98-F-PQA-678

Properties of Alternative Liquids to

Mineraloil for Transformers

H. Borsi, E. Gockenbach

University of Hannover, Institute of Electric Power Systems,

Division of High Voltage Engineering, Schering-Institute
Callinstr. 25 A, D 30167 Hannover GERMANY

Key Words: Transformer insulation, Mineral oil,

ester liquid, breakdown voltage, gassing

Abstract Furthermore the performance of ester liquid

Since many years ester liquids are in use as an
alternative insulating liquid to mineral oil in
distribution transformers. The major
advantage, forcing the application of these
fluids, is their improved environmental
compatibility. But these liquids comprise
several additional advantages, which are at
first their lower inflammability. Power
transformers contain several tons of insulating
liquid, that may cause a long lasting pool fire
in case of a transformer tank rupture due to
winding failures.
Meanwhile there are a lot of good experiences
concerning the use of the ester liquid Midel
7131 in distribution transformers. This good
experience encourages the manufacturer of
transformers to use this liquid in power
transformers. Due to larger dimensions of
power transformers in comparison to
distribution transformers special consideration
is necessary.
The contribution presents some results of
investigations concerning the electric and
dielectric behaviour of ester liquids in
comparison to mineral based transformer oil.
Midel 7131 and mineral oil mixtures
concerning the electric behaviour is
introduced.
1. Introduction
Since the mid eighty the transformers have
been filled with different synthetic liquids
such as silicone, ester, perchlorethylene etc.
They have good dielectric, heat transfer and
aging properties, but because of their
relatively high cost their use has been limited
to special transformer applications [1]. One of
the major advantages, forcing the application
of ester liquids, is their improved
environmental compatibility. Additionally
these liquids comprise several extra
advantages, which are at first their low
inflammability. Transformers can contain
several tons of insulating liquid that may
cause a long lasting pool fire in case of a
transformer tank rupture due to winding
failures.

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20th International Power System Conference

Ester liquid and mineral oil are of an almost
similar density. They are completely miscible
at any ratio. Almost all electrical and
dielectrical properties of ester liquids are
similar to mineral oils despite the relative
permittivity εr, which is higher than those of
mineral oils. This is an additional benefit if
the ester liquid is used for impregnating
cellulose as the relative permittivity is closer
to the one of cellulose (about 5.6), thus
resulting in a more uniform electrical field
distribution within the combined insulation.
Some of the physical and electrical properties
of mineral based transformer oil and an ester
liquid Midel 7131 are shown in table 1. The
paper presents some results of investigations
on ester liquid Midel 7131and mixtures of
Midel 7131 with mineral oil. The investigated
mixtures are a combination of a widely
available mineral oil and a specific amount of
ester liquid, which has similar electrical
properties combined with fewer
environmental risks, less fire hazards and high
hygroscopicity.

Standard Midel 7131 Mineral oil *)

General physical properties
Density DIN 51757
at 20°C 0,96 g/cm3 0,856 g/cm3
at 90°C 0,915 g/cm3 0,810 g/cm3
Pour point -50 °C -20 °C
Toxicity non-toxic slightly toxic
Ability to biodegradability very high high
Water saturation
at 20 °C max. 2700 ppm max. 45 ppm
at 100 °C max. 7200 ppm max. 650 ppm
Heat transfer capability
Cinematic viscosity DIN 51561
at 20°C 63 mm2/s 16 mm2/s
at 90°C 7,7 mm2/s 2,3 mm2/s
Calorific capacity
at 20°C 0,165 W/(m K) 0,135 W/(m K)
at 90°C 0,155 W/(m K) 0,125 W/(m K)
Specific heat
at 20 °C 1,81 kJ(kg K) 1,85 kJ(kg K)
Expansion coefficient 7,5 10-4/K 6,9 10-4/K
Fire properties
Flash point DIN ISO 2590 310°C 150-175°C
Flame point DIN ISO 2592 257°C 130-135°C
3
Combustion heat 36,8 kJ/kg 10 46 kJ/kg 103
Self ignition temperature DIN 51794 405°C 330°C
Electrical properties (all the data are relative to a temperature of 23°C)
Breakdown strength (ac) DIN IEC 156
VDE 0370 Part 5 55 kV 60 kV
Permitivity εr
(50 Hz) DIN 57370/1 3,3 2,2
Dissipation factor DIN IEC 247
tan δ (90°C) VDE 0370 part 2 10 10-4 <10 10-4
Volume resistivity IEC 247 20 10-12 Ω cm 100 10-12 Ω cm
*) The data are mean value obtained from many manufacturers.
Table 1 : Technical properties of ester liquid Midel 7131 and mineral oil

