics, respectively. The distance between the needle
electrode and bar is 5 mm in simulation. The radius of curvature of needle
electrode is 10 μm. The applied voltage to the needle electrode is 25 kV standard
lightning impulse voltage. Streamer development as well as the related physics
parameters for the needle-bar electrode model was solved using equations (6.1) -
(6.11). Experiment was also performed under the same conditions with the
simulation model.
Many studies of streamers in transformer oil are conducted under a non-
uniform geometry such as needle-sphere or needle plane electrode geometries [17,
62, 118]. The non-uniform geometries generate a highly divergent electric field
distribution, thereby localizing all high field activity, such as streamer initiation,
near the needle electrode tip [17]. Application of the 100 kV impulse voltage to
the needle electrode creates a non-uniform electric field distribution with a large
field enhancement near the sharp needle tip, causing ionization to initiate
streamers.
Figure 6.8 shows result of numerical model to simulate the positive streamer
propagation at mineral oil and pressboard interface at 100 kV. The characteristics
of the electric field dynamics and the charge density dynamics is dependent
molecular ionization model correlate well. As shown in Fig. 6.9, the full
ionization model simulation results show the development of an electric field
wave, which propagates from the needle electrode’s tip towards to the bar
electrode. The initial process of analysis, high electric field region is formed
around needle electrode according to electric field distribution, and then creepage
discharge propagate along oil/pressboard interface at electric field level 5.5 × 108
V/m. The results on electric potential indicate that electric potential drops in the
electric field wave’s tail (the streamer channel). The potential drop in the electric
field wave’s tail given by these results ranges from 3 to 5 × 107 [V/m]. Potential
drops of this level are an order of magnitude greater than 2 to 4 × 106 [V/m]
range for the average drop in the tail of a streamer, which is stated as being
appropriate for the potential drop in a streamer in transformer oil [123, 124].
Figure 6.10 shows space charge density and electron density. The space charge
peak value is the same with electron density and electric field peak value as a
function of time, meaning that the space charge is concentrated, where the peak of
the electric field is formed. The free electron move to the needle electrode at a
high speed than ions, and the ion charge carriers with relatively slow speed remain
in space and then leading to ionization, dissociation, recombination and electron
attachment. In this reason, the level of electron free charge carrier density
decreases as a function of time as shown in Fig. 6.10. Figures 6.11 and 6.12 show
temperature variation at the needle electrode tip by discharge energy and
temperature distribution as a function of time step, meaning that the movement of
the free charge generated by field ionization due to the electric field contributes to
Joule heating that increases the temperature. We found that the high temperature
distribution is formed at creepage discharge streamer head and needle electrode
tip as shown in Fig. 6.12. These results are consistent with other reference works
[17, 40, 62]. Figs. 6.13 (a) and (b) show discharge from in simulation result and
experimental results. Discharge current for simulation is current derived from the
integration of current density during the creepage discharge propagation. The
result revealed that the peak value of simulation calculated discharge current is
around 0.68 A, which is greater than the peak of experimental measured discharge
current about 0.43 A.
[17, 127]. High permittivity has been shown to dramatically affect streamer
propagation and breakdown time, such that streamers in the oil are attracted
towards the pressboard surface [17, 121, 128]. The result of discharge velocity is
accords with reference papers [46, 128].
Figure 6.15 Creepage discharge propagation velocity and BDV with different
𝜀r′ [127]
6.5 SUMMARY
be in good agreement with the experimental results in terms of BD time and BDV.
The BD time of simulated creepage discharge shows similar order with
experimental results. Further work is needed on physical parameters such as
charge generation and conduction mechanism of each dielectric as well as PB
parameters such as surface roughness.
CHAPTER 7
7.1 CONCLUSIONS
The work presented in this thesis has also made a significant contribution to the
development of a computational simulation model of surface discharge at the
oil/pressboard interface. A 2-D axial symmetry model has been developed using
COMSOL Multiphysics, an FEA software package. In general, the electric field
dependent molecular ionization mechanism plays an important role in the
discharge inception and propagation at the oil-pressboard interface. On the other
hand, the composite insulation model is developed by considering Poole-Frenkel
model for solid insulation. The numerical results were found to be in good
agreement with the experimental results in terms of BD time and BDV. The BD
time of simulated creepage discharge shows similar order with experimental
results.
and to verify the nanoparticle effect under AC voltage or/and impulse polarity
should be performed.
