F E A T U R E A R T
50 Years in the Development
of Insulating Liquids
Key words: dielectric coolant, mineral oil, vegetable oil, ester, silicone liquid, liquid-filled equipment
Introduction
The role of electrical insulation is critical for the proper op-
eration of electrical equipment. Power equipment cannot oper-
ate without energy losses, which lead to rises in temperature.
It is therefore essential to dissipate the heat generated by the
energy losses, especially under high load conditions. Failing to
do so results in premature aging, and ultimately to failure of the
equipment. Heat dissipation can be achieved by circulating cer-
tain liquids, which also ensure electrical insulation of energized
conductors. The insulating-fluids market is therefore likely to
be dominated by liquids, leaving to gases (such as compressed
air and SF6) limited applications in power equipment such as
circuit breakers and switchgear [1]–[3]. Several billion liters of
insulating liquids are used worldwide in power equipment such
as transformers (power, rectifier, distribution, traction, furnace,
potential, current) [4], resistors [5], reactors [6], capacitors [7],
cables [8], bushings [9], circuit breakers [10], tap changers [11],
thyristor cooling in power electronics, etc. [12].
In addition to their main functions of protecting solid insu-
lation, quenching arc discharges, and dissipating heat, insulat-
ing liquids can also act as acoustic dampening media in power
equipment such as transformers. More importantly, they provide
a convenient means of routine evaluation of the condition of
electrical equipment over its service life. Indeed, liquids play a
vital role in maintaining the equipment in good condition (like
blood in the human body). In particular they are responsible for
the functional serviceability of the dielectric (insulation) system,
the condition of which can be a decisive factor in determining
the life span of the equipment [13]. Testing the physicochemical
and electrical properties of the liquids can provide information
on incipient electrical and mechanical failures. In some equip-
ment, liquid samples can be obtained without service interrup-
tion.
The sixth of a series of invited reviews
to be published during 2013 to mark
the 50th anniversary of DEIS.
September/October — Vol. 29, No. 5 0883-7554/12/$31/©2013/IEEE
I C L E
I. Fofana
Canada Research Chair
on Insulating Liquids and Mixed Dielectrics
for Electrotechnology (ISOLIME),
Université du Québec à Chicoutimi,
Québec, Canada
The importance of liquids in the field
of dielectrics and electrical insu-
lation is highlighted. Engineering
problems in using these liquids in
electrical equipment are discussed.
Their applications and perspectives
are addressed.
Petroleum-based oil, so-called mineral oil, has been the main
insulating liquid in industrial power systems since the 1900s
[14]–[16] because of its good aging behavior, low viscosity,
ready availability, and low cost [14]. Because of the necessity
of operating distribution transformers in locations where high
fire security standards were required, polychlorinated biphenyl
(PCB)-based insulating liquids were introduced in the early
1930s. Until the 1960s they did not raise environmental concern.
However, since the 1970s the public has been increasingly criti-
cal of the use of PCB-based transformer oils [1]–[4]. While most
PCB oils have now been replaced with PCB-free liquids, the lat-
ter have not been widely accepted as alternatives to mineral oils
in power equipment. Driven by the desire for a safer nonflamma-
ble and environmentally acceptable insulating liquid for use in
power equipment, researchers and engineers have investigated
countless alternatives to mineral oil, and significant advances
have been achieved during the last four decades [17]–[25].
13
 In this review article some of the developments in the field
over the past 50 years are described.
Classification of Insulating Liquids
Various liquids are being used as lubricating agents. How-
ever, they will not be considered in this article. Insulating liquids
can be subdivided into different categories based on their chemi-
cal structures or their fire points. In Table 1 (updated version of a
table published in [22]) 14 categories of insulating liquids used
during the last 50 years are listed.
Mineral Oils
Mineral oils are complex mixtures of hundreds of different
organic compounds, consisting mainly of carbon and hydro-
gen in molecules with different structures [22]–[24]. They are
made by refining a fraction of the hydrocarbons collected during
the distillation of petroleum crude stock. The physicochemical
properties of an oil may vary significantly from one batch to
another, even from the same supplier.
There are three categories of crude oils, namely paraffinic,
naphthenic, and mixed crudes [14]–[16], [22], [24]:
(a) Paraffinic crudes contain a small amount of naphthenic
hydrocarbons and can be subdivided into normal par-
