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Liquids dielectrics

Liquids can be described as highly compressed gases in which the molecules are very closely arranged.
They are classified in between the two states of matter, that is gaseous and solid insulating materials.
The additional functions of oils:
impregnation of insulation in thin layers of paper or other materials Sebastian Ziani de Ferranti, Deptford
cooling action by convection (transformers, oil fiiled cables)
filling of the voids
arc extinction in oil circuit breakers
high capacitance (power capacitors).
Adamczewski I., Jonizacja i przewodnictwo ciekych dielektrykw. PWN Warszawa 1965, 70 citations
Gzowski O., Prebreakdown luminiscence pulses in liquid dielectrics. Nature, Vol. 209, No. 5058, 1966, pp. 185-187
-----------------------------------------------------------------
Skowroski J.I., Beroual M., Fleszyski J.,
Angerer L., Grawley G., Investigation of the electrical breakdown of transformer oil in Skowronskis cup-sphere
spark gap. Proc. IEE 113 (1966) No. 6
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Felici N.
Classification of liquid dielectrics
Organic dielectrics are basically chemical compounds containg carbon, the most important for power
equipment are mineral oils.
There is a large number of synthetic organic liquids. The chlorodiphenyles, although possesing some some
special properties, are not widely used because of being unfriendly to human beings and very costly.
Halogenfree synthetic oils like polyisobutylene or silicone oils offer better dielectric and thermal properties
than mineral oils but are more expensive.
Mineral oils
Molecular structure and proportion of basic constituent of mineral oils
Mineral oils are the mixtures of different hydrocarbons obtained by fractional distillation of natural petroleum.
These oils mainly consist of saturated hydrocarbons of paraffinic or naphthenic structures (C
n
H
2n
) and
unsaturated aromatic hydrocarbons (C
n
H
2n-6
).
Naphthenic oils are more in use as dielectrics because they do not have the wax type constituent which reduces
their fluidity at low temperatures.
Vegetable oils
Some vegitable oils have also found their application in electrical equipment. A large number of vegitable
oils are available for example castor, (rycyna) linseed (olej lniany), rapeseed (rzepak), soya, groundnut, corn,
olive, sunflower, mustard, clove, almond, mangooseed, cottonseed, palm oils etc.
Castor oil C
18
H
32
OHCOOH has a relative permitivity between 4,2 and 4,5. It has therefore found application
as impregnating agent in power capacitors. Turpentile oil can dissolve lac, and thus serves as a solvent.
Rape-seed oil
Rape is the most popular oil plant in Poland. The rape-seed oil is added to the petrol.
The 50 Hz breakdown voltage is comparable to normal mineral oil, e.g. more than 50 kV / 2,5 mm. New rape-
seed oil has c
r
of 3,18 and tan o of 0,015. These data demonstrate that rape-seed oil is usable as an insulating
liquid. The dynamic viscosity of rape-seed oil is about 70 mm
2
/s at 40C, that means it is much higher than
of mineral oil, and at temperatures under - 5C rape-seed oil even becomes solid. So, additional substances
must be used to regulate the viscosity in appropriate ranges.
Huge difficulties emerge from the aging of rape-seed oil. If exposed to humidity and air rape-seed oil is not
stabil in the long term. Only if it is completely dried and used in a hermetic casing, it can be an alternative to
mineral insulation oils.

