IEEE Transactions on Dielectrics and Electrical Insulation Vol. 23, No.

5; October 2016 2957

Conductivity and Permittivity of Midel 7131: Effect

of Temperature, Moisture Content, Hydrostatic Pressure
and Electric Field
Torstein G. Aakre, Torbjørn A. Ve and Øystein L. Hestad
SINTEF Energy Research
Sem Sælands vei 11
NO-7465 Trondheim, Norway

ABSTRACT
Knowledge of the conductivity and permittivity of materials used in subsea connectors
is needed to predict the electric field distribution in the connectors. The synthetic ester
Midel 7131, being one of several dielectric liquids used in subsea connectors, has been
chosen as a relevant candidate material. The conductivity and permittivity of Midel
was measured by an IRLAB conductivity meter and an IDA insulation diagnostic
analyzer. The temperatures were 30, 60 and 90 °C, the hydrostatic pressures were 0.1,
1 and 10 MPa (1, 10 and 100 bar), the water content varied between 20 and 5600 ppmw,
and the applied electric fields varied between 2.5 V/mm and 9.4 kV/mm. The results
show that the conductivity increases linearly with increasing levels of water content,
whereas the temperature dependency follows an Arrhenius relation. The conductivity
was found to increase slightly with increased pressure, the differences between samples
were higher, rendering this increase insignificant. Measurements of the permittivity
showed a linear increase in permittivity with increasing water content. The measured
permittivity was found to follow the Clausius-Mossotti relation when varying the
temperature and hydrostatic pressure. Based on the dependence of the conductivity
and permittivity on water content, it seems that water molecules in Midel have a
reduced degree of mutual interaction compared to liquid water.
Index Terms — Conductivity, dielectrics, oil insulation, permittivity, reliability,
subsea connectors.

1 INTRODUCTION
ELECTRIC subsea installations are essential for a series of
applications including subsea factories for oil and gas
production, and off-shore wind farms. In order to facilitate the
creation of reliable modular systems that can be assembled
and disassembled subsea, the development of subsea
connectors is required. Currently these connectors are only
available for medium and low voltage AC. In order to develop
the next generation of subsea connectors for higher voltages
and for DC, it is important to be able to predict the electric
field distribution in the system over time. To do so accurately,
the permittivity and conductivity, as well as how they are
affected by factors such as hydrostatic pressure, water content,
temperature and electric field, need to be known. This is
directly related to the short and long term reliability of the
connectors, which is of special importance for subsea
application where the cost of repair and replacement of broken
units is extremely high.
Manuscript received on 14 April 2016, in final form 6 July 2016,
accepted 8 July 2016.
DOI: 10.1109/TDEI.2016.005992
The results presented in this paper have been obtained with
a synthetic ester, Midel 7131, which is a well-known
dielectric liquid used for high voltage applications. The main
reason for using this kind of liquid in subsea connectors is that
it can absorb a large amount of water compared to traditional
mineral oils, has a high fire point, and are biodegradable. The
ability to absorb water is critical, as water will enter the
system over time, as dissolved water through diffusion, or as
liquid water during subsea mating and de-mating. A reservoir
of dielectric liquid able to absorb such excess water will limit
the impact on the rest of the connector, reducing the risk of
connector failure and increasing lifetime.
To evaluate if absorbed water will affect the electric field
distribution, the dielectric properties of Midel at different
levels of water content, at relevant temperatures and at
relevant hydrostatic pressures, must be known. Therefore,
measurements of the conductivity and permittivity of Midel
with water content between 20 and 5600 ppmw were
conducted at temperatures of 30, 60 and 90 °C, at hydrostatic
pressures of 0.1, 1 and 10 MPa (1, 10 and 100 bar). The
applied electric fields were between 2.5 V/mm and
9.4 kV/mm.