affins (straight chain wax-type molecules) and isopar-
affins (branched paraffins). Isoparaffins are preferred
over normal paraffins because of their lower pour
points.
(b) Naphthenic crudes have higher naphthenic compound
content than do paraffinic crudes.
(c) Mixed crudes are intermediate between paraffinic and
naphthenic crudes.
The early mineral oils were paraffin based, but after 1925
they were replaced with naphthenic oils because of the high pour
points of paraffinic oils [14]. In addition, paraffinic crudes con-
tain waxes, whereas naphthenic crudes contain very little wax.
Since naphthenic oils have lower viscosities than paraffinic oils,
the former become thinner and less viscous at elevated operating
temperatures and therefore provide, at least theoretically, better
heat exchange.
Modern petroleum refining has changed dramatically over
the last 30 to 40 years. Improved technology, specifically cata-
lytic hydroprocessing, has brought many benefits and efficien-
cies. Reviews of various refining technologies exist [14], [15],
[26], [27]. Refined oils are very complex blends and may consist
of more than 3,000 different hydrocarbons, principally paraf-
finic (40–60%), naphthenic (30–50%), and aromatic (5–20%)
chains of carbon atoms [14]–[16], [19], [24]–[27]. Aromatic hy-
drocarbons contain unsaturated ring molecules and have many
names, e.g., polynuclear aromatics, polycyclic aromatics, and
polyaromatic hydrocarbons. Aromatic content is the main factor
that determines the difference in the water solubilities of differ-
ent oils [13]. Polyaromatic hydrocarbons may present a health
concern; recent studies suggest that naphthenic oils with more
than 2% polyaromatic hydrocarbon content are potentially car-
cinogenic [13], [28].
14 IEEE Electrical Insulation Magazine
Naphthenic oils are typically manufactured by solvent refin-
ing processes with hydroprocessing/hydrotreating or mild hy-
drofinishing. Such processes leave residual substances in oil,
including sulfur compounds and aromatic nitrogen [26], [27],
[29]. Naphthenic isoparaffinic liquids are highly refined using
hydrocracking and hydroisomerization, which eliminate almost
all contaminants from the liquid, leaving it almost free of sulfur
[26], [27]. Isoparaffinic oils have better heat transfer capabilities
than do naphthenics [30].
Synthetic Insulating Liquids
Although mineral oils play a very important role in the power
industry, synthetic liquids are used when special properties are
sought, e.g., fire resistance, partial discharge resistance, negative
gassing tendency (gas absorption). A large number of synthetic
insulating liquids are available, e.g., halogenated hydrocarbons,
aromatic hydrocarbons, high molecular weight hydrocarbons,
polybutenes and phthalates.
Halogenated Hydrocarbons
(Nonflammable Liquids)
Nearly all nonflammable liquids are classified as halogenat-
ed hydrocarbons, typically including chlorine or fluorine [31]
which react with hydrogen atoms to form HCl and HF.
Because of the desire for nonflammable liquids, PCBs were
used for insulation purposes between 1929 and 1977 [32]. These
liquids (generic name askarels = fire resistant) were mixed
with varying quantities of trichlorobenzene or tetrachloroben-
zene [19], [22], [24] and marketed as insulating fluids under the
name Aroclors (one of the most commonly known trade names
for PCB mixtures). Technical specifications of askarels can be
found in CEI 60588-3 [33]. They were used primarily in trans-
formers (for their fire resistance), capacitors (for their resistance
to partial discharges), and hydraulic machines requiring stable,
fire-retardant materials [19], [22], [24]. When it became clear
that PCBs may cause adverse health effects, their manufacture
was banned after 1978 [32]. In the European Union, equipment
containing more than 50 ppm of PCBs was to be destroyed by
incineration by the end of 2009 [24].
Researchers have tried countless combinations of chemicals
to remove PCBs from older equipment and to find other insulat-
ing liquids with which to fill new equipment. Various chlorinated
fluids, e.g., benzyltoluene, perchlorethylene, trichlorobenzene,
and dichlorotoluene were developed as replacements for PCBs
in applications where nonflammability was important [34]–[36].
The most popular include polychloro-diphenyl-methanes and
chlorinated diphenyl (or benzyltoluene) substitutes. Polychloro-
diphenyl-methanes are readily biodegradable and do not form
dioxins in case of fire [22], [24].
PCB-free halogenated hydrocarbons have had limited indus-
trial success, mainly because of strong resistance to chlorination
[22], [24]. Fluorinated products have been investigated in the
United States, but their high cost has inhibited their develop-
ment [24]. Perfluorinated polyethers were proposed in 2000 for
capacitors in which resistance to fire is of great importance [1],
[24].
 Table 1. Application of Insulating Liquids in Electrical Power Equipment (Updated Version of a Table Published in [22]).