Chlorinated diphenyles
Chlorinated diphenyles have very good electrical properties for usage in power capacitors. These are
produced by replacing two to five hydrogen atoms of each molecule by chlorine atoms.
C
12
H
7
Cl
3
trichlorodiphenyle
C
12
H
5
Cl
5
pentachlorodiphenyle
Because of electronegative effect of chlorine atoms, the chlorodiphenyles have comparatively higher c
r
of the
order of 5,6 at 20C. The relative permitivity of paper is of the order of 6,8, therefore the impregnation of paper
with these oils gives rise to more uniform distribution of field compared to natural mineral oils which have
relatively lower permitivity of the order of 2 to 2,3.
However, the chlorodiphenyles cause serious problems as they do have a number of undesirable properties. They
appear to dissolve organic matter to minor extend and cause damage to such materials. They also get decomposed
by electric arcs and above all, are injurious to the health.
PolyChlorinated Biphenyls (PCBs) are mixtures of synthetic organic chemicals
that were produced in the U.S. between the 1920s and the 1970s. They were used
extensively in electrical equipment, especially transformers and capacitors, because
of their electrical insulating properties and non-flammability. Responding to
environmental concerns raised about PCBs, production was stopped in 1979.
Non-PCB Transformer
Halogenfree synthetic oils
Polyisobutane and dodecylbutane are used as high viscosity impregnating agent for mass impregnated power
cables and condensers.
The most important halogenfree synthetic insulating liquids are pure polydimethylsiloxane as shown below,
Although incorect, these are commonly known as silicone oils. They are very stable liquids and do not show
signs of ageing under the working conditions of electrical equipment. They are stable thermally upto 300 C.
Since silicone oils have a very low surface tension, these are water resistive, that is, wqater collects as separate
drops instead of getting mixed with the oil silicone oils have a property to reject water.
An extensive use of silicone oils is restricted only because of their high cost.
Inorganic liquids
Extremely puryfied water has a relative permitivity of the order 80 and posses comparatively a high
conductivity. Ethylene glycol is added to water to allow low temperature operation without freezing.

High Temperature Superconductivity, 1986
Transformers, generators, motors, cables, magnets, fault current limiters (FCL)
April 2008, first HTS cable 138 kV, 570 MW, cooled by liquid nitrogen, 600 m long, New York, Long
Island
HTS wires conduct 150 times the electricity of similar sized copper wires.
The completed HTS link at the Holbrook
substation end with three phases emerging
from the ground to connect to the HV
terminations (the vertical parts)
American Superconductor Corporation
AMSC
The cut model of the 500-m HTS power cable manufactured in Japan in 2005. The electrical insulation layer
consist of polypropylene (PP) laminated papers with a nominal thickness of 125 m wound on a high
voltage conductor with 1/3 wrapping, immersed into liquid nitrogen (LN2)
Dr. Bartek Glowacki
Reader in Applied Superconductivity
MSc University of Wroclaw
PhD Polish Academy of Science
www.msm.cam.ac.uk/ascg
From http://www.sayedsaad.com/index.htm
Property
Transformer
Oil
Cable
Oil
Capacitor
Oil
Askarels
Silicone
Oils
Breakdown strength (20C,
2.5mm sphere gap)
150 300 200 200-250 300-400
Relative Permittivity (50Hz) 2.2-2.3
2.3-
2.6
2.1 4.8 2-73
Loss Tangent (50Hz) .001 .002 0.25E-3 0.60E-3 .001
Loss Tangent (1 kHz) .0005 .0001 0.10E-3 0.50E-3 0.1E-3
Resistivity (Ohm -cm) 1e12-1e13
1e12-
1e13
1e13-1e14 2e12 3e14
Specific Gravity at 20 C 0.89 0.93 0.88-0.89 1.4 1.0-1.1
Viscosity at 20 C (cStokes) 30 30 30 100-150 10-1000
Refractive Index 1.4820 1.4700 1.4740 1.6000
1.5000-
1.6000
Saponification 0.01 0.01 0.01 <0.01 <0.01
Thermal Expansion 7e-4/deg 7e-4 7e-4 7e-4 5e-4
Max permissible Water
content (ppm)
50 50 50
<30
negligble
<30
negligible

kV/cm
AC power frequency voltage is applied to a 2,5 mm gap between two identical elecrodes. These electrodes are
placed in a container and filled with about 300 cc of the sample of oil. The measurement is conducted by increasing
the voltage at a rate of 2 3 kV/s upto breakdown. Electrodes used accorging to VDE-0370 have the Schwaiger
factor of uniformity q = 0,97.
IEC-156
Electric conduction in insulating liquids
In not highly purified liquids, when subjected to fields upto a few kV/cm the conduction is primary ionic. The
DC voltage current characteristic is similar to that observed in gases.
Conduction current in oil and liquid nitrogen for negative needle
plane electrode gap of 4 mm with increasing voltage. Oil at 20C
and LN
2
at 77 K.
According to Vant Hoffsch law, the conductivity k within a certain range of temperature follows the relaion:
) / exp( kT F
o
=k k
k
o
- material constant, F activation energy (kcal/mole)
However, Vant Hoffsch law is valid only in the region where the conduction current follows the ohmic behaviour
(region I). There are two temperature regions. In low temperature region, that is, room temperature and lower, the
conductivity is governed mainly by ionic carrier mobility. However, in the high teperature region, it is
characterized by thermal dissociation of impurities as well as carrier mobility.
A schematic of DC conductivity of an insulating oil with
respect to time of applied voltage
A E
A E
d
A U
R
U
i
dc
ins ins dc
dc
=