APPENDIX A
List of Publications
The following papers have been peer reviewed and presented at International
Conferences:
(No. 6 and 7 are scheduled to present a paper at International Conference on
Dielectric Liquids at Manchester Univ. in 2017)
8. Choi Jin-Hyun, Kim Su-Hun, Jang Kyunghoon, Hikita Masayuki, Lee Se-Hee,
“Finite Element Analysis for Surface Discharge Due to Interfacial Polarization at
the Oil-Nanocomposite Interface”, 21st International Conference on the
Computation of Electromagnetic Fields, June 18-22, 2017
A.4 Patent
【Patent certificate】
【Document name】
【Number】10778
【Recipient】Commissioner of the patent and trademark office
【International patent classification】C01B 33/145
【Inventor】
【Address】千葉県袖ヶ浦市北袖11番1 日産化学工業株式会社材料科学
研究所内
【Name】末村尚彦
【Inventor】
【Address】千葉県袖ヶ浦市北袖11番1 日産化学工業株式会社材料科学
研究所内
【Name】石田智久
【Inventor】
【Address】福岡県北九州市戸畑区仙水町1番1号国立大学法人九州工業
大学内
【Name】小迫雅裕
【Inventor】
【Address】福岡県北九州市戸畑区仙水町1番1号国立大学法人九州工業
大学内
【Name】匹田政幸
【Inventor】
【Address】福岡県北九州市戸畑区仙水町1番1号国立大学法人九州工業
大学内
【Name】チャン ギョンフン
【Inventor】
【Address】福岡県北九州市戸畑区仙水町1番1号国立大学法人九州工業
大学内
【Name】赤星卓勇
【An applicant for a patent】
【Identification number】000003986
【The name or title】日産化学工業株式会社
【An applicant for a patent】
【Identification number】504174135
【The name or title】国立大学法人九州工業大学
【Agent】
【Identification number】100101236
【Patent attorney】
【The name or title】栗原浩之
【Erected agent】
【Identification number】100166914
【Patent attorney】
【The name or title】山▲崎▼ 雄一郎
【Patent attorney fee】
【予納台帳番号】042309
【Amount of payment】14,000円
【List of submission】
【物件名】明細書1
【物件名】特許請求の範囲1
【物件名】要約書1
【物件名】図面 1
【Comprehensive mandate number】1212778
【Document name】明細書
【Title of invention】沿面放電の発生を抑制する方法
【Technical field】
【0001】
本発明は、高電圧(電力)機器の絶縁材料の沿面放電発生を抑制する技術
に関する。
【背景技術】
【0002】
高電圧(電力)機器において、固体絶縁材料の表面は高電圧により沿面放
電が起きやすい箇所である。ここで表面とは、液体/固体、気体/固体、