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2. THE WATER IN INSULATING
LIQUID/PAPER
The water in the liquid originates from air
moisture in the case of ‘open-breather
transformer’ or ‘oil-conservator’ types, and as
a by-product of oxidation reactions taking
place in the liquid (and the thermal
decomposition of cellulose-based solid
insulating materials). Water can exist in
liquids in three states namely dissolved,
emulsified and dispersed. Insulating liquids,
such as transformer oil, have a low affinity for
water (however, the solubility increases
markedly with temperature for normally
refined naphthenic transformer oil). Their
electrical parameters are strongly influenced
by the water content, and a high moisture
level decreases the operational safety.
Moisture increases electric conductivity and
dissipation factor and worsens electric
strength [1-3]. Moisture in oil is measured in
parts per million (PPM) using the weight of
moisture divided by the weight of oil (µg/g).
When the moisture in oil exceeds the
saturation value, there will be free
precipitated from the oil in suspension or
drops. The oil in a transformer becomes
increasly contaminated as the transformer
ages in service. Contaminants include
particulate debris from thermal, oxidative, or
electrical degradation of oil or solid
insulation. The amount of absorbed furans
depends on the partition coefficients at given
temperature and the humidity in the paper. At
lower temperature, the absorption of furans is
higher and will be enhanced by a higher
amount of absorbed water. Absorbed water
can be released to the oil from the cellulose
insulation during thermal excursions, and
product water can be formed by cellulose
degradation during service ageing. Water in
mineral oil transformers also brings through
this procedure the risk of bubble formation
when desorption of water from cellulose
increases the local concentration of gases in
the liquid.
The purpose of the low limits suggested for
water in new oil contained in new
transformers is to insure that both the paper
3
insulation in a transformer and the oil itself
are adequately dry prior to filling the
transformer.
The relative Humidity
The relative humidity for oil is the dissolved
water content of the oil relative to the
maximum capacity of moisture that the oil
can hold. Because the saturation mixing ratio
is a function of pressure, and especially of
temperature, the relative humidity is a
combined index of the environment and
reflects more than water content.
The relative humidity Wrel for a given
temperature T, is defined in terms of the
absolute water content in liquid Wabs versus
the saturation limit WL(T) so that:
Wrel =
Wabs
(1)
WL (T )
The water maximum solubility at an absolute
T can be expressed in this form:
−
H
W L = K .e T (2)
The constants H and K depending on the
liquids itself are to be determined
experimentally.
The water saturation of the pure liquids as
well as the mixtures have been experimentally
determined. The samples were exposed for a
few weeks in a closed artificial humid
environment at a given temperature. The
water content was regularly controlled. The
saturation limit was achieved when the
obtained water content is found to remain
constant. Figure 1 depicts the saturation limit
of the pure liquids as well as for the mixtures.
Mathematical approach of data suggests the
existence of some kind of relationship
between the saturation limit WL of the
mixture, the temperature and the ester
amount. The saturation limit WL of the
mixture can be describe as a mathematical
function of the temperature T and the ester
amount X:
 Surface Degradation of Outdoor Polymeric Insulators Resulting from Electrical and Environmental Stress
20th International Power System Conference
⎛ − 0.17T + 4.2 ⎞
W L = (4.9T − 37 ) exp⎜ X⎟ (3)
⎝ 1000 ⎠ impregnated paper is shown in figure 2
Such a function can be useful for providing
information concerning each amount of
mixture.
Oil and other materials in a transformer
degrade with time in service and many of the
products of degradation are reflected in the
acid number, the water content of oil in a
transformer as it ages and consequently on
the dielectric properties of the oil.
The water in the oil equilibrates with water
retained in the paper insulation of the
transformer. The correlation of moisture
10000
1000
100
WL [ppm]
10
1
4.2E-3 3.8E-3
-25
