5.

LIQUID DIELECTRICS
5.1. INTRODUCTION
electrical insulating liquids are used abundantly in a variety of
components of power system networks, such as transformers, power
cables, circuit breakers, power capacitors, bushing and switches. Here
they serve various functions either alone or in combination with solid
insulating materials, such as to insulate components from each other
or the ground, to impart cooling action, to fill up voids in composite
dielectrics, to impregnate thin sheet insulation, to control and provide
high capacitance in power capacitors, for are extinction in high voltage
switches/circuit breaker and also to act as lubricants in tap changers
and circulating pumps.
A wide variety of natural and synthetic oils are being used in the
electric power industry. Mineral oil is the cheapest and most commonly
used oil. However, selection of a typical dielectric fluid depends on its
physico-chemical and electrical properties besides the nature of the
service it will perform. This chapter provides details of various
important aspects of insulating liquids. These include general
classification of liquids, essential characteristics of most commonly
used and recently introduced oils, reconditioning of service aged oils
beside details on conduction and breakdown mechanisms. The
references selected for different topics are chosen from a vast
literature to assist both research scholars and engineers in gaining indepth knowledge of the topic concerned.
5.2. CLASSIFICATION OF INSULATING OILS
Insulating oils can be broadly divided into two categories : organic and
inorganic. The most commonly used organic liquid dielectrics for
electrical power equipment are mineral oils. Beside the naturally
occurring oils, a variety of synthetic organic insulating liquids are also
available in the market. Most common of these are silicone oils and
chlorodiphenyles. Recently some new synthetic organic oils such as
high molecular weight hydrocarbons and tetrachloroethylene have also
been introduced. They possess excellent dielectric and thermal
properties but are expensive. Among inorganic insulating liquids, highly
purified water and its aqueous solution are being used for pulsed
power applications, such as capacitors and modulators. At present,
water-filled discharge lines for pulsed power are under intensive
investigation and development. Similarly, liquefied insulating gases are
commonly employed for cryogenic applications. A brief description of
most commonly used insulating liquids is given below.
5.2.1. PETROLEUM OILS

The main elemental constitutes of petroleum are carbon and hydrogen

to gether with trace amount of sulphur, oxygen and some metals.
These are joined together to from three commonly occurring
structures/compounds : paraffins, naphthenes and aromatics.
Examples of some of these are shown in figure 5.1. these compounds
are treated and mixed to form insulating oils to meet the desired
physio-chemical and electrical properties. Sometime they are also
treated with additives. An additive is defined as a substance not
normally present in petroleum but its blending becomes necessary to
influence the oxidation, gas absorption and pour point characteristics
of oils. Antioxidants are widely used in some countries, whereas gasabsorbing additives are used for high voltage cable oils. Pour point
depressants are necessary for waxy oils of paraffinic type.
An oil is considered as naphthenic or paraffinic based, if the
content of either of them exceeds the other. Furthermore, an oil is
considered weakly aromatic if the presence of aromatic is less than 5%
and highly aromatic when these exceed 10%. Most of the mineral oils
that are being used today in high voltage apparatuses are low pour
point naphthenic based because the paraffinic based oils have the
tendency of wax formation when operated at low temperatures.
5.2.2. Synthetic Hydrocarbons
Among synthetic liquid dielectrics, polyolefins are the dielectrics
of choice for applications in power cables and some other electrical
systems. Over 55% of synthetic materials produced worldwide today
are polyolefins. Most commonly used olefins are poly-butylene and
alkyl-aromatic hydrocarbons (e.g., alkyl-benzene). Their composition is
simpler than mineral oils, but the general characteristics are very
similar.
Poly-butylenes
These are produced by the polymerization of short chain length
hydrocarbons. Figure 5.2. illustrates their structure. The carbon chain
extends in the range C9 to C25 . their gas absorption characteristics and
dielectric properties are slightly better than petroleum oils.
Alkyl-benzenes
These are available in a range of mixtures composed of compounds
having alkyl chains up to 25 carbon atoms attached to a benzene ring.
Table 5.2.
Shows their properties. They are unstable in presence of O 2 and are
therefore not suitable with breathing transformers. However, they
possesses high gas absorption characteristics as shown in figure 5.3.