= = k

The DC conductivity, which is very high initially (region A), is determined by the orientation of dipoles.
In region B, the conductivity is determined by the movement of free charge carriers under the influence of
applied electric field. The magnitude of conductivity in this region also represents the AC power frequency
conductivity k
ac
.
The region C represents the development of space charge in front of the electrodes.
The steady ion current due to dissociation is depicted by region D.
Polarization
c = c
o
c
r
c
o
= 8,85 10
-12
F/m
, , ,
_
r r r
jc c c =
For the mathematical analysis taking into account the
polarization process in the dielectrics, it was neccessary
to introduce the complex relative permitivity:
The effect of polarization is analytically described by
the relative permitivity c
r
.
In vacuum the electric flux density is given by,

= E D
o
o
c
and in an insulating material

= E D
r o
ins
c c
Dielectric power losses in insulating materials
) (
) (
Re
total c
total R
i
i
Power active
Power Active
tg = = o
o e tg U C U i P
total R ac
= =
2
) (
Variation of measured values of tgo and c
r
with
temperature for synthetic insulation liquid Clophen A
at 50 Hz constant AC voltage
Loss tangent of a transformer oil measured with
increasing voltage / field intensity/ (50 Hz) at different
constant temperatures and for different moisture contents
in oil.
Breakdown in pure liquids
Liquid
Max Breakdown Strength
MV/cm
Hexane 1.1-1.3
Benzene 1.1
Transformer Oil 1.0
Silicone 1.0-1.2
Liquid Oxygen 2.4
Liquid Nitrogen 1.6-1.9
Liquid Hydrogen 1.0
Liquid Helium 0.7
Liquid Argon 1.10-1.42