Power
transformers Distribution Traction Instrument Special Tap Terminal Circuit Loading
Insulating liquid1 and reactors transformers transformers transformers transformers Bushings changers boxes breakers Capacitors Cables resistance

Mineral oils X X X X X X X X O O O  
Polychlorinated biphenyls   —       — —     —    
(PCB)

September/October — Vol. 29, No. 5

Other halogenated   O                    
hydrocarbons

Silicone oils   X X       X          
High-molecular-weight   X         X          
hydrocarbons

Tetraester of pentaerythritol   X X       X         X

Alkylbenzenes       X   X       X X  
Aromatic hydrocarbons       X           X    
(M/DBT, PXE, MIPB, etc.)

Vegetable oils   X               X    
Phthalates (DOP, DNP)                   X    
Polybutenes                     X  
Liquefied gases or cryogenic   X       X            
liquids

Nanofluids   X                    
Mixed liquids   X               X X  
X : In use in the equipment.
O: No longer recommended for the equipment, but still in use here and there.
—: Banned, and therefore should not be in use anywhere.
1
M/DBT = mono/dibenzyltoluene; PXT = phenyl-xylyl-ethane; MIPB = mono-isopropyl-biphenyl; DOP = dioctyl phthalate; DNP = di-isononyl phthalate.