and also lack in reaction with copper. They are therefore employed
extensively in EHV and UHV oil filled cables either alone or mixed with
mineral oil.
5.2.3. Chlorinated Hydrocarbons
Two aromatic hydrocarbons, benzene and diphenyle, are chlorinated to
produce chlorinated aromatic compounds called askarels or simply
polychlorinated biphenyl (PCB). They posses high fire point and
excellent electrical properties. In recent years their use has been
banned throughout the world. Because once they are discharged in the
environment they exhibit a strong resistance to biodegradation. They
accumulate in biological organisms and end via the food chain in
human body, thus posing a serious health hazard.
5.2.4. silicone Oils
Silicone oils represent an alternative to PCBs but they are rather
expensive. Their molecular structures main chain consists of silicone
and oxygen and
Table 5.1. chemical and electrical properties of poly-butylenes
Characteristic
Breakdown
voltage,
kV (2.5 mm)
Dielectric dissipation
factor at 90C
Resistivity m at 90C
Relative
permittivity
at 90C
Neutralization number
mg KOH/g
Water content (ppm)

IEC
40

ASTM
>35

0.0005

0.0003

1.5 x 1012
2.2

>1010
2.2

0.03

<0.04

40

Table 5.2. essential properties of alkyl-aromatic hydrocarbons

Gassing characteristics (hydrogen
atmosphere) ml/min-1 at 80C
Breakdown voltage, kV (2.5 mm)
Impulse breakdown voltage, kV
(25 mm)
Positive
Negative
Dielectric dissipation factor at
90C
Resistivity, -m at 90C
Relative permittivity at 90C

<70
>60

92
312
0.0004
1012
2.15-2.5

Organic groups constitute the side chain. The chemical configuration of

polymethylesiloxane is shown in figure 5.4. chain lengths of up to 800
siloxane units and relative molecular weights up to 60.000 can be
found.
Table 5.3. compares some important properties of commonly
used mineral and silicone oils. The dissipation factor of silicone oils is
independent.
Of frequency and temperature. Their high long-term thermal stability at
150C is particularly notable. Silicone oils are resistant to most
chemicals. They are oxidation resistant, even at higher temperature.
On thermal dissociation in an arc, nonconducting silicone dioxide
(quartz) is formed from the main chain. The higher admissible working
temperature compared with mineral oil allows volume-saving designs.
Silicone oil is an acceptable substitute for PCBs in transformers despite
its slightly inferior nonflammable properties. Its major drawbacks are
its poor gas absorption and large water content absorption. However, it
is compatible with mineral oil and PCBs, which make it well suited for
retrofilling contaminated transformers.
Table 5.3. properties of commonly used insulating oils
property
Breakdown field
strength
Volume
resistivity ()
Dielectric
constant r
Dissipation
factor at 25C
(1 MHz)
Tan
Density
Thermal
conductivity
Specific
heat
(Cp)
Thermal
stability limit
Flash point
Neutralization
number
(acidity)
Pour point

unit
kV/mm

Mineral oil
28

Silicone oil
10

-m

10-1 - 1011

1011

2.2

2.8

0.001

0.0002

g/cm3
W/Km

0.91
0.14

0.96
0.16

Cal/g/C

0.53

0.36

90

150

C
Mg KOH/g

145
<0.03

>300
-

-40

-55

Dielectric
impulse
breakdown,
Negative needle
to sphare (25.4
mm gap)
Water content

kV

145

ppm

25

50

5.2.5. Esters
Natural ester such as castor oil has been used as a capacitor
impregnant for many years, but currently two types of synthetic esters
are being used : organic esters and phosphate esters. Others are under
investigation.
Organic esters have high boiling points in relation to their viscosity
and, therefore, have high fire points. They have a good
viscositytemperature relationship, and respond to inhibitor treatment
to produce products of excellent stability. The permittivity of selected
esters is higher than that of mineral and the silicone oils, but is lower
than that of the askarels. They are used extensively in capacitors.
The phosphate esters have a better fire resistance than silicone oil, but
not as good as the askarels. They have poor viscosity-temperature
characteristics, relatively poor electrical properties, but a higher
permittivity than mineral and silicone oils. They also generally have a
poor hydrolytic stability. Due to their high boiling point and low
flammability, they are therefore potential candidates both for
transformers that are to be installed in hazardous areas as well as in
switchgear, where are suppression in a fluid system is of major
importance.
5.2.6. some recently introduced oils
At present there is considerable short supply of naphthethic-based
crude oils. Moreover, in a continuing effort to replace PCBs and
continue the search for better quality oils, some new oils have been
introduced in recent years. These are being marketed under different
commercial names, such as high temperature or high molecular weight
hydrocarbon oil, tetrachloroethylene, perfluoropolyether and many
others.
High temperature or high molecular weight hydrocarbon oils
These are alternative to PCB fluids and are called HTHs. They have
good electrical insulating properties and adequate heat transfer
properties. These are chemically similar to regular mineral transformer