Authorized licensed use limited to: UNIVERSIDAD MANUELA BELTRAN. Downloaded on May 04,2020 at 01:19:07 UTC from IEEE Xplore. Restrictions apply.
2958 T. G. Aakre et al.: Conductivity and Permittivity of Midel 7131: Effect of Temperature, Moisture Content, Hydrostatic Pressure

This paper has been divided into five sections including this 1 h 0

 
a  (4)
introduction. In the next section, a short recap of the theory of
conductivity and permittivity of dielectric liquids is given.
  A 
i
i
2  Gi 2 e 2 k B TK
 qi      

The third section describes the methods used to measure the which can be simplified to
conductivity and permittivity of Midel 7131. After this, the
Ea
main section of the paper follows, in which the results are a 
presented and discussed. Finally a short conclusion is given.   i
 i0  Ai   e
2 k B TK
(5)

Here, the activation energy is Ea = - Δh0/2, and

2 THEORETICAL CONSIDERATIONS
Ai  
2
An outline of the known theory of conductivity and  i0

 Gi0.5   
qi   i   i is a species-specific constant
 Ai  

permittivity in liquids is given in this section. This is not
intended as a review, but rather as an aid when discussing the for the conductivity containing the mobility and charge of the
measurements. The reader is referred to the works by Denat ions. In equations (1) to (4) the concentrations were given in
[1] and Schmidt [2] for more information on this topic. #/m3, denoted by curly brackets. In equation (5), and in the
rest of this paper, the concentrations are given in kg/106 kg
2.1 ELECTRIC CONDUCTIVITY IN LIQUIDS (ppmw), denoted by square brackets. The conversion is
The conductivity σ of a medium is a measure of its ability A  Ai  M m1   , where Mm is the molar mass of the species
to transport charge in an electric field. The conductivity is and ρ the density of the liquid, approximated to the density of
dependent on the mobility μ of the charge carriers [2] Midel.

  ni  qi
all species i
 i
(1) 2.1.2 EFFECT OF WATER
Inserting the relevant numbers for Midel and water into
where ni is the density of free charge carriers, such as ions, equation (5), gives an approximate formula for the
and qi is the charge of the charge carrier. Dissociation of conductivity of humid Midel:
molecules into ions is typically considered the main source of Ea Ew
1  
(6)
charge carriers in dielectric liquids [1].   Midel  2
0
 M e k B TK
 H 2O    w0 e k B TK

where Ea and Ew are the activation energies for dissociation of

2.1.1 EFFECT OF TEMPERATURE
The dissociation of a molecule A into ions B+ and C- in a
liquid is given by
kD
(2)
a  A  b  B  c C 
kR
where kD and kR are the dissociation and recombination
coefficients, and a, b and c are stoichiometric coefficients. In
the following, b = c = 1 which gives the concentration of ions
B+ and C- as {B+} = {C-} = ni = n/2. Dissociation of water has
a = 2 [3] and Midel is assumed to have a = 1.
The equilibrium constant K is the relation between the
concentrations of the molecules and ions
0
Midel and water, and  M and  w0 are constants for Midel
and water, respectively. The relative concentration of Midel is
close to 1 since the relative concentration of water is small.
The activation energy for water, Ew, is estimated to 0.54 eV,
based on data for the equilibrium constant for dissociation of
water molecules [5].
An important assumption is that the main contributor to the
conductivity in wet Midel is dissociation of water and Midel
molecules into ions. Thus the contribution from other
contaminants/molecules is not explicitly included in equation
(6). Note, however, that the contribution from other
contaminants will be included in the first term of the equation,
giving the conductivity for dry Midel, thus the conditioning of
the liquid will influence that term.

h 0
2.1.3 EFFECT OF PRESSURE
K
Aa  Aa  Gi  e

k B TK (3) Walden's rule states that the mobility of ions, μ, multiplied
Bb  Cc ni2 by the dynamic viscosity, η, is constant [2]
  const (7)
where the temperature dependence originates from the
van't Hoff equation [4] where Δh0 is the difference in the The viscosity increases slightly with pressure. The pressure
enthalpy between the two states, TK is the temperature in dependence of the viscosity of water is approximately given
degrees Kelvin, G is a constant and kB is the Boltzmann by a linear function η ≈ αp + β where α and β are linearization
constant. constants [6]. Midel has a compressibility similar to water.
A temperature dependent expression for the conductivity is Assuming a linear dependence to pressure is therefore a
found by combining equations (1) and (3) reasonable approximation for Midel as well. Based on this

Authorized licensed use limited to: UNIVERSIDAD MANUELA BELTRAN. Downloaded on May 04,2020 at 01:19:07 UTC from IEEE Xplore. Restrictions apply.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 23, No. 5; October 2016 2959

approximation the pressure dependence of the conductivity is electric susceptibility. At low frequencies the current will be
given by dominated by the conductivity of the dielectric.
1 1 1   (8) The Clausius-Mossotti equation gives the relation between
    1  p    ' ' p the density ρ and permittivity [12],
 p      
1  2
The viscosity of a liquid changes with temperature [2]  r    , (14)
1  
Ub
(9)
 (TK )  k BTK  e k BTK where  is the molecular polarizability of the liquid.