15
 Aromatic Hydrocarbons
These liquids are mainly used in capacitors and cables [19].
Their technical specifications are defined in IEC 60867 [37].
Alkylbenzenes
In the 1960s a new family of insulating liquids known as al-
kylbenzenes became available. Their stability under partial dis-
charge is their most important property for today’s applications.
They have considerably greater ability (relative to mineral oil) to
absorb gas produced by partial discharges [38] and are therefore
often used in hermetically sealed equipment. Their low viscos-
ity is another important property, especially for oil circulating
in cables. Heavier alkylbenzenes are used for filling capacitive
dividers [22], [24]. The addition of about 30% of alkylbenzene
liquid (by volume) to mineral oil used for impregnation of cable
systems greatly improves the gas absorbency of the oil [22],
[24], [38].
Polyarylalcanes
Polyarylalcanes were primarily developed to replace PCBs
as impregnating liquids for capacitors [22], [24]. Among the
first generation developed in the 1970s were phenyl-xylyl-eth-
ane, mono-isopropyl-biphenyl, and di-isopropyl-naphthalene.
Mono-isopropyl-biphenyl is no longer used in North America,
but phenyl-xylyl-ethane and di-isopropyl-naphthalene are still
used in Asia [24]. In the 1980s phenyl-xylyl-ethane and mono-
isopropyl-biphenyl were replaced by diphenyl-methane deriva-
tives, specially developed for capacitors, e.g., mono/dibenzyl-
toluene 75/25 and benzyl-toluene/diphenyl-ethane 60/40. (The
numbers indicate the mass percentages in the mixtures.) Mono/
dibenzyltoluenes have been used in power capacitors for more
than 25 years. They have also been approved for other electrical
equipment such as capacitive voltage transformers and bushings
[19]. Polyarylalkanes are also used for filling capacitive divid-
ers. Their dielectric properties, much better than those of alkyl-
benzenes and mineral oils, improve their competitiveness [24].
Polyarylalcanes have kinematic viscosities less than 8 mm2/s
at 40°C [22], [24], so that removing moisture from them under
vacuum is much easier than from mineral oils. Their thermal sta-
bility is much better than that of mineral oils and alkylbenzenes.
However, they are more polar, and their dielectric properties are
more sensitive to contaminants. Because of their high aromatic
content they generate very little gas under partial discharge and
have high hydrogen absorbance capacity. Their low solubility in
water limits their biodegradability. Their toxicity is very low, as
is the rate at which they accumulate in the environment.
Polyolefins
Polyolefins are unsaturated hydrocarbons with double bonds.
The polybutenes, especially polyisobutenes, are the most widely
known and used. Polybutenes are nontoxic and environmentally
friendly and are used as insulants in cables and LV metalized
capacitors because of their high viscosities. Their technical
specifications are given in CEI 60465 [39]. Polyolefins recently
emerged as alternatives to mineral oils in transformers. They
are nontoxic and biodegradable, and their flashpoints are in the
range 240 to 250°C [24]. However, their use has been limited by
their high cost.
16 IEEE Electrical Insulation Magazine
Phthalates
The phthalates include two liquids, namely di-isononyl
phthalate and dioctyl phthalate. They were developed as al-
ternatives to PCBs in LV and medium-voltage capacitors, but
their use has declined significantly over the last 30 years, as a
result of the development of dry-type metalized polypropylene
film capacitors. However, dioctyl phthalates are still used for LV
capacitors because their good dielectric properties facilitate the
manufacture of capacitors that are more reliable than dry-type
metalized polypropylene units. Their most important property
is their high relative permittivity (5.2 at 20°C), which leads to
higher capacitances than those achievable using polybutenes or
silicone oils. The main properties of dioctyl phthalate are listed
in IEC 61099 [40].
High-Fire-Point Liquids
High-flash-point liquids, also known as “less flammable” liq-
uids, were developed as replacement impregnants in transform-
ers formerly filled with PCBs. Qualifying liquids must have a
minimum open-cup fire point of 300°C [31], [35]. Because of
this high degree of resistance to ignition, they are specified for
transformers in locations with significant fire risks. At present,
most high-flash-point liquids are produced from four different
chemical bases, namely high-molecular-weight hydrocarbons
(HMWHs), synthetic esters, dimethyl silicone, and vegetable
oils [22], [24], [25].
High-Temperature or High-Molecular-Weight
Hydrocarbons (HMWHs)
Other alternatives to PCB liquids are the HMWHs or high-
temperature hydrocarbons. These liquids are chemically similar
to regular petroleum-based mineral oils used in transformers.
However, they have higher boiling points and higher molecu-
lar weights, and therefore much higher fire points. HMWHs
are classified as paraffinic, consisting mainly of saturated com-
pounds with long, straight-chain structures. They have good di-
electric and lubricating properties. They also have a higher vis-
cosity, which reduces their heat-transfer capabilities.
HMWH-based liquids have been used in transformers fitted
with load break devices such as load tap changers [41] and in
unit substations, pad-mounted transformers, and oil retrofills
[31]. Combined with Aramid insulation materials, they are also
used in high-temperature transformers, i.e., those with 175 to
185°C hot spots [30] found in mobile or double-ended substa-
tions.
Synthetic Esters
Esters are a broad class of organic compounds synthesized
from organic acids and alcohols. They do not generate dioxins or
other toxic products in the presence of fire, and have good bio-
degradability [42], [43], forming only carbon dioxide and water.
Ester liquids have been developed to resist oxidation and can ab-
sorb considerably more moisture than mineral oils before their
performance as insulants deteriorates significantly. Previous
work [35] has shown that ester liquids can be used for retrofill-
ing mineral oil–filled transformers. Mixing ester liquid with up
to 3% mineral oil does not degrade the electrical and dielectric
properties of the insulating system. Several types of esters are
used in electro-technology:
(1) Tetraesters (or pentaerythritol esters) are environmen-
tally friendly liquids, but their high costs compared
to those of other less-flammable fluids limit their use
to traction and mobile transformers and other special
applications. Their properties are listed in IEC 61099
[40], and a guide for maintenance of ester-filled trans-
formers is available [44]. In hermetically sealed trans-
formers operating at normal temperatures, tetraesters
can absorb moisture produced by thermal degradation
of cellulose (paper) present in the windings, and are
unlikely to require maintenance during the life of the
transformer. In breathing transformers the need for
liquid-insulator servicing depends on operating con-
ditions and on the performance of breathing devices.
Tetraesters can absorb much larger quantities of water
than mineral oil, because of their carbonyl structure
[35], [41], [42]. Since the viscosity of ester liquids is
higher than that of mineral oil, a more efficient heat-
transfer system is required with the former [35]. The
higher moisture content results in some hydrolysis of
the liquid, forming the mild free fatty acids typical of
ester-based liquids.
Tetraesters have been used as alternatives to PCBs
in compact railroad traction transformers since 1984,
and in klystron modulators where their high lubricity
and low pour points (close to that of mineral oils) jus-
tify their higher cost [31]. Following the replacement
of askarels with polyol esters, failure rates of traction
transformers have significantly decreased.
(2) Phosphoric esters have been proposed for various ap-
plications (capacitors, transformers) because of their
high fire point and permittivity. However, their use is
very limited [19], [22], because of the environmental
risks that they pose [45]. Dibutyl sebacate, dioctyl-seb-
acate, and benzyl-neocaprate were used as impregnat-
ing fluid for capacitors in the past, but not today be-
cause of health hazards [19].
Silicone Oils
Silicone oils are known chemically as poly-dimethyl silox-
anes or PDMS [22], [24]. They were introduced in the 1970s
as substitutes for PCBs and have proven popular in retrofilling
transformers [40], [42]. However, their use has been limited to
situations where fire could pose a risk to personnel and property.
Their chemical structure has been described [25], [46], [47].
Silicones are environmentally friendly and flame retardant, age
well, and are strongly resistant to oxidation and sludge forma-
tion [48]. As far as their cooling and insulating properties are
concerned, they compare well with mineral oils. Silicone oils are
colorless, and have very low pour points compared with mineral
oils, even though their viscosities at 20°C are much higher. In
order to avoid large temperature rises during operation, silicone-
filled transformers must be de-rated (up to 10%) or provided
with additional cooling capacity.
Vegetable Oils
Vegetable oils are readily available natural products, and
therefore should be considered as ideal raw materials for fully
biodegradable insulating liquids [49]–[52]. They consist essen-
tially of triglycerides, which are naturally synthesized by esterifi-
cation of the tri-alcohol glycerol with three fatty acids. The fatty
acid composition of some vegetable oils is shown in Table 2 [17].
Experimental investigation of vegetable oils as dielectric
coolants began around the early 1900s, concurrently with min-
eral-oil trials [48]. Their poor dissipation factor and oxidation
stability, and higher pour point, relative permittivity, and vis-
cosity [31] have been their main disadvantages as dielectric flu-
ids. A literature survey [17], [22], [24] indicates that for many