Pure liquids often have much higher breakdown strengths than commercial liquids. For instance, the addition
of 0.01% water to insulating oil reduces its breakdown strength to 20% of the "dry" value. Compare, for
example, the breakdown for Transformer Oil is usually taken as 150 kV/cm (see above table), but when highly
purified, it is almost 8 times that, or 1000 kV/cm.
The breakdown strength of any dielectric is distinguished into two broad categories known as intrinsic and the
practical breakdown strength. The intrinsic breakdown of a dielectric is defined as the highest value of breakdown
strength obtained after eliminating all known secondary effects which may influence the breakdown.
The mean free path of an electron in insulating oils is very short, of the order of 10
-6
cm. Therefore, there is no
evidence of ionization by electron collision in liquidsas as in the case of gases. For this type of ionization the field
ntensity is in the order of 10 000 kV/cm.
The most likely process of ionization in hydrocarbon liquids is excitation or molecular vibration for which
only 200-400 kV/cm of field intensity may be sufficient.
Electrodynamic motion EHD
In highly purified liquids when the field intensity reach the value in the order of a few hundred kV/cm, the
conduction current is augmented predominantly by charge carriers injected into the liquid from the electrode
surfaces. The space charge of density q, gives rise to a Coulombs force of density qE. Due to the action of
this force, hydrodynamic instability is caused, developing motion in the liquid.
Schematic representationof space charge zone and liquid motion streams between knife-plane elecrodes and the
field distribution along the axis.
At extremely high field intensities (1000 kV/cm) approaching the intrinsic strength of liquid dielectrics, the the
field emission at the electrode surfaces affects the conducton phenomenon. Under these conditions, the
conduction current is dominated by electrons.
Practical breakdown strength
The peak value of electrical breakdown strength of commercially available purified oils is about 350 kV/cm. This is
much less than the intrinsic strength of the order of 1000 kV/cm. It is due to secondary effects as: electrode
configuration, surface finish, temperature, pressure, purification dissolved water, gas, othe form of contamination.
If the condition of the liquid is very bad (impure), its electric strength could be as low as 10 kV/cm only.
The breakdown strength is in fact strongly affected by the state of moisture in the insulating oils. As soon as the
moisture content in oils acquires the emulsion state, that is tiny water droplets are unevenly distributed instead of a
solution state of moisture in the oil, the lowest breakdown strengths are measured, irrespective of an increase in ppm
water content.
AC 50 Hz breakdown voltage of a transformer oil at different costant temperatures with increasing water content.
Water droplet in Castor oil between spark gap of 5 mm distance. DC voltage
rapidly increased from 0 to 50 kV during 2 s.
Film speed 1000 frames/s. The numbers on the right side are the numbers of
following frames.
Skowroski J.I., Badania wyadowa w dielektryku ciekym. Postpy Techniki
Wysokich Napi, zeszyt 9, Conference Wyadowania w Dielektrykach Ciekych,
Dom Pracy Twrczej MO i SW Ustronie koo Kpna, 1967
Suspended solid particle mechanism
Oil with high content of cellulose fibers.
Skowronskis cup-sphere spark
gap
This force is directed towards a place of maximum stress if > liq but for bubbles < liq., it has
the opposite direction. The force increases as the permittivity of the suspended particle ()
increases, and for a conducting particle for which the force becomes
Equation gives a breakdown strength E
o
after a long time as a function of the size of the suspended
impurities. This relationship has been checked experimentally and reasonable agreement has been
obtained with calculations.
Figure 6.15 shows a plot of eqn (5 ) for a range of sizes up to 50A in radius at temperature T = 300
K, for the case where
liq
<< .
( 5 )
Breakdown in extremely nonuniform fields
Like in geseous dielectrics, in insulating liquids stable PD occur in extremely nonuniform fields before the
breakdown. The mechanism of breakdown is more or less similar to that in gases, but the causs and sources of charge
carriers are different. The negative and positive streamers appear at low density regions. The initial stage in the
breakdown of point-plane gap involve the growth of a vapour cavity from the point electrode.
A schematic showing the development of positive streamer in oil, Fiebig.
Within the vapour channel, displacement of the positive and negative charges takes place. This causes an
enhancement of field intensity at the tip giving rise to new avalanche process.
The dynamics od the development of prebreakdown cavities and channelshave been studied using photographic
techniques of pulsed schlieren and shadowgraph. Both bush and tree type streamer develop.
a b
Development of streamer in transformer oil between point-plane gaps, Fiebig
a) Tree type positive streamer in a gap length of 50 mm at 60 kV ac (peak)
b) Bush type negative streamer in a gap length of 50 mm at 60 kV ac (peak)
The ultimate breakdown is achieved when an instable leader discharge bridges the gap.
Discharge in transformer oil in extremely
nonuniform field with an insulating barrier at the
plane for SI of negaive polarity, showing leader
developing in backward direction, Hauschild.
Negative streamer (bush type) in a vegetable oil in
point-point gap length of 40 mm, DC voltage of 160
kV, Skowroski.
Ageing
Ingress of moisture and oxygen from the atmosphere may take place in storage, handling and in service. In presence
of the metallic parts of apparatus for example copper, lead, aluminiumand others, the catalytic effects of metal ions
accelerate the oxidation reactions in oils at high working temperatures. This gives rise to various oxidative products,
such as peroxides, alcohols, ketones, esters and acids.
Insoluble oxidative products not only darken the oil colour but in advanced stage of oxidation lead to sludge (mu)
formation.
There is an increase in corrosive sulphur-index of the mineral oils when subjectd to light. The degradation of
electrical properties of oils is found to be much slower by thermal ageing than under ultraviolet radiation. The
sulphur compounds in oil change rapidly to corrosive sulphur under irradiation and accelerate corrosion on the
copper surface.
Degradation of electric strength of oil due to ageing.
Reconditioning of oils by means of filters, centrifuges and vacuum dehydrators, Indian Standard IS-1866.
Static electrification in power transformer, SE
When oil is forced through the tank and coolers, it acquires an electrostatic charge, i.e. it contains
an equal number of positive and negative ions. When the oil passes the paper and solid insulation
in the windings, the insulation becomes negatively charged and the oil positively charged with the
charge separation occurring at the oil-insulated interface (figure below).
Schematic of flow electrification density in transformers
Structural diagram of the spinning device
and rotating electrometer.
Illustration of initial transitory processes at a speed
of 600 rpm.
Dariusz Oktawian Zmarzy, Jzef Kdzia, A noise analyser for monitoring static electrification current.
Journal of Electrostatics 63 (2005) 409422
Conventional spinning measuring system
Different oils have different electrostatic charging tendencies (ECT).
Transformer fire video
http://www.metacafe.com/watch/39058/transformer_fire_video/

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