where Ub is a potential barrier. 2.2.1 EFFECT OF TEMPERATURE

The temperature dependence of the density of Midel is
2.1.4 EFFECT OF ELECTRIC FIELD known from literature [13]
Ions in a liquid with an applied electric field may remain in  TC   0.7339  TC  985 (15)
the liquid, or become localized at the electrodes. A useful
number to distinguish between these regions is the ratio where ρ is given in kg/m3 and TC is the temperature in degrees
between the transit time and ionic relaxation time [1] Celsius.
Combining equations (15) and (14) gives an estimate of the
tm  d2
C0    0
td 
    0  rV  (10) temperature dependence of the relative permittivity of Midel
as
where tm is the transit time, td is the relaxation time of ions, σ0 1  2  0.7339  TC  985 (16)
is the low field conductivity, and d the distance between the    rMidel TC    
1    0.7339  TC  985
electrodes. If C0 1, then the transit time is higher than the
relaxation time and there is an equilibrium between
dissociation and recombination. The conductivity is in this 2.2.2 EFFECT OF WATER
case Ohmic. If C0 1 the transit time is smaller than the
relaxation time and a sweep-out of ions occur. A new An empirical formula for the relative permittivity of water
equilibrium is then established, where the conductivity is as a function of temperature is known [14],
limited by the dissociation process.  rH O  87.740  0.40008TC  9.398  10 4 TC2 (17)
2
A reasonable value for ionic mobility in Midel is 6
2×10-7 m/Vs [7]. Using this, together with a conductivity  1.410  10 TC3 .
value of 10 pS/m and a relative permittivity of 3, which are A linear combination of the water permittivity and Midel
typical values for Midel [8], results in C0 1 for the voltage permittivity can be assumed if there is a good mixing of water
range in this study, E < 10 kV/mm. The conductivity as a and Midel [15]. This assumption requires that the permittivity
function of the electric field E is therefore given by the quasi- contribution per unit of each component does not change with
Ohmic relation [1] concentration. Combining equation (14), (15) and (17) gives

 ( E )  '0 

F E / TK2  (11)
the following relation for permittivity in humid Midel

E  r  p, TC , H 2O   Midel   rMidel  p, TC  (18)

 
where F E / TK2 is given in [1, 9] and σ'0 is a fitting constant.  H 2O   rH O  p, TC .
2

Ultra-pure liquid water has a conductivity of 5 μS/m and a

relative permittivity of 78 at 25 °C, and the mobility of ions in 2.2.3 EFFECT OF PRESSURE
water can be approximated to 2 10-7 m/Vs [10], results in
The compressibility κ of liquids is defined as
C0 1 for the voltage range in this study, E < 10 kV/mm. The
1  (19)
electric field dependent conductivity will therefore be given   
by the Onsager relation [1, 9]  p
which gives
 
1 (12)
 ( E )  '0 F E / TK2 2 (20)
   0 e p
2.2 PERMITTIVITY IN LIQUIDS
where ρ0 is a constant. Thus the increase in pressure will have
The current density J in a dielectric stressed by an AC field
a small effect on the density of the liquid, and thus on the
is given by [11]
permittivity of the liquid. Both Midel and water are nearly
    (13) incompressible, meaning that this can typically be neglected at
J    i 0 1   '    i   ' '    moderate pressures. Water has compressibility κ~10-4 MPa-1
 
   0  [5], which means that equation (20) can be linearized for
where ω is the angular frequency of the voltage, and χ is the pressures below 100 MPa (1000 bar).