真空/固体などの異質の界面を意味する。この場合、沿面放電は固体中で
はなく、液体、気体、真空中のいずれかで発
生する。
【0003】
従来、樹脂表面の沿面放電を抑制する技術としては、沿面放電が生じる可
能性のある固
体絶縁材料の誘電率制御による電界緩和(この場合、液体・気体・真空の
誘電率に合わせるべく、固体の低誘電率化を行うこと)、誘電率の空間的
な傾斜分布による電界緩和、導電率の非線形性による電界緩和、表面の凹
凸による沿面距離の増加、などが報告されている。つまり、沿面放電を防
止する対策としては、電界緩和あるいは物理的な沿面距離を取る方策しか
実施されていない。
【先行技術文献】
【特許文献】
【0004】
【特許文献1】特開2012-110206号公報
【特許文献2】特開2016-031845号公報
【発明の概要】
【発明が解決しようとする課題】
【0005】
本発明は、固体絶縁材料である樹脂硬化体自体の電界緩和(即ち樹脂の低
誘電率化)に頼ることなく、樹脂硬化体の表面の沿面放電の発生を抑制す
る方法を確立することを課題
とする。
【課題を解決するための手段】
【0006】
本発明は、固体絶縁材料である樹脂中にナノサイズの無機微粒子を分散さ
せたナノコンポジット絶縁材料を用いることで、樹脂表面の沿面放電の発
生を抑制するという知見に基づいて完成されたものである。
【0007】
上記目的を達成する本発明は、ナノサイズの無機微粒子を樹脂中に分散さ
せて樹脂硬化体の表面の沿面放電の発生を抑制することを特徴とする、沿
面放電の発生を抑制する方法
にある。
【0008】
ここで、無機微粒子としては、シリカ、アルミナ、チタニア、ジルコニア、
酸化亜鉛、酸化錫、酸化アンチモン、酸化鉄、酸化マグネシウム、又はこ
れらを主成分とする複合酸化物微粒子を用いることができる。
【0009】
ナノサイズの粒子とは、一般的には、ナノメートル(nm)オーダーの大
きさを持つ粒子のことで、一般的には1~数百nmの大きさの粒子をいう
が、本発明では、平均粒子径が1~400nmのものとする。なお、平均
粒子径は、後述するとおり、比表面積による
ものとする。
【0010】
本発明で用いる無機微粒子は、その平均粒子径が5~200nmであるの
が好ましい。樹脂としては、エポキシ樹脂などの一般的な熱硬化性樹脂を
用いる。ナノコンポジットにおける無機微粒子の添加率は0.1~50質
量%である。
【発明の効果】
【0011】
本発明を用いることで、固体絶縁材料の電界緩和や物理的な沿面距離増加
を施さずとも、樹脂硬化体の固体表面の沿面放電発生電圧を向上すること
ができ、GIS(ガス絶縁開閉装置)の 絶縁スペーサや油入り変圧器の
プレスボード用コーティング樹脂等へ好適に利用さ
れうる。
【図面の簡単な説明】
【0012】
【図1】沿面放電の測定系の概略構成を示す図である。
【発明を実施するための形態】
【0013】
本発明に用いられる絶縁樹脂としては、例えば、エポキシ樹脂、ポリイミ
ド樹脂、ポリアミドイミド樹脂、シリコーン等の熱硬化性樹脂が挙げられ
る。また、ポリエチレン、ポリプロピレン等の熱可塑性樹脂も挙げられる。
【0014】
本発明に用いられるエポキシ樹脂としては特に限定されるものではないが、
ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、脂
環式エポキシ樹脂等が挙げられる。通常、これらエポキシ樹脂と硬化剤等
を組み合わせて配合された後、注型・熱硬化して所望の形状に成形される。
【0015】
本発明に用いるエポキシ樹脂の硬化剤としては、フェノール樹脂、アミン
類、ポリアミド樹脂、イミダゾール類、ポリメルカプタン、酸無水物等が
挙げられる。
【0016】
フェノール樹脂としては、例えばフェノールノボラック樹脂、クレゾール
ノボラック樹脂等が挙げられる。
【0017】
アミン類としては、例えばピペリジン、N,N-ジメチルピペラジン、ト
リエチレンジアミン、2,4,6-トリス(ジメチルアミノメチル)フェ
ノール、ベンジルジメチルアミン、2-(ジメチルアミノメチル)フェノ