oils, but they possess higher boiling points and higher fire points.
However, they have higher viscosity which reduces heat transfer
capability. General properties of HTHs are given in table 5.4.
Tetrachloroethylene (C2Cl4)
This is also a nonflammable insulating fluid. It can be used in mixtures
with mineral oil. It has very low viscosity and therefore gives excellent
heat transfer properties. Its mixtures with mineral oils also remain
inflammable.
Table 5.4. some typical properties of HTH and C2Cl4 fluids
property
Flash point, C
Fire point, C
Expansion coefficient
cc/cc/C at 25C
Pour point, C
Viscosity, cSt
100C
50C
25C
Specific gravity, g/cm3
Dielectric
strength,
ASTM D-877, kV
Impulse
breakdown,
kV
Negative polarity
Positive polarity
Dielectric constant, r
Dissipation factor (%)
100C
50C
25C

HTH
285
312
0.0008

C2Cl4
None
None
0.00102

-30

-22

16
85
350
0.877
43

0.36
0.42
0.55
1.620
43

118
85
2.38

2.365

0.4
0.4
<103

0.05
-

However some toxic effects of this insulating fluid are also reported.
Perfluoropolyether
This has recently been introduced in the European market with the
trade name galden HT40 as replacement for PCBs. It is nonflammable
oil, as its boiling point exceeds 400C. it possess low vapor pressure,
thus it can be used as a good heat transfer medium. Its molecular
structure is given in figure 5.5. since it has no C-H bonds and C-F bonds
are much stronger (single bond energy 4.6 eV), bond scission does not
take place at normal stress. Therefore no gaseous products are formed.

Another interesting feature of HT-40 is the lack of moisture sensitivity,

as it has no affinity for water and it does not absorb or mix with water.
If any fluorine evolves during service it does not react with water to
form any acid (unlike PCBs which produce highly corrosive HCl).
Because of their higher density, water accumulated in transformer will
float on top
Of the oil surface rather than at the bottom, as is the case in
conventional petroleum mineral oils. However, its viscosity and cost
are high.
5.3. essential characteristics of insulating oils
Table 5.5 outlines a list of the most important characteristics of
insulating oils along with their typical accepted values. However, for
the purpose of design and operation, the following are very essential
and are therefore dealt with in some detail:
Table 5.5. properties of mineral insulating oils considered prior to,
during and after their long use
Characteristics
Dielectric
strength

ASTM
method
D-877

test

IEC publication

Typical values

156

30 kV (1.0
mm)
28 kV (1.02
mm)
0.1 0.5 %
(90C)
145 kV

D-1816
Dissipation
factor
Impulse
strength
Dissolved-gas
content
Density, specific
gravity
Viscosity

D-924

247

D-3300

897

D-831

567

D-1298

296

825-890 kg/m3

D-445

296-A

Pour point
Neutralization
number
Antioxidant
content
Water content
Gassing
characteristic
Interfacial
tension
Resistivity

D-97
D-974

296-A
296

3 ~ 16 cSt
(140C)
-30C
0.5 mg KOH/g

D-2668

666

0.3%

D-1533
D-2300 (AB)

733
628(A,B)

D-971

296

<80 ppm
-35
to
+35
3
mm /min
40 ~ 60 mN/m

D-1169

247

3 ~ 10 Gm

1. Thermal transfer characteristics

2. Chemical stability against electrical stresses
3. Dielectric properties
5.3.1. thermal transfer characteristics
In a liquid filled system (transformer, cable, circuit breaker, etc), heat is
transferred mainly by convection. Under natural atmospheric cooling
conditions convection (N) is given as :