Authorized licensed use limited to: UNIVERSIDAD MANUELA BELTRAN. Downloaded on May 04,2020 at 01:19:07 UTC from IEEE Xplore. Restrictions apply.
2960 T. G. Aakre et al.: Conductivity and Permittivity of Midel 7131: Effect of Temperature, Moisture Content, Hydrostatic Pressure

Table 1. The test matrix is all permutations of the listed variables. cylindrical electrodes made of stainless steel, within a steel
Parameter Unit Range Test container, Figure 1. A 10V square wave of 0.5 Hz is applied
over the electrodes, and the current flowing through the liquid
Temperature °C 30, 60, 90 Both
Pressure MPa 0.1, 1, 10 IRLAB is measured. The IRLAB equipment is able to measure
Relative Saturation % 0, 50, 90 Both
conductance values as low as 2×10‐14Ω‐1, corresponding to a
Voltage kV 0.2, 5, 10, 15, 20, 25, 30 IDA conductivity of 3.75×10-15 S/m, with an error of less than 1 %.
Frequency Hz 1 mHz to 100 Hz IDA The conductivity is measured according to IEC 60270.
The IRLAB test cell was placed in a temperature controlled
2.3 WATER SATURATION IN MIDEL pressure vessel filled with Midel 7131.
The relative water saturation concentration in Midel, The test cell was filled with conditioned Midel and placed
follows an Arrhenius relation [16] in a pre-heated pressure vessel containing Midel. The two
B Midel volumes were not mixed. A data logging unit recorded

H 2Os TK   A  e k B TK
,  (21) the conductance, pressure and temperature every five minutes.
where A = 458600 ppmw and B = 0.138 eV. The water content Measurements were performed at 0.1, 1 and 10 MPa (1, 10
in Midel is given as relative saturation (RS) in percent: and 100 bar) at 30, 60 and 90 °C. The initial pressure was 0.1
RS 
H 2O 100% . MPa (atmospheric pressure) and was increased after a stable
H 2Os conductance was achieved. The test cell was pressurized for 1
hour at both 1 and 10 MPa (10 and 100 bar) before
3 METHOD AND MATERIALS measurements were done. In addition, the conductance was
logged during a 3 minute stepwise pressure reduction from 10
The major part of the measurements have been performed
to 0.1 MPa (100 to 1 bar), where a delay of 30 seconds was
with an IRLAB test cell, model Cl-2 [17, 18]. An IDA 200 HV
used between each measurement.
unit was used to verify the results obtained with the IRLAB unit,
and to study the effect of increased electric field. The test matrix Some water may diffuse into/out of the IRLAB test cell.
for the measurements of both IRLAB and IDA is shown in Table The water content was therefore measured by Karl Fischer
1. titration before and after each measurement series, and a linear
interpolation is used to obtain a more realistic estimate of the
3.1 PREPARATION OF SAMPLES water content at the time of measurements.
The samples were prepared by drying Midel in a vacuum
chamber at 80 °C for at least 48 hours until the liquid had 3.3 CONDUCTIVITY AND PERMITTIVITY
reached a water content of approximately 20–40 ppmw, MEASUREMENTS WITH IDA
corresponding to a relative concentration of 1-2 % at 30 °C. The IDA 200 HV unit was connected to a test cell of
The different humidity levels were obtained by humidifying approximately 2 liters with two circular electrodes (Ø 12 cm)
the dried liquid in a custom made climate chamber. The in a parallel plane configuration, see Figure 2. The gap
humidity was monitored by a relative humidity sensor, and between the electrodes is 3.2 mm, giving a capacitance of
typically stabilized after approximately six hours. The samples 22.5 pF in air, which is the same as the capacitance of the
were left in the setup for 24 hours to ensure ample time for the IRLAB test cell.
sample humidity to stabilize. The test cell was first filled with conditioned Midel and
3.2 CONDUCTIVITY AND PERMITTIVITY placed in a heating cabinet. All measurements using the IDA
MEASUREMENTS WITH IRLAB setup were conducted at atmospheric pressure.
The IRLAB test cell has an internal volume of The IDA unit was used to find the frequency dependence of
approximately 200 mL. It consists of two concentric the complex permittivity. At low frequencies, losses are
mainly due to the conductivity of the liquid. The conductivity

Figure 1. Sketch of the conductivity test setup with IRLAB. The IRLAB
test cell Cl-2 is placed in a temperature controlled pressure vessel. The test
cell consists of two concentric cylinders within each other placed in a
closed container (Faraday cage).
Figure 2. Sketch of the IDA 200 HV test setup. A closed test cell is
placed in a heating cabinet for temperature control. The gap between the
high voltage electrode and the guarded measurement electrode is 3.2 mm.
The electrodes are connected to the IDA 200 HV unit that measures the
dielectric losses.