Table 2. Typical Fatty Acid Composition of Some Vegetable Oils [17].

Unsaturated fatty acids, %

Vegetable oil Saturated fatty acids, % Mono- Di- Tri-

Canola oil1 7.9 55.9 22.1 11.1

Corn oil 12.7 24.2 58 0.7

Cottonseed oil 25.8 17.8 51.8 0.2

Peanut oil 13.6 17.8 51.8 0.2

Olive oil 13.2 73.3 7.9 0.6

Safflower oil 8.5 12.1 74.1 0.4

Safflower oil, high oleic content 6.1 75.3 14.2 —

Soybean oil 14.2 22.5 51 6.8

Sunflower oil 10.5 19.6 65.7 —

Sunflower oil, high oleic content 9.2 80.8 8.4 0.2

1
Low erucic acid variety of rapeseed oil. Recently canola oil with more than 75% monounsaturated content has been developed.

September/October — Vol. 29, No. 5 17

 Table 3. Boiling Points of Common Cryogenic Liquids.
  Ar He H2 N2 O2 Ne
Boiling point −186 −269 −253 −196 −183 −246
(1 atm), °C
years they were considered suitable only for capacitor use. Their
unsaturation confers good gas-absorbing properties, which are
desirable in capacitors, cables, and instrument transformers.
However, the unsaturated parts of the chain are vulnerable to
oxidation, resulting in poor oxidation stability. Castor oils have
been widely used in capacitors (with cellulose insulation) since
1962 [17], [53], [54]. Unlike other vegetable oils, which are fatty
acid esters, castor oil is 80% hydroxy-acid ester, the acidic part
being ricin-oleic acid.
In the 1990s, mainly because of environmental concerns,
utilities became interested in fully biodegradable insulating liq-
uids, particularly for use in transformers located in coastal areas
where oil spills would contaminate water [31]. Many vegetable
oils, currently available, therefore contain additive chemical
packages that reduce the pour points and enhance oxidation sta-
bility. Typically a 10°C lowering of the pour point, with negligi-
ble change in electrical conductivity, can be achieved by adding
a polymethyl-acrylate derivative at concentrations below 1%. In
some cases the packages contain an antimicrobial agent or cop-
per deactivator [17], [48]–[53]. Recently, a new vegetable-based
insulating oil for transformers, called palm fatty acid ester, has
been proposed. Relative to mineral oil its dynamic viscosity is
60% lower and its relative permittivity is 30% higher [55], [56].
Using chemical treatment of filtered samples, Abderrazzaq et al.
[57] significantly improved the acidity of olive oil.
Nanoliquids
Nanotechnology is now being used or considered for use
in many engineering applications, with the aim of improving
equipment efficiency. Nanofluids are finding applications in a
wide variety of industries, from transportation to power engi-
neering, in microprocessors and in micro-electro-mechanical
systems (MEMS), and in biotechnology [58], [59]. A review of
the most commonly used nanoliquid production methods can be
found in the literature [58]–[62]. They consist of a base liquid
in which nanosized particles (1–100 nm) are suspended. The
addition of nanoparticles can greatly improve the thermal and
dielectric properties of the liquid, more specifically extending
transformer lifetime and increasing loading/cooling capacity.
The most commonly used nanoadditives include metals and
metal oxides. Yue-Fan et al. [2] developed a nanoliquid by dop-
ing mineral transformer oil with TiO2 nanoparticles, in order to
enhance its dielectric performance. Choi et al. [62] evaluated
dispersions of nanosized Al2O3 and AlN powders in transformer
oil, with small amounts of oleic acid as a dispersant. Nano-dia-
mond particles were found to increase the dielectric strength and
life of transformer oil [59], [63]. It has been suggested that the
addition of magnetic nanoparticles may also increase the dielec-
tric strength of transformer oil [64], [65]; although the dielectric
18 IEEE Electrical Insulation Magazine
strength of the magnetic nanoliquids may be up to 13% higher,
their increased loss factors may cause thermal problems under
operational conditions. Recently, nanoliquids containing a new
type of semi-conductive nanoparticles were investigated [66]. It
was found that the semi-conductive nanoparticles improve the
insulating and anti-aging properties of mineral oil, but have little
effect on other electrical parameters, e.g., conductivity/resistiv-
ity and dissipation factor.
Cryogenic Liquids and Liquefied Gas
The discovery of superconductivity by Onnes in 1911 was
followed by the development of high temperature superconduc-
tivity in 1986 [67]. The latter has found many applications in
power engineering, e.g., in generators, magnetic energy storage
systems, power transmission lines, transformers, and fault cur-
rent limiters.
One of the critical components for superconducting devices
is the liquid used to achieve cryogenic temperatures. In cables
and transformers the cooling liquids must act simultaneously as
insulating liquids under the relevant voltage stress. These liq-
uids are condensed from atmospheric gases. The boiling points
(at a pressure of 1 atmosphere) of some common cryogenic liq-
uids are listed in Table 3. Carbon dioxide and nitrous oxide have
slightly higher boiling points.
Liquid helium is an established cooling and insulating agent.
Since the development of high-temperature-superconductivity
materials, liquid nitrogen, with its superior dielectric breakdown
strength, has become the preferred cooling and insulating liquid.
A comparison of the dielectric properties of liquid helium and
liquid nitrogen is available [67].
The feasibility of substituting CF4 gas for SF6 gas as insulant
for the bushings of high-temperature-superconductivity materi-
als was recently explored [68]. Mixtures such as liquid oxygen/
nitrogen may exhibit better cooling performance than liquid ni-
trogen [69]; however serious risk associated with highly chemi-
cally reactive oxygen may arise under partial discharge or arc-
ing.
Superconductors cooled by a cryogenic liquid have consider-
able industrial and research potential because they facilitate high
current densities without Joule heating [70]–[76]. However,
much work is needed to exploit this potential to the full.
Mixed Insulating Liquids
In order to obtain stable insulating liquids with specific di-
electric, flash point, and thermal properties, various mixtures
have been investigated over the last 50 years [22], [24], [77]–
[81]. Some examples are listed in Table 4. Generally, the physi-
cochemical properties of the mixture are intermediate between
those of the constituents, depending on the mixture ratio.
Physicochemical and Dielectric Properties
of Insulating Liquids
Despite great progress in power-equipment design in recent
years, the weak link in the chain still remains the insulation sys-
tem. A low breakdown voltage compromises operational safe-
ty, and the irreversible aging process shortens life expectancy.
 Table 4. Examples of Mixed Insulating Liquids.

Mixture Application

Mineral oil + alkylbenzene Oil-impregnated-paper capacitor (to improve the gassing tendency)

Mineral oil + perchloroethylene (C2Cl4) Distribution transformers (C2Cl4 oil blends have been classified as nonflammable)

Polychlorinated biphenyl (PCB) + trichloro-benzene (TCB) Distribution transformers (to improve viscosity)

Tetracholorobenzyltoluene (TCBT) + TCB Distribution transformers (to improve viscosity and biodegradability)

Alkylbiphenyl + alkyldiarylalcane Capacitors (biodegradability)

Ester + TCB Capacitors (PCB substitute)

Ester phosphate + alkyldiarylalcane Capacitors (PCB substitute)

Ester phosphate + aromatic hydrocarbon Capacitors (PCB substitute)

Tetracholorodifluoroethane + perchloroethylene (C2Cl4) Traction transformer

Synthetic ester + mineral oil Distribution transformers (to improve fire point, hygroscopicity, and biodegradability)