Figure 1: saturation limit of the pure and mixed insulating liquids versus temperature.
3. Investigated parameters
The aim of the investigations was to
determine those physical, electrical, dielectric
and aging properties, which, according to the
IEC standards, are used to classify
transformer oils as to guarantee their quality
and life. Although all the properties listed in
table 1 are important, some have a special
content of the insulating liquids and
exemplary for cellulose paper impregnated
with mineral oil, silicone liquid and ester
liquid.
As can be seen, there is no significant
difference between the silicone liquid and the
mineral oil. This behaviour is due to the
moisture content of the liquids, which is
almost the same for the investigated
temperature (20°C). The curves also show
that using an insulating liquid with a high
water saturation limit (ester liquid) is
combined with a lower water content in the
paper compared to other insulating liquid with
the same absolute water content but a lower
water saturation limit.
Mineral oil
Mineral oil + 10% ester
Mineral oil + 20% ester
Mineral oil + 50% ester
Ester liquid
3.4E-3 3.0E-3 2.6E-3
1/T [1/K]
0 25 50 100
T [ C]
merit for the characterisation of an insulating
liquid, especially those, that are likely to vary
significantly with the oil purity and
composition as well as with temperature and
electric field. The most important properties
are the electrical strength and viscosity,
followed by dissipation factor (tan δ), water
content and neutralisation number. The water
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 Surface Degradation of Outdoor Polymeric Insulators Resulting from Electrical and Environmental Stress
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content varied between 10 and 40 ppm for the
mineral oil, between 10 and 185 ppm for the
mineral oil plus 10% ester liquid, between 10
and 365 ppm for the mineral oil plus 20%
ester liquid and between 10 and 1120 ppm for
mineral oil plus 50% ester liquid
3.1 Breakdown voltage
The AC electric strength, also known as
breakdown voltage at power frequency, is the
most often controlled parameter describing
the function of a liquid as an insulator.
For measurements of the electric strength at
various temperatures and for various water
10
WPaper [%]
0.1
1 10
WLiquid [ppm]
Figure 2: Moisture equilibrium of different liquids - cellulose paper complex at 20°C
Almost all the transformers are exposed to
outdoor conditions, they are therefore subject
to temperature variation. For example during
cold winter days, the temperature can fall
under 0°C, while in tropical regions and
during hot summer days the temperature can
rise up to 30°C or more. The temperature
variation for the investigations (0 - 100°C)
was chosen in order to simulate normal
operating conditions as well as critical
situations in a transformer.
The measuring set-up of the AC breakdown
voltage is depicted in our previous work [1].
The temperature dependencies of the results
concerning the mineral oil and the mixtures
5
contents, the respective specimens were
placed in the virtually homogeneous field of
the VDE hemispherical set-up and subjected
to a
50 Hz voltage increased at a rate of 2 kV/s up
to breakdown. Between individual
measurements, a glass stirrer was used to
remove any solid decomposition products
appearing between the electrodes, and to take
away any gaseous decomposition products
back in the liquid. Before and after each
measurements series, the electrodes were
purged of the decomposition products of
preceding breakdowns.
Ester liquid
Silicon liquid
Mineral oil
100 1000
with ester liquid of the average values from
all water contents at a given temperature are
summarised in figure 3. The values for the
aged mixtures specimens are sometimes
found to be higher than those of new
specimens particularly at high amount of ester
liquid. This effect is more highlighted through
the addition of 50% of ester liquid on the
mineral oil. A general increase of the
breakdown voltage at low temperatures in
connection with ester liquid amount is
observed, while the difference between the
electric strength of the mineral oil and these
mixed liquids at higher temperature is
somewhat smaller.
 Surface Degradation of Outdoor Polymeric Insulators Resulting from Electrical and Environmental Stress
20th International Power System Conference