Authorized licensed use limited to: UNIVERSIDAD MANUELA BELTRAN. Downloaded on May 04,2020 at 01:19:07 UTC from IEEE Xplore. Restrictions apply.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 23, No. 5; October 2016 2961

can therefore be estimated based on the measured losses at
frequencies below 1 Hz using equation (13). The
measurement was performed in the range from 1 mHz to 100
Hz.
activation energy for water Ew obtained from literature [5]. The
regression was performed using unconstrained nonlinear
multivariable minimization based on the Nelder-Mead
algorithm. The activation energies are assumed to be constant
and independent of the concentration of water. A similar
calculation was performed for the IDA measurement results.
The fitted parameters for both IRLAB and IDA measurements
are given in Table 2.
The R2 value of the IRLAB measurements is higher than for
IDA. This is due to a larger spread in water content for the
samples tested with IRLAB, and there being fewer samples
tested with IDA. Similar values were obtained for all parameters
with the two methods. The activation energy in mineral oil has
been reported to be 0.54 eV [19], which is relatively close to the
values found for Midel in this study, 0.42–0.45 eV.

4.1.1 EFFECT OF TEMPERATURE

Figure 3. Illustration of the electric field dependent conductivity for
Midel and water. Color denotes temperature and line style denotes liquid.
The figure follows equations (11) and (12). Additionally two concentration
dependent mixtures are plotted with water content as used in the
measurements.
The temperature dependence of conductivity as presented in
Figure 4 shows that equation (6) fits the results very well,
confirming that the temperature dependence follows an
Arrhenius relation. This indicates that the ionic dissociation of
two donor species is the dominant charge generation
mechanism for the temperatures included in the
measurements.

4.1.2 EFFECT OF WATER

Liquid water has strong intermolecular forces. Groups of
mutually interacting water molecules will therefore behave
significantly different from solitary molecules. Equation (6)
assumes that the ionic dissociation of water occurs with two
water molecules as the reactants, producing two ions. The
good fit between equation (6) and the measurement results
imply that most water molecules in Midel are in contact with
other water molecules (water clusters). By using equation (6),
it is assumed that the dissociation of water molecules has
similar temperature dependence in the water clusters as in
liquid water.
at The second part of equation (6) gives the contribution from
Figure 4. Conductivity as function of water content in Midel 7131
ambient pressure measured using the IRLAB setup. Different levels o
f water to the conductivity of humid Midel. By inserting the
relative saturation are shown for the different temperatures. The solid lines values obtained by IRLAB in Table 2 into equation (6), at
r
are given by equation (6) with the parameters given in Table 2. Values fo 30 ˚C and 2000 ppmw water gives the conductivity
0 °C are extrapolated.
contribution from water to be 3 pS/m. Equation (1) gives the
Table 2. Fitted parameters and R2 value for the conductivity, according to relation between conductivity, mobility and the number of
equation (6). charge carriers. Inserting the conductivity contribution from
IRLAB IDA water, together with an ionic mobility of 2×10-7 m2/Vs [10]
Number of 21 5 yields the concentration of water ions as 9.7×1012 ions/m3. A
experiments
S/(m ppmw) 2.21×10-4 1.39×10-4
concentration of 2000 ppmw water corresponds to 6.7×1025
σ0,Midel
Ea eV 0.45 0.42
molecules/m3, which gives a ratio between ions and neutral
σ0,H2O S/(m ppmw) 1.83×10-6 3.55×10-6 molecules of 1.44×10-12 ions per water molecule. The
R2 - 0.92 0.65 concentration of ions in pure liquid water is 2×10-7 ions per
water molecule. There are as such 105 times more ions in
4 RESULTS AND DISCUSSION liquid water than in the water in Midel. This indicates that the
4.1 ELECTRIC CONDUCTIVITY water molecules in clusters produce fewer ions than molecules
Conductivity in Midel 7131, as measured with the IRLAB in liquid water, indicating a weaker collective effect. The
test cell, versus water content for different temperatures is conductivity contribution from water is lower than would be
shown in Figure 4. The data were fitted to equation (6), with the expected in a concentration-weighted combination where the

Authorized licensed use limited to: UNIVERSIDAD MANUELA BELTRAN. Downloaded on May 04,2020 at 01:19:07 UTC from IEEE Xplore. Restrictions apply.
2962 T. G. Aakre et al.: Conductivity and Permittivity of Midel 7131: Effect of Temperature, Moisture Content, Hydrostatic Pressure

total conductivity is a mass-weighted combination of the

conductivity of Midel and water.
4.1.3 EFFECT OF PRESSURE
Increasing the pressure from 0.1 to 10 MPa (1 to 100 bar)
resulted in a decrease in the measured conductivity of
approximately 5% when the same sample was used.
However, the change in conductivity with pressure was too
small to be significant when compared to the difference
between samples.