ール、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレン
ペンタミン、ジエチルアミノプロピルアミン、N-アミノエチルピペラジ
ン、ジ(1-メチル-2-アミノシクロヘキシル)メタン、メンセンジア
ミン、イソフオロンジアミン、ジアミノジシクロヘキシルメタン、1,3
-ジアミノメチルシクロヘキサン、キシレンジアミン、メタフェニレンジ
アミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等が挙
げられる。これらの中で液状であるジエチレントリアミン、トリエチレン
テトラミン、テトラエチレンペンタミン、ジエチルアミノプロピルアミン、
N-アミノエチルピペラジン、ジ(1-メチル-2-アミノシクロヘキシ
ル)メタン、メンセンジアミン、イソフオロンジアミン、ジアミノジシク
ロヘキシルメタン等は好ましく用いることができる。
【0018】
ポリアミド樹脂としては、ダイマー酸とポリアミンの縮合により生成する
もので、分子中に一級アミンと二級アミンを有するポリアミドアミンであ
る。
【0019】
イミダゾール類としては、2-メチルイミダゾール、2-エチル-4-メ
チルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾリウムト
リメリテート、エポキシイミダゾールアダクト等が挙げられる。
【0020】
ポリメルカプタンは、例えばポリプロピレングリコール鎖の末端にメルカ
プタン基が存在するものや、ポリエチレングリコール鎖の末端にメルカプ
タン基が存在するものであり、液状のものが好ましい。
【0021】
本発明に用いる酸無水物としては一分子中に複数のカルボキシル基を有す
る化合物の無水物が好ましい。これらの酸無水物としては、無水フタル酸、
無水トリメリット酸、無水ピロメリット酸、無水ベンゾフェノンテトラカ
ルボン酸、エチレングリコールビストリメリテート、グリセロールトリス
トリメリテート、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテ
トラヒドロ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸、メ
チルエンドメチレンテトラヒドロ無水フタル酸、メチルブテニルテトラヒ
ドロ無水フタル酸、ドデセニル無水コハク酸、ヘキサヒドロ無水フタル酸、
メチルヘキサヒドロ無水フタル酸、無水コハク酸、メチルシクロヘキセン
ジカルボン酸無水物、クロレンド酸無水物等
が挙げられる。
【0022】
これらの中でも常温、常圧で液状であるメチルテトラヒドロ無水フタル酸、
メチルエンドメチレンテトラヒドロ無水フタル酸、メチルブテニルテトラ
ヒドロ無水フタル酸、ドデセニル無水コハク酸、メチルヘキサヒドロ無水
フタル酸が好ましい。これら液状の酸無水物は粘度が25℃での測定で1
0mPas~1000mPas程度である。
【0023】
また、上記硬化物を得る際、適宜、硬化促進剤が併用されても良い。硬化
促進剤としてはトリフェニルホスフィンやトリブチルホスフィンなどの有
機リン化合物、エチルトリフェニルホスフォニウムブロマイド、メチルト
リフェニルホスホニウムリン酸ジエチル等の第4級ホスフォニウム塩、1,
8-ジアザビシクロ(5,4,0)ウンデカン-7-エン、1,8-ジア
ザビシクロ(5,4,0)ウンデカン-7-エンとオクチル酸の塩、オク
チル酸亜鉛、テトラブチルアンモニウムブロミド等の第4級アンモニウム
塩、ジメチルベンジルアミン等の3級アミン等が挙げられる。これらの硬
化促進剤は、硬化剤1質量部に
対して、0.001~0.1質量部の割合で含有することができる。
【0024】
本発明に用いられるナノサイズの無機微粒子としては、絶縁性や分散性の
観点から、金属酸化物微粒子が好ましい。金属酸化物微粒子の好ましい例
としては、シリカ、アルミナ、チタニア、ジルコニア、酸化亜鉛、酸化錫、
酸化アンチモン、酸化鉄、酸化マグネシウム又はこれらを主成分とする複
合酸化物微粒子が挙げられる。このうち、シリカは誘電率が4程度と低く、