K AC
N=f
v

Where K = thermal conductivity, A = coefficient of expansion, C =

specific heat per unit volume, v = kinematic viscosity, and n = 0.25 ~
0.33 it is clear that heat transfer is dtrongly dependent on K and to
lesser degree on A and C, whereas it inversely varies as viscosity.
Generally in liquids, A and C do not vary much, but v varies greatly.
Therefore, the main factors that control heat transfer are K and v.
obviously, an increasing value is preferable for systems likely to
operate continuously at a high temperature. On the other hand, a low
value of K and high viscosity can lead to localized overheating or even
electrical burn out. Figure 5.6 shows the variation of viscosity with
temperature. It is an important feature
Of the liquid that as temperature increases its viscosity falls off. This
greatly enhances the cooling effect.
Silicone oils do not exhibit this property appreciably, therefore this
viscostatic property coupled with poor heat capacity and falling
thermal conductivity can pose severe overheating problems at high
temperature in systems based on such insulants. Thermal conductivity
and specific heat values are therefore much more useful for evaluating
temperature gradients and possible hot-spot formation in places where
the oil is trapped. Inside oil-impregnated paper insulation, for instance,
a temperature gradient of 15C has been reported across a layer of
only 0.4 mm of oil-impregnated paper covering a copper conductor.
5.3.2. chemical stability under electrical stress
In service, insulating liquids are subjected to thermal and electrical
stresses in the presence of materials like O2, water, fibers and
decomposition products of solid insulation, as well as oil soluble
constituents of impregnating varnishes and resins. Tehse, either singly
or in combination, promote degradation of the liquid with the result

that soluble solid and gaseous products are formed, which can result in
corrosion, impairment of heat transfer, deterioration of electrical
properties, increased dielectric losses, discharges and arcing. In the
absence of any remedial action, this cycle continues and produces an
ever-worsening liquid and equipment condition.
Degradation due to electrical and severe thermal stresses is indicative
of an equipment design or fault conditions, while the oxidation
constitutes the most important in-service deteriorating property of
insulating liquids in equipment subject to breathing. The rate of
oxidation is increased by the presence of materials acting as catalysts.
Copper is one of the most active of such materials. Improper
impregnation, however, results in enhanced catalysis due to attack on
the conductors by varnish acids. It also produces heavy sludge deposits
when incompletely cured impregnants dissolve in the liquid filling and
precipitate after polymerizing or curing.
To retard oxidation, oils are inhibited with additives called antioxidants.
A widely used antioxidant additive is DBPC (2.6 di-tert-butyl peresol)
and, to a lesser extent, DBP (2.6 di-tert-butyl phenol). Antioxidants do
not prevent copper dissolution in oil (figure 5.7) but as long as they are
present (induction period) they prevent the formation of free-radical
peroxides, especially from the saturated hydrocarbon fraction, and the
subsequent chain oxidation reactions. During this period they
themselves are slowly oxidized and deactivated and, when they have
been almost completely consumed (end of the induction period), the
above protection is no longer available. Accelerated formation of
peroxides is then observed, followed by acids and polar oxidation
compounds and, finally, by oil-soluble and insoluble sludges. The
relative saturation in the final stage of oxidation results from the
buildup of inhibiting phenolic forms of the aromatics. The electrical
properties (tan and conductivity) are closely related to the observed
oxidation steps and the mechanism applies to paraffinic as well as
naphthenic oils.
The electrical characteristics such as electric strength, impulse
strength, DC volume resistivity, dielectric dissipation factor and relative
permittivity are generally of much importance. The maintenance of
electrical properties at an acceptable level ensures satisfactory
equipment performance, reduces ohmic losses and limits discharge
inception within the liquid. The level of test results is affected by the
chemical constitution of the liquid, but with the exception of impulse
strength and permittivity, is predominantly due to the presence of
conducting contaminants such as fibers, water, particulate matter (dirt)
dipolar and ionic or dissociated compounds.

Liquids can vary widely in electric strength. Power frequency

breakdown depends considerably on the level of moisture and
contaminating particles. Similarly these factors also effect the
dielectric loss and resistivity of insulating oil. However, with filtration
and removal of moisture these can be considerably improved.