80
0% unaged
kV
70 0% aged

10% unaged
60
10% aged

50 20% unaged
Breakdown voltage

20% aged
40
50% unaged

30 50% aged

20

10 Limit for new

oils under
IEC 296 or
0 DIN VDE 0370
0 20 60 90 C
Temperature
Figure 3 : Average values of the breakdown voltage of the mineral oil and
the mineral oil mixed with different amount of the ester liquid.

The most important and therefore most often
controlled parameter of a liquid insulant is the
breakdown voltage according to IEC 60296.
At low temperatures and after an aging with
copper, zinc, aluminium, each one 3 g/l as
Catalysts the blends performed in most cases
better than the pure mineral oil. The
breakdown behavior for different relative
moisture contents of mineral oil and Midel
7131 is depicted by Figure 4. The breakdown
voltages shown are the average values for all
water contents at a given temperature.
The behavior of the blend is somewhat similar
to mineral oil. The difference between the
mineral oil and a mixture of mineral oil/Midel
7131 and the reason for the improved
performance of the mixtures at low
temperatures is the fact, that the absolute
water content of the mixture is higher than
that of the pure oil to reach a certain grade of
relative saturation. Thus the breakdown
voltage, which is mainly influenced by the
relative water content at a certain temperature
is, for the same absolute water content, for the
6
blend higher than those of the pure mineral oil
as the relative humidity is lower.
The breakdown voltage of the mixtures is less
temperature-dependent than those of the pure
mineral oil. The reason is the difference in the
water saturation limit. All the breakdown
voltages for new and aged liquid mixtures are
greater than the limit of 50 kV at 20°C
required by VDE for unused oils.
The ester liquid is beneficial for aged mineral
oil as well as when they are both aged
together. This aspect can be very helpful
when retrofilling service-aged mineral oil
filled transformers with liquid mixtures.
Another important factor is the breakdown
behavior of the cellulose that is immersed in
the liquid. The cellulose PSP 3010 has been
representing approximately 30 years of
transformer operation. It becomes obvious,
that in all cases the mixtures perform better
than the pure mineral oil. Also the aging of
the cellulose is lowered by the application of
Midel what may be traced back to the lower
generation of acids during aging.
 Surface Degradation of Outdoor Polymeric Insulators Resulting from Electrical and Environmental Stress
20th International Power System Conference
80
kV
70
60
U1
50
40
U2
30
20
10
0
0 20 40R1 60 R2
Relative water content Wrel (%)
Figure 4 : the AC breakdown voltage versus the relative humidity for the mineral oil and ester liquid.
3.2 Gassing behaviour of the insulating
liquids at thermal stress
Insulation damages during operation are
normally accompanied by gas production (and
can cause PD). The gas can either be solved in
the liquid or they remain unsolved. The
solved gases are detected with Diagnostic Gas
Analysis (DGA) methods [4]. The unsolved
gases which are generally produced by large
faults in a short time or by a small faults long
time after gas saturation in the liquid arrive on
their way up into the Buchholz-relay. The
solved and unsolved gases have been used
since many years ago for the determination of
the insulation condition (over-voltage, over-
current, temperature of the hottest point, etc.).
The thermal stress of the liquid specimen are
simulated in a set up according to (figure 5).
It consists of a Borosilicat-vessel and a teflon-
2.5 mm
E Mineral oil
B Mineral oil + 20% Ester liquid
Limit for unaged oil
Limit for aged oil
80 100 120 140 160
cover with clamps to fix the heating wire. The
heating wire is made of Konstantan.
The temperature around the heating wire is
assumed to be constant, it was measured with
a NiCrNi-temperature sensor. The heating
current is delivered via a power current
transformer. With an ampere-meter connected
to the primary and secondary circuits the
temperature at the wire can be regulated. The
funnel-shaped teflon device over the heating
wire allows the generated gases to go directly
to a burette from where they can be measured.
This test set up allows a local controlled
heating of the liquid up to over 1000°C. The
calculation of the local temperature of the
liquid surrounding the heating wire is
obtained using thermodynamic approach. In
the area of the heating wire, the temperature is
considered to be constant, the radiated heating
energy is therefore.
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 Surface Degradation of Outdoor Polymeric Insulators Resulting from Electrical and Environmental Stress
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1 2 4 5
A

230 V
50 Hz 6
V

A 3

11 10

1. Auto-transformer 7. Clamps
2. Current transformer 8. Funnel
3. Measuring transformer 9. Heat element
4. to Argon 5,6 vessel 10. Test vessel
5 Sampling for gas Chromatography 11. Equalising vessel
6. Measuring burette

Figure 5 : Test vessel and set up for local heating of the insulating liquid.

⎡⎛ T ⎞ 4 ⎛ T ⎞ 4 ⎤ T2 : liquid
Q ab = α Em. ⋅ AHeating ⎢⎜⎜ 2 ⎟⎟ − ⎜⎜ 1 ⎟⎟ ⎥ (4) dH : Surrounding temperature (T ≈298 K)
⎢⎣⎝ 100 ⎠ ⎝ 100 ⎠ ⎥⎦
lH : Temperatur im Bereich dϑ
Q zu = P = I 2 ⋅ R (5) Diameter of the heating wire
ρ ⋅lH Length of the heating wire
Q zu = I 2 ⋅ (6)
d H 2 ⋅π / 4
ρ ⋅lH With the assumption of a constant
4
I2 ⋅ temperature around the heating wire
4 ⎛ T ⎞ d H 2 ⋅π / 4
T2 = 100 ⋅ ⎜⎜ 1 ⎟⎟ + (7) (10mm≤dϑ≤20mm) and a radiation coefficient
⎝ 100 ⎠ α Sr . ⋅ d ϑ ⋅ π ⋅ l H
αStr.=3...5,77W/m2K4, the results of the
calculation of the heating temperature (around
where: the wire) are depicted by figure 6.
Qab : Radiated heat power This figure shows the results of the
Qzu : Supplied thermal output power investigations performed for a maximal
ρ : Specific resistivity current of 50 A, on the assumption of a
αStr. : Radiation coefficient (3...5,77 W/m2K4) homogeneous heating area lH of
dϑ : Area of constant temperature (φ ≈10-20 approximately 15 mm around the heating wire
AHeating : mm) with maximal temperatures of over 800°C.
T1 : Heating wire surface in the isolating