熱膨張率も低いため、本発明に用いられる無機微粒子として好適に用い
られる。
【0025】
本発明に用いられるシリカは、粒子形態のシリカであり、平均粒子径が2
00nm以下、例えば5nm~200nm、好ましくは10nm~100
nmであり、より樹脂の沿面放電を抑制する観点から、好ましくは20n
m~80nmである。粒子径が200nmよりも大きい、または5nmよ
りも小さいと、沿面放電抑制効果が小さくなる。
【0026】
本発明に用いられるシリカ粒子の平均粒子径とは、窒素吸着法により測定
された比表面積値から算出される平均粒子径値である。
【0027】
特に本発明では、上記平均粒子径の値を有するコロイダルシリカを好適に
使用でき、該コロイダルシリカとしては、シリカゾルを用いることができ
る。シリカゾルとしては、ケイ酸ナトリウム水溶液を原料として公知の方
法により製造される水性シリカゾル及び該水性シリカゾルの分散媒である
水を有機溶媒に置換して得られるオルガノシリカゾルを原料として使用す
る事が出来る。また、メチルシリケートやエチルシリケート等のアルコキ
シシランを、アルコール等の有機溶媒中で触媒(例えば、アンモニア、有
機アミン化合物、水酸化ナトリウム等のアルカリ触媒)の存在下において
加水分解し、縮合して得られるシリカゾル、又はそのシリカゾルを他の有
機溶媒に溶媒置換したオルガノシリカゾルも原料として用いることができ
る。
【0028】
上述のオルガノシリカゾルにおける有機溶媒の例としては、アルコール類、
エーテル類、ケトン類、エステル類、アミド類、炭化水素類、ニトリル類
等が挙げられる。
【0029】
アルコール類としては、メタノール、エタノール、1-プロパノール、2
-プロパノール、1-ブタノール、イソブチルアルコール、2-ブタノー
ル、エチレングリコール、グリセリン、プリピレングリコール、トリエチ
レングリコール、ポリエチレングリコール、ベンジルアルコール、1,5
-ペンタンジオール、ジアセトンアルコール等が挙げられる
。
【0030】
エーテル類としては、ジエチルエーテル、ジブチルエーテル、テトラヒド
ロフラン、ジオキサン、エチレングリコールモノメチルエーテル、エチレ
ングリコールモノプロピルエーテル、プロピレングリコールモノメチルエ
ーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコー
ルモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエ
チレングリコールモノブチルエーテル等が挙げられる。
【0031】
ケトン類としては、アセトン、メチルエチルケトン、2-ペンタノン、3
-ペンタノン、メチルイソブチルケトン、2-ヘプタノン、シクロヘキサ
ノン等が挙げられる。
【0032】
エステル類としては、ギ酸エチル、酢酸メチル、酢酸エチル、酢酸プロピ
ル、酢酸ブチル、エチレングリコールモノエチルエーテルアセタート、エ
チレングリコールモノブチルエーテルアセタート、プロピレングリコール
モノメチルエーテルアセタート等が挙げられ
る。
【0033】
アミド類としては、アセトアミド、N,N-ジメチルホルムアミド、N,
N-ジメチルアセトアミド、N-メチルピロリドン等が挙げられる。
【0034】
炭化水素類としては、n-ヘキサン、シクロヘキサン、ベンゼン、トルエ
ン、キシレン、ソルベントナフサ、スチレン等があげられ、更にハロゲン
化炭化水素類としてはジクロロメタン、トリクロロエチレン等が挙げられ
る。
【0035】
ニトリル類としては、アセトニトリル、グルタロニトリル、メトキシアセ
トニトリル、プロピオニトリル、ベンゾニトリル等が挙げられる。
【0036】
上記オルガノシリカゾルの市販品の例としては、例えば商品名MA-ST
-S(メタノール分散シリカゾル、日産化学工業(株)製)、商品名MT
-ST(メタノール分散シリカゾル、日産化学工業(株)製)、商品名M
A-ST-UP(メタノール分散シリカゾル、日産化学工業(株)製)、
商品名MA-ST-M(メタノール分散シリカゾル、日産化学工業(株)
製)、商品名MA-ST-L(メタノール分散シリカゾル、日産化学工業