When electrical equipment fails, the fault can usually be traced
to defective insulation [13].
Dielectric Behavior
During the last 50 years much work has been done with the
aim of improving our basic knowledge of insulating liquid per-
formance. Understanding the fundamental causes of insulation
breakdown, i.e., the conditions necessary for electron avalanche
formation, is essential to ensure reliable design of liquid-filled
equipment. Earlier studies were concerned with the physical
phenomena involved in electro-hydrodynamic processes [82]–
[84], and with streamer initiation and development [85]–[94].
Reviews are available [23], [88]. Mathematical models have
been developed to simulate the fundamental processes govern-
ing discharges in oil [95]–[98]. Pioneering work by Forster has
clarified the mechanisms by which high-voltage fields interact
with insulating oils [99]. Static electrification is another impor-
tant factor threatening the safety of power transformers [100]–
[106]. Using modern laboratory testing techniques, researchers
have improved our understanding of the physical mechanism
by which discharges are initiated in dielectric liquids. However,
much work is still required.
Insulating Liquid Gassing
Fundamental investigations have also been carried out on
the gassing of oils [100]–[106]. Knowledge of the resistance
of insulating fluids to gassing under high electrical stress is of
utmost importance to electrical equipment designers and opera-
tors [107]. While in service, insulating liquids undergo a slow
but steady decay process under the impact of electrical, thermal,
mechanical, and environmental stresses. Incipient failures such
as hot spots and partial discharges are responsible for the gassing
of oil. Since the resulting fault gases dissolve in the oil, the dis-
solved gas analysis technique was developed in order to detect
incipient failures at an early stage, and is now probably the most
frequently used in-service tool for detecting faults in liquid-
filled electrical equipment [108]. About 20 dissolved gas analy-
sis interpretation techniques have been developed so far [109],
e.g., IEC 60599, IEEE C57.104, Duval’s Triangle and the Key
Gas method [110]–[113]. Since all these methods are heuristic
in nature, i.e., not based on scientific formulation, combining
several of them may reduce the risk of mistaken diagnostics and
enhance accuracy [114]. Dissolved gas analysis techniques are
being developed for liquids other than mineral oil [115]–[117].
A Powerful Tool for Life Management
In addition to gases, insulating liquid decay generates aging
by-products, which promote further degradation [118]–[120].
Aged or moistened liquids may be treated by drying out, de-
gassing, reclamation, re-refining. and reconditioning [121]. A
review of the present state of knowledge of liquid treatment pro-
cedures is presented in [122].
The presence of moisture (considered the main enemy of in-
sulation) in solid and liquid transformer insulation is known to
play a critical role in transformer life [123]–[125]. The mois-
ture content of the oil can change quickly within an operational
transformer. Direct measurement of moisture content in paper
insulation (cellulose) is complex; moisture partitioning curves
between oil and paper under equilibrium conditions have been
published by several authors [126], [127], so that, the moisture
content of the oil having been measured, the moisture content in
the paper can be quickly estimated and the probability of failure
predicted. A comprehensive review and comparison of various
partitioning curve sets has been published [126]. Complications
due to fast dynamic diffusion processes arise. Another problem
with the partitioning diagrams is that they are based on new oil
and do not take into account the effects of aging by-products
found in aged transformer oil. Diagnostic techniques, based on
dielectric spectroscopy, for assessing the condition of the insula-
tion in aged transformers are reviewed in [108].
In free breathing units such as transformers, the insulation
system ages under the influence of electrical stress, moisture,
dissolved oxygen, and excessive heat. The chemical aggressive-
ness of oxygen facilitates the formation of soluble oxidation
products and insoluble sludge, which are detrimental to solid