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 Surface Degradation of Outdoor Polymeric Insulators Resulting from Electrical and Environmental Stress
20th International Power System Conference

Completing measurements acknowledged the

calculation.
For the mineral oil the first noticeable un-
dissolved gas initiation appear at a
temperature ranging from 250 to 300°C while
for the ester liquid a temperature of 350 to
400°C is required.

1400

α str. = 3 und dυ = 10 mm
C
1200
α str. = 3 und dυ = 20 mm
α str. = 5,77 und dυ = 20 mm
1000

T2 800

600

400

200

0
0 5 10 15 20 25 30 35 40 45 50
Heizstrom I (A)
Figure 6 : Calculated temperature T2 at the heating wire versus the heating current for different emission
coefficient and different zones with constant temperature around the heating wire (αStr. = 3...5,77 W/m2K4).

Through a small increase in the temperature, a
exponential gassing tendency for the
investigated insulating liquids is to be
observed. At a given temperature, the total
un-dissolved gas generated by mineral oil is
much higher than that of ester liquid as
previously investigated. As for example, the
behaviour of the mixture with 20% ester
liquid is depicted in figure 7.
At a given temperature, mineral oil generates
much higher unsolved gas than ester liquid
and the mixture of mineral oil with 20% of
ester liquid.
It is to be noticed that the solubility of gases
such as hydrogen is low in insulating liquids
and gas bubble readily can form in the liquid
(in the vicinity of discharge of local heating.
Gas bubbles are weak dielectrics and their
presence can intensify the discharge – corona-
or initiate further breakdown in highly
stressed regions nearby.
The higher the gassing tendency, the higher
the risk of breakdown inception in the
insulating liquid. Adding ester liquid to
mineral oil helps decreasing the gassing
tendency under local thermal stresses.

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6
Ester liquid
5 Mineral oil + 20% Ester

Mineral oil
4
Gas content (ml)

0
0 200 400 600 800 C 1000
Temperature

0 5 15 25 36 A 50
Heizstrom I
Figure 7 : Gas content evolution versus temperature of
different insulating liquids submitted to local heating for a period of 180 s.

4. Conclusions 7131 and mixtures of Midel and mineral oil

Ester liquid Midel 7131 has good electric, have in comparison to mineral oil a lot of
dielectric, thermal, aging and environmental advantages as insulating and cooling medium
characteristics. Furthermore it has - in in transformers.
comparison to mineral oil - much lower
inflammability and thus much lower fire risk. 5. References
As moisture is ’enemy number one‘ for [1] Borsi, H., Gockenbach, E., Fofana I., Bastian, J.
transformer insulations, the high saturation "Verfahren zur Verbesserung der elektrischen
limit of ester liquid, almost more than 50 und Alterungseigenschaften von
mineralölgefüllten Hochspannungsgeräten durch
times higher than that of mineral oil, reduces Beimischung einer hygroskopischen
the moisture content in the solid insulation Isolierflüssigkeit", Deutsches Patent und
due to water diffusion into the liquid, and as a [2] A Sierota and J. Rungis, "Electrical Insulating
result, the dielectric properties of the mixed Oils- Part 1: Characterization and Pre-
liquids are changed slightly. If necessary, treatment of New Transformer Oils", IEEE
excess moisture can be removed from the Electrical Insulation Magazine, Vol. 11, No.
fluid using standard techniques. Altogether, if 8, pp. 8-20, 1995.
[3] K. Dumke, "Untersuchungen an einer
the transformer usually operates at very low Esterflüssigkeit als Isolierstoff für
temperatures, the application of the mineral Transformatoren", PhD Thesis University of
oil and ester liquid midel 7131 mixtures offers Hanover, 1998.
increased insulation reliability. The dielectric [4] Kan, H., and Miyamoto, T. "Proposals for an
strength at low temperatures is higher, than improvement in transformer diagnosis using
that of pure mineral oil. Therefore, the lower Dissolved Gas Analysis", IEEE Electrical
Insulation Magazine,Vol. 11, No. 6, pp. 15-
risk of breakdown of the insulating liquid at 21, 1995, Markenamt DE 199 46 641 A1,
low temperatures reduces the probability of a April 200
transformer malfunction. Ester liquid Midel
10