(株)製)、商品名IPA-ST-S(イソプロパノール分散シリカゾル、
日産化学工業(株)製)、商品名IPA-ST(イソプロパノール分散シ
リカゾル、日産化学工業(株)製)、商品名IPA-ST-UP(イソプ
ロパノール分散シリカゾル、日産化学工業(株)製)、商品名IPA-S
T-L(イソプロパノール分散シリカゾル、日産化学工業(株)製)、商
品名IPA-ST-ZL(イソプロパノール分散シリカゾル、日産化学工
業(株)製)、商品名NPC-ST-30(n-プロピルセロソルブ分散
シリカゾル、日産化学工業(株)製)、商品名PGM-ST(1-メトキ
シ-2-プロパノール分散シリカゾル、日産化学工業(株)製)、商品名
DMAC-ST(ジメチルアセトアミド分散シリカゾル、日産化学工業
(株)製)、商品名XBA-ST(キシレン・n-ブタノール混合溶媒分
散シリカゾル、日産化学工業(株)製)、商品名EAC-ST(酢酸エチ
ル分散シリカゾル、日産化学工業(株)製)、商品名PMA-ST(プロ
ピレングリコールモノメチルエーテルアセテート分散シリカゾル、日産化
学工業(株)製)、商品名MEK-ST(メチルエチルケトン分散シリカ
ゾル、日産化学工業(株)製)、商品名MEK-ST-UP(メチルエチ
ルケトン分散シリカゾル、日産化学工業(株)製)、商品名MEK-ST
-L(メチルエチルケトン分散シリカゾル、日産化学工業(株)製)及び
商品名MIBK-ST(メチルイソブチルケトン分散シリカゾル、日産化
学工業(株)製)等を挙げることができるが、これらに限定されない。
【0037】
本発明に使用されるシリカ粒子の表面は疎水化処理されていても良い。
疎水化処理剤としては、シラザン、シロキサン又はアルコキシシラン及び
その部分加水分
解物若しくはその重合した2量体~5量体のオリゴマーが挙げられる。
【0038】
シラザンとしては、例えばヘキサメチルジシラザン、及びヘキサエチルジ
シラザンが挙げられる。
【0039】
シロキサンとしては、例えばヘキサメチルジシロキサン、1,3-ジブチ
ルテトラメチルジシロキサン、1,3-ジフェニルテトラメチルジシロキ
サン、1,3-ジビニルテトラメチルジシロキサン、ヘキサエチルジシロ
キサン及び3-グリシドキシプロピルペンタメチルジシロキサンが挙げら
れる。
【0040】
アルコキシシランとしては、例えばトリメチルメトキシシラン、トリメチ
ルエトキシシラン、トリメチルプロポキシシラン、フェニルジメチルメト
キシシラン、クロロプロピルジメチルメトキシシラン、ジメチルジメトキ
シシラン、メチルトリメトキシシラン、テトラメトキシシラン、テトラエ
トキシシラン、テトラプロポキシシラン、テトラブトキシシラン、エチル
トリメトキシシラン、ジメチルジエトキシシラン、プロピルトリエトキシ
シラン、n-ブチルトリメトキシシラン、n-ヘキシルトリメトキシシラ
ン、n-オクチルトリエトキシシラン、n-オクチルメチルジエトキシシ
ラン、n-オクタデシルトリメトキシシラン、フェニルトリメトキシシラ
ン、フェニルメチルジメトキシシラン、フェネチルトリメトキシシラン、
ドデシルトリメトキシシラン、n-オクタデシルトリエトキシシラン、フ
ェニルトリメトキシシラン、ジフェニルジメトキシシラン、ビニルトリメ
トキシシラン、ビニルトリエトキシシラン、ビニルトリス(βメトキシエ
トキシ)シラン、γ-メタアクリルオキシプロピルトリメトキシシラン、
γ-アクリルオキシプロピルトリメトキシシラン、γ-(メタアクリルオ
キシプロピル)メチルジメトキシシラン、γ-メタアクリルオキシプロピ
ルメチルジエトキシシラン、γ-メタアクリルオキシプロピルトリエトキ
シシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシ
シラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキ
シプロピルメチルジエトキシシラン、γ-グリシドキシプロピルトリエト
キシシラン、N-β(アミノエチル)γ-(アミノプロピル)メチルジメ
トキシシラン、N-β(アミノエチル)γ-(アミノプロピル)トリメト