4.1.4 EFFECT OF ELECTRIC FIELD

The expected conductivity for dry Midel and pure water,
based on equations (11) and (12) with the fitting of Midel
from this study and the fitting of water from [20], is shown
Figure 5. Conductivity as function of electric field in Midel 7131 at
in Figure 3. It is seen that both the water and Midel different temperatures and humidity.
conductivity is constant for increasing electric field. In
been suggested based on the conductivity measurements in
addition, the conductivity of a combination of Midel and
this paper. Therefore, a modification to the equation was
water is plotted through a concentration-weighted linear
made. The contribution from water is reduced by a factor γ,
combination of equations (11) and (12). Two levels of water
content are used, 60 and 1530 ppm, corresponding to levels 1  2 TC 
r     H 2 O   rH O TC  (22)
of water content in the measurements. 1   TC  2

Figure 5 shows the conductivity as a function of electric

field as measured by IDA. The general trend is that the
conductivity is decreasing for dry samples and increasing
for wet samples for increasing electric field.
Comparing this to the field dependent conductivity shown
in Figure 3 it is seen that the change in conductivity with
electric field, as well as the numeric values of conductivity,
is different between the measurement results and what is
predicted by the theory. A concentration-weighted
combination results in the contribution from water
dominating the conductivity, resulting in a much higher
conductivity value and uniformly increasing conductivity at
higher fields. This is not the case for the measured values,
which increase or decrease with electric field, depending on
temperature and water content. The contribution from water
also increases the conductivity in the measurements, but the
effect is much smaller than what is observed for
concentration-weighted combination. The differences may
originate in the previously suggested clustering of water in
Midel, in which groups of water molecules are loosely
grouped together.
where the Midel permittivity is assumed to completely follow
Clausius-Mossotti in relation to the density change as function
of temperature and  rH O is from equation (17). The measured
2
permittivity, as well as a fit to equation (22) with parameters,
are shown in Figure 6.
4.2.1 EFFECT OF TEMPERATURE
The change in permittivity with temperature, as seen in
Figure 6, can be explained by the change in density with
temperature, following the Clausius-Mossotti relation,
equation (14).
4.2.2 EFFECT OF WATER
The simple mixing rule given by equation (18) does not

4.2 PERMITTIVITY
The permittivity is a measure of the dielectric's ability to
polarize the molecules. This ability is closely connected to
the density of the dielectric, as described by the Clausius-
Mossotti relation, equation (14). A concentration weighted
linear superposition of the permittivities of Midel and water,
equation (18), was fitted to the results and found to be
inadequate. The permittivity of water is strongly dependent
on the collective behavior of the water molecules [21].
Figure 6. Relative permittivity as function of water content and
When water is absorbed in Midel, the interaction between temperature in Midel 7131. Values for 0 °C are interpolated from
water molecules is reduced compared to liquid water, as has equation (22). Relative saturation (RS) concentration of water in Midel is
given versus temperature in the plot.