September/October — Vol. 29, No. 5 19

 insulation. Use of antioxidant additives, nitrogen cushions, and
elastic rubber or plastic bags is advantageous because it limits
access of oxygen to the liquid insulant. Recently, an environ-
mentally friendly on-line innovative maintenance procedure was
found to remove a large fraction of the oxygen and water dis-
solved in the oil of freely breathing transformers [128].
The easiest and most convenient way to diagnose the state of
the insulation in liquid-filled equipment is to use the liquid as a
diagnostic medium. The development of several new laboratory
testing procedures for insulating liquids over the past 50 years
has resulted from cooperation between refiners, manufacturers,
and users of insulating oils. Mutually acceptable standards and
test requirements have been written, e.g., [33], [37], [39], [43],
[44], [47], [129]–[134].
Use of Additives
Various additives expected to improve the dielectric or physi-
cochemical properties of oil have been investigated during the
last 50 years. They include various chemicals that act as inhibi-
tors, passivators, electron scavengers, or pour-point depressants
[15], [23]. Small amounts of these additives improve oxidation
stability, optimize gas absorption and/or gas evolution, increase
dielectric strength or partial discharge inception voltage, protect
against catalytic reactions, and reduce electrostatic charging. In-
hibitors/additives are blended into the oil during the manufactur-
ing process or introduced during routine servicing.
Two primary phenolic antioxidants are approved for use in
electrically insulating oils, namely 2,6-ditertiary-butyl para-
cresol and 2,6-ditertiary-butyl phenol. ASTM D3487 [133] and
IEC 60296 [134] specify 0.08% (by mass) of 2,6-ditertiary-
butyl para-cresol, butylated hydroxytoluene, or 2,6-ditertiary-
butyl phenol for Type I oils; ASTM D3487 specifies 0.3% and
IEC 60296 specifies up to 0.4% for Type II oils. These addi-
tives enhance the resistance of the oil to oxidation and therefore
increase the expected lifetime of the insulation. Severe hydro-
processing, which effectively removes natural contaminants and
pro-oxidants such as sulfur, nitrogen, and oxygen compounds,
and some aromatics, enhances the effect of added synthetic anti-
oxidants [135]. The antioxidants perform better in these cleaner
oils since they do not have to counteract the negative aspects of
contaminants [135]. The cleaner the oil, the better is its antioxi-
dant function and the longer is the life of the transformer.
Aromatic compounds influence the oxidation resistance, gas-
sing properties, and impulse strength of oil. However the poly-
cyclic aromatic hydrocarbons are environment pollutants, and
some of them are recognized as cancer initiators. The 16 main
polycyclic-aromatic-hydrocarbon pollutants are listed in [136].
The polycyclic-aromatic-hydrocarbon content of oil must be
less than 0.1% (by volume) [13], [136], [137]. In order to avoid
labeling as carcinogenic, mineral oils are hydrotreated, which
results in the removal of most aromatic hydrocarbons, including
those that are beneficial [136]. Mono/dibenzyl-toluene, a new
type of impregnant for all-film power capacitors, has therefore
been added to mineral oil or to in-service oil-filled power trans-
formers since 2000 in order to increase the aromatic content of
the oil [24]. The addition of a few percent of mono/dibenzyl-tol-
uene can transform a gas-generating oil into a gas-adsorbing oil.
20 IEEE Electrical Insulation Magazine
In recent years, several failures of transformers and reactors
because of copper sulfide formation in the cellulose insulation
have been reported worldwide [138]–[140]. The concentration
of sulfur in mineral oil depends on the parent crude oil and the
degree and method of refinement. Under high electrical stress,
high temperature, and dissolved oxygen, sulfur can become cor-
rosive and react chemically with copper. Some transformer and
oil manufacturing companies recommend the use of metal pas-
sivators (Irgamet 39) in at-risk transformers. A concentration
of 100 ppm can be added to the oil during hot oil filtration or
refurbishment. Metal passivators react chemically with the sur-
face of a metal, forming a microscopic protective coating against
catalytic reaction.
Conclusions and Perspectives
Insulating liquids are a vital part of the electrical insulation
system in many types of electrical power equipment, includ-
ing transformers, bushings, cables, and capacitors. Each ap-
plication requires an insulating liquid with specific electrical,
chemical, and physical characteristics. However, research and
development on oil-filled circuit breakers and cables have al-
most stopped; extruded insulated cables (mainly polypropylene
or cross-linked polypropylene) have replaced oil-filled cables,
and circuit breaker technology has evolved toward the use of SF6
at high voltage and vacuum at medium voltage.
Mineral oils have been used in electrical apparatus for over
a century, and they have a long and proven track record. Qual-
ity and stability requirements have become more stringent over
time; the last 50 years have seen much improvement in quality
as refining technology has advanced through the use of catalytic
hydro-processing [26]. Because of their excellent performance,
availability, and low cost, mineral oils have met with little com-
petition. Concern over fire safety has prompted the development
of high-temperature mineral oils for critical applications.
PCBs, once promoted for their excellent fire-safety proper-
ties, have fallen out of favor since the mid-1970s because of the
health hazards that they present and their environmental per-
sistence. Their banning led to the development of several other
nonflammable halogenated liquids such as perchloroethylene,
which are however no longer marketed [65], mainly because of
strong public resistance to chlorination.
Growing demands for improved fire safety, material sustain-
ability, environmental friendliness and extended asset service
lifetimes have driven the development of alternative insulat-
ing liquids. Since the end of the 1970s, natural/synthetic esters,
which are less-flammable than mineral oils, have been developed
mainly for fire-safety applications. Hydrocarbon-based fluids
are only approximately 30% biodegradable, silicone oils have
very low biodegradability, poly-α-olefins have approximately
70% biodegradability, and pentaerythritol-based ester and veg-
etable oils are fully biodegradable. Nevertheless, mineral insu-
lating oil is still used extensively. Concomitant development of
advanced new materials (for high-temperature insulation) will
ensure a significant upgrade in the reliability of liquid-filled
power equipment. Reliable long-term performance of a biode-
gradable insulating liquid is crucial in any power equipment
[141]. It must have a sufficiently high withstand voltage over
the equipment lifetime, say at least 30 years, in order to ensure
return on investment.
No liquid is superior to all the others. Each has its advantages
and disadvantages, and must be used in specific applications.
Table 5 summarizes the main features and applications of sev-
eral types of insulating liquid.
Table 5. Properties of Insulating Liquids Used in the Last 50 Years (Updated Version of a Table Published in [19]).
Category Type of liquid
Mineral oils Naphthenic, paraffinic
High-molecular-weight Paraffinic
hydrocarbons
Vegetable oils Castor, soybean, cotton, palm, etc.
Synthetic liquids  
  Synthetic hydrocarbons Polybutenes
Alkylbenzenes
Alkylated hydrocarbons with
condensed aromatic rings (DIPN)
Alkylbiphenyls (MIPB)
Alkyldiarylalcanes (BT, DBT)
  Halogenated hydrocarbons Askarels (PCB)
Polychoro-diphenyl methanes
Polychoro-alcanes
  Silicone oils Poly-dimethyl siloxanes or PDMS,
poly-methylphenyl siloxanes
  Organic esters Simple esters
Phtalates
Complex esters, tetraester of
pentaerythritol
  Other liquids Ethers (alkyl-diphenyl ether,
ditolyl-ether)
Nanofluids
Mixed liquids
Cryogenic dielectric liquid (nitrogen)
September/October — Vol. 29, No. 5 21
What Does the Future Hold?
The inherent properties of mineral oils ensured their use as
electrical insulants over the last century, and will ensure their
continued use for decades to come. However, there are two rea-
sons why we should be seeking alternative natural insulating
liquids. These are the poor biodegradability of mineral oil, and
Applications Particular properties
Liquid-filled power equipment • Good resistance to oxidation
(transformers, circuit breakers, • Good viscosity index
load tap changer, etc.) • Relatively low fire point
• Low moisture tolerance
• Possible sulfur corrosion
Transformer, load tap changer • High flash point
Capacitors, transformers • Low dielectric losses at frequency higher that
1 kHz
• Readily biodegradable
• Low oxidation stability
   