キシシラン、N-β(アミノエチル)γ-(アミノプロピル)トリエトキ
シシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピル
トリエトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシ
ラン、γ-メルカプトプロピルトリメトキシシラン、3-イソシアネート
プロピルトリエトキシシラン、トリフルオロプ
ロピルトリメトキシシラン、ヘプタデカトリフルオロプロピルトリメトキ
シシラン、n-デシルトリメトキシシラン、ジメトキシジエトキシシラン、
ビス(トリエトキシシリル)エタン及びヘキサエトキシジシロキサンが挙
げられる。
【0041】
本発明における樹脂中のナノシリカの配合量としては、例えば0.1~5
0質量%であり、好ましくは0.2~30質量%であり、より樹脂の沿面放電
を抑制する観点から、好ましくは0.5~20質量%、より好ましくは1~15
質量%である。
【0042】
ナノシリカの配合量が50質量%よりも多いと樹脂硬化物の誘電率が上昇
し、放電抑制効果が小さくなる。また、ナノシリカの配合量が0.1質
量%よりも少ないとシリカを添加した効果が小さくなり、樹脂の放電抑制
効果が得られない。
【0043】
上述のオルガノシリカゾルを、例えばエポキシ樹脂と混合して脱溶媒する
ことで、ナノシリカが分散したエポキシ樹脂を得ることが出来る。この樹
脂に適宜、硬化剤を添加して、注型・加熱等によって硬化反応を行い、所
望の絶縁樹脂成型物が得られる。
【実施例】
【0044】
(材料の準備)
ビスフェノールAジグリシジルエーテルJER828(三菱化学(株)製、
エポキシ価185g/eq.)に、平均粒子径12~500nmのシリカ
粒子を分散させたエポキシモノマー分散シリカゾルをシリカ濃度30.5
質量%となるよう調整した。平均粒子径500nmのシリカ粒子には、ア
ドマファインSO-C2(アドマテックス(株)製)を用いた。平均粒子
径は、シリカの300℃乾燥粉末の比表面積を比表面積測定装置モノソー
ブ(登録商標)MS-16(ユアサアイオニクス(株)製)を用いて測定
し、平均粒子径(nm)=2720/比表面積(m2/g)の換算式により
算出した。
【0045】
【表1】
【0046】
実施例1~実施例10表1で準備したエポキシモノマー分散シリカゾルと、
酸無水物(リカシッドMH-700、新日本理化(株)製)、反応促進剤
(ジメチルベンジルアミン、東京化成)を表2に記載の配合比で混合しエ
ポキシ樹脂硬化用組成物を得た。得られたエポキシ樹脂硬化用組成物を注
型板(離型フィルムPL#400(フタムラ化学(株)製)で被覆された
ガラス板3mm厚)に流し込み、70℃で2時間、90℃で2時間、15
0℃で8時間の硬化条件で加熱処理を行い、エポキシ樹脂硬化体を得た。
【0047】
【表2】
【0048】
(沿面放電の測定方法)
沿面放電の測定系の概略構成を図1に示す。この装置は、各印加電圧時の
時間波形及び発光像を取得し、沿面放電発生確率を算出するものである。
【0049】
試料1としては、実施例1~10で作製したエポキシ樹脂硬化体を用いた。
試料1の厚さは、3mmである。
【0050】
図1に示すように、試料1の表面に針電極2と、平板電極3とをギャップ
長g=50mmで配置した。これらの試料1及び針電極2と平板電極3と
の電極系は、試験容器4内に配置した。試験容器4内に鉱油5を充填し、
試料1及び電極系を鉱油5内に配置した。
【0051】
針電極2の直径は1mmで、先端曲率半径は10μmであり、試料1の表
面に対してθ=30°傾けて配置した。針電極2をインパルス電圧発生装
置6に接続し、平板電極3は50Ωの抵抗を介して接地した。針電極2に、
分圧器7を介して、正極性標準雷インパル電圧(1.2μs/50μs)
を、35kV~75kVまで、5kVステップで、印加間隔1分間で印加
し、 沿面放電の発生をイメージインテンシファイア付きのCCDカメラ
8を用いて確認した。試料1の数は3枚、試験回数は各電圧で5回実施し、
計15回の実験で沿面放電発生確率を算出した。
【0052】
また、試料1の比誘電率は誘電率計測器を用いて評価した。
【0053】
試料条件、試料の比誘電率の測定結果、および沿面放電試験結果を表3に
示した。表3からシリカ微粒子の充填率が増加すると比誘電率が増加する
傾向がわかる。一方で、シリカ微粒子の粒径が500nmの試料以外は放
電発生確率が低下し、放電発生電圧が増加することがわかる。また、放電
発生確率が100%に到達する電圧も、粒径が500nmの試料以外は5
~15kV上昇した。つまり、本提案の手法を用いることで、樹脂の比誘
電率はほぼ不変あるいは増加するにも関わらず、樹脂表面の沿面放電の発
生を抑制できるこ
とになる。
【0054】
【表3】
平均粒子径130nmのシリカ粒子を分散させたエポキシモノマー分散シリカゾルを
シリカ濃度30.5質量%となるよう調整した。
【表4】
粒子径 エポキシ樹脂 SiO2(%)
モノマーゾル6 130nm ビスフェノールA型 30.5
実施例1~10と同様の条件で、下記組成にて実施例11及び比較例3の硬化物を作成
した。
【表5】
モノマーゾル(g) エポキシ樹脂(g) 酸無水物(g) 促進剤(g) SiO2(%)
実施例11 モノマーゾル3 0.81 26.3 21.7 0.3 0.5
比較例3 モノマーゾル6 5.0 23.5 21.7 0.3 3.0
上記と同様の装置を用い、沿面放電の発生を光電子増倍管9を用いて確認した。光電
子増倍管9は、信号用9aと、ノイズ用9bとを用いた。
【表6】
シリカ粒子径 シリカ添加率 比誘電率 35kVにおける 放電発生確率が
[nm] [wt%] (@100 kHz) 放電発生確率[%] 100%の電圧[kV]
実施例1 12 3 3.46 31 50
実施例2 22 3 3.50 20 50
実施例9 80 3 3.53 31 45
試料条件、試料の比誘電率の測定結果、および沿面放電試験結果を表4に示した。シリ
カ微粒子の粒径が130nm以上の試料以外は放電発生確率が低下し、放電発生電圧が
増加することがわかる。また、放電発生確率が100%に到達する電圧も、粒径が50
0nm以上の試料以外は5~10kV上昇した。つまり、本提案の手法を用いることで、
樹脂の比誘電率はほぼ不変あるいは増加するにも関わらず、樹脂表面の沿面放電の発生
を抑制できることになる。
【産業上の利用可能性】
【0055】
本発明によって、本発明を用いることで、固体絶縁材料の電界緩和や物理
的な沿面距離増加を施さずとも、固体表面の沿面放電発生電圧を向上する
ことができ、GIS(ガス絶縁開閉装置)の 絶縁スペーサや油入り変圧器のプ
レスボード用コーティング樹脂等へ好適に利用されうる。
【符号の説明】
【0056】
1 試料
2 針電極
3 平板電極
4 試験容器
5 鉱油
6 インパルス電圧発生装置
7 分圧器
8 カメラ
9 光電子増倍管
9a 信号用
9b ノイズ用
【書類名】特許請求の範囲
【請求項1】
ナノサイズの無機微粒子を樹脂中に分散させて樹脂硬化体の表面の沿面放
電の発生を抑制することを特徴とする、沿面放電の発生を抑制する方法
【請求項2】
前記無機微粒子がシリカであることを特徴とする、請求項1に記載の方法。
【請求項3】
前記樹脂が熱硬化性樹脂である請求項1又は2に記載の方法。
【請求項4】
前記無機微粒子の添加率が0.1~50質量%である請求項1~3のいず
れか一項に記載の方法
【請求項5】
前記無機微粒子の平均粒子径が5~200nmである請求項1~4のいず
れか一項に記載の方法。
【書類名】要約書
【要約】
【課題】固体絶縁材料である樹脂自体の電界緩和(即ち樹脂の低誘電率化)
に頼ることなく、樹脂表面の沿面放電の発生を抑制する手法を確立するこ
と。
【解決手段】ナノサイズの無機微粒子を樹脂中に分散させて樹脂硬化体の
表面の沿面放
電の発生を抑制することを特徴とする、樹脂表面の沿面放電の発生を抑制
する方法による。
【選択図】なし
【書類名】図面
【図1】
APPENDIX B
APPENDIX C
COMSOL Multiphysics
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