Cables • Low dielectric losses
• Adjustable viscosity
Bushing, cables, capacitive dividers • Gas absorbing under partial discharges
• Good lightning impulse breakdown strength
Capacitors • Good lightning impulse breakdown strength
Capacitors • Readily biodegradable
• Gas absorbing under partial discharges
Capacitors • Gas absorbing under partial discharges
Capacitors and distribution • Nonflammable
transformers • Thermal stability
Transformers • Nonflammable
• Biodegradable
Transformers • Thermal stability
Traction and distribution • Good viscosity index
transformers • High flash point
• Gas absorbing under partial discharges
• High oxidation stability
• Low biodegradability
Capacitors • Relative permittivity, at 20°C, higher than 5
PCB substitute • Used to increase flash points of some liquids
Traction and distribution • High flash point
transformers • High moisture tolerance
• Readily biodegradable
• High oxidation stability
Capacitors • Relative permittivity, higher than 3 at 20°C
• Adaptability
Transformers • Adaptability
Capacitors, transformers • Adaptability
Superconductivity and cryogenic • Reduction or suppression of Joule heating
applications
 the growing demand for petroleum products, which could lead
to serious shortages as soon as the mid-21st century.
Given growing environmental concerns, fully biodegradable
oils, improved with suitable additives, will be important in the
future. Natural and synthetic esters are generally limited to dis-
tribution, traction, and mobile transformers, and other special-
ized applications. It is not yet known whether the use of natu-
ral esters in power transformers over lengthy periods will have
any adverse outcomes. Collection of track records for in-service
equipment, and continuing fundamental investigations, would
be expected to increase the use of natural esters in power trans-
formers [115]–[117], [142]–[145].
Nanotechnology is poised to affect the insulating-liquid in-
dustry dramatically [58]. The dielectric properties of nanoliq-
uids have not been fully explored. Although nanoparticles such
as metal oxides are already widely used, research in this area
is still at an early stage. It has been demonstrated that the heat
transfer properties of oils can be significantly improved by us-
ing nanoparticle additives [58], [67]. Ongoing research will in-
crease our knowledge of the fundamental mechanisms through
which nanoparticles interact with liquid matrices. The ever-
growing demand for electrical power will lead to a demand for
more highly rated oil-filled apparatus. A potential alternative in
many cases is the replacement of mineral oil with appropriately
modified nanoparticle liquids, with considerable cost savings.
Another important potential benefit of nanofluids is an increase
in breakdown voltage, which should allow more compact elec-
trical apparatus design.
Smart fluids, whose flow properties can be changed through
application of a low-power control signal, have also emerged
during the last decade [146], [147]. Two main classes of smart
fluid are available, namely electrorheological and magnetorheo-
logical. Electrorheological fluids generally consist of semi-con-
ducting particles suspended in a dielectric oil, whereas magneto-
rheological fluids use magnetizable particles suspended in a non-
magnetizable carrier liquid. In both cases the flow mechanism is
the same; excitation of the fluid by the appropriate field (electric
or magnetic) causes polarization and subsequent alignment of
the particles suspended within the liquid. It is believed that smart
liquids containing multifunctional nanoparticles could be cus-
tomized with specific properties, e.g., reduced dielectric loss, for
application in liquid-filled power equipment.
Superconductivity is also going to affect the future of insulat-
ing liquids. The critical temperatures of several high-tempera-
ture superconductors are around 135 K [148]. Around the world,
many research projects to develop commercial superconducting
devices are underway, seeking new materials with higher critical
temperatures [48]–[51], [58]–[76]. Cryogenic liquids are there-
fore going to play an important role in the future.
Acknowledgments
The author is much indebted to Dr. R. J. Fleming, co-editor-
in-chief EIM, for his help in improving the English expression
and quality of the manuscript.
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Issouf Fofana (M ’05, SM ’09)
received the electro-mechanical
engineering degree in 1991 from
the University of Abidjan (Côte
d’Ivoire) and the master’s and PhD
degrees from the Ecole Centrale de
Lyon–France in 1993 and 1996, re-
spectively. He was a postdoctoral re-
searcher in Lyon in 1997, and, from
1998 to 2000, at the Schering Insti-
tute of High Voltage Engineering
Techniques, University of Hanover,
Germany. He was a Fellow of the Al-
exander von Humboldt Stiftung from
November 1997 to August 1999. He joined the Université du
Québec à Chicoutimi (UQAC), Quebec, Canada, as an associate
researcher in 2000, and is now a professor there. Dr. Fofana has
held the Canada Research Chair, tier 2, of insulating liquids and
mixed dielectrics for electrotechnology (ISOLIME), since Sep-
tember 2005. He is registered as a professional engineer in the
province of Quebec, and is currently a member of the Executive
and Technical Committees of the IEEE CEIDP and the Interna-
tional Advisory Committee of the IEEE ICDL. He is a member
of the IEEE Task Force on atmospheric icing performance of
line insulators, and member of the ASTM D27 Task Group to
develop a test method for partial discharge inception voltage. He
has authored or coauthored more than 200 scientific publications
and holds 3 patents.