Authorized licensed use limited to: UNIVERSIDAD MANUELA BELTRAN. Downloaded on May 04,2020 at 01:19:07 UTC from IEEE Xplore. Restrictions apply.
IEEE Transactions on Dielectrics and Electrical Insulation
fully apply. Dissolving water in Midel reduces the interaction
between water molecules and hence introduce the parameter γ
to the permittivity. This parameter describes the reduction of
the collective effect of water. Contribution of water ions of the
total permittivity is reduced to 37 % as the effective
permittivity of water is lowered from 75 to 28 at 30 °C. Water
dipoles with no interaction with each other will give a relative
permittivity of 18 at 30 °C [21]. Thus, for water molecules in
Midel, which is suggested in this paper to group in clusters,
there will be some interaction between water molecules, but
this interaction is largely reduced compared to the interaction
between water molecules in pure water. This may be due to
weak interaction between water molecules in different
clusters. It may also be an effect of water molecules in a
cluster being only loosely associated.
4.2.3 EFFECT OF PRESSURE
The measured permittivity in Midel has a small pressure
dependence, increasing with about 0.3 % from 0.1 to 10 MPa
(1 to 100 bar). The permittivity increased with increasing
pressure, at the same order as the density, equation (20). The
density of both water and Midel increases about 0.4 % for an
increase in pressure of 10 MPa (100 bar). The observed
change in permittivity was close to the sensitivity of the
equipment. However, the change in permittivity is in
accordance with the Clausius-Mossotti relation, equation (14).
4.2.4 EFFECT OF ELECTRIC FIELD AND
FREQUENCY
Figure 7 shows the complex permittivity at 200 V, 5 kV
and 30 kV for a medium wet sample at 56 °C and 30% RS.
There is no difference between the permittivity at different
applied voltages at frequencies above 5 Hz. The main
contribution to the losses at frequencies between 1 mHz and
100 Hz is the conductivity.
The real permittivity increases below a certain frequency,
the value of which is increasing with electric field. This is
probably related to the separation of ionic pairs occurring
more rapidly at higher electric fields, and thus having a
Figure 7. Real and imaginary part of the permittivity as function of
frequency. Sample parameters: 56 °C and 30% relative saturation.
Authorized licensed use limited to: UNIVERSIDAD MANUELA BELTRAN. Downloaded on May 04,2020 at 01:19:07 UTC from IEEE Xplore. Restrictions apply.
Vol. 23, No. 5; October 2016 2963
marked effect on the permittivity at higher frequencies at
higher voltages. The apparent decrease/saturation in real
permittivity for small frequencies at the highest applied
voltage is probably due to ionic charge carriers being swept
out of the gap, giving a saturation of the system.
5 CONCLUSION
This study has shown that the conductivity and permittivity
in Midel is highly temperature dependent, dependent on the
water content and electric field, and nearly independent of the
pressure.
The conductivity follows an Arrhenius relation with
temperature, and the ionic contribution from water makes the
conductivity increase linearly with the concentration of water.
The linear increase indicates that a dissociating water
molecule in Midel interacts with other water molecules. This
effect would be expected if water in Midel occurs in loosely
associated clusters. The much smaller effect of water on the
conductivity in Midel when compared to a concentration-
weighted combination also indicates that the mutual
interaction between water molecules in Midel is reduced when
compared to liquid water.
The permittivity follows the Clausius-Mossotti relation with
regard to temperature and pressure. It is linearly dependent on
the water content as is expected for a mixture. The effect of
the water content is smaller than expected for a concentration-
weighted combination, however, indicating a lower degree of
interaction between water molecules than in liquid water. This
is in accordance with the observations in the conductivity
measurements.
Combined, the results indicate that water contributes less to
changes in conductivity and permittivity than would be
expected of a concentration-weighted combination, indicating
a weaker interaction between water molecules in the mixture
than in pure water. In spite of the reduced interaction, there is
clear indication of some degree of association between the
molecules, suggesting that water in Midel occurs in loose
clusters.
ACKNOWLEDGMENT
This work is funded by the project “High Voltage Subsea
Connections (SUBCONN)”. The project is supported by The
Research Council of Norway (Project No. 228344/E30), and
by the following industrial partners: ABB AS, Aker Solutions
AS, Deutsch Offshore, Chevron Norge AS, Det Norske
Oljeselskap ASA, Nexans Norway AS, Shell Technology
Norway AS and Statoil Petroleum AS.
REFERENCES
[1] A. Denat, "Conduction and breakdown initiation in dielectric liquids,"
IEEE Int'l. Conf. Dielectr. Liquids, pp. 1-11, 2011.
[2] W. Schmidt, Liquid State Electronics of Insulating Liquids: Taylor &
Francis, 1997.
[3] S. Zumdahl, Chemical Principles: Cengage Learning, 2007.
[4] K. A. Dill and S. Bromberg, Molecular Driving Forces: Statistical
Thermodynamics in Chemistry and Biology: Garland Science, 2003.
2964 T. G. Aakre et al.: Conductivity and Permittivity of Midel 7131: Effect of Temperature, Moisture Content, Hydrostatic Pressure

[5] D. R. Lide, CRC Handbook of Chemistry and Physics, 84th Edition: Torstein G. Aakre was born in Tønsberg, Norway
Taylor & Francis, 2003. in 1988. He received the M.Sc. degree from the
[6] J. W. P. Schmelzer, E. D. Zanotto, and V. M. Fokin, "Pressure Norwegian University of Technology and Science,
dependence of viscosity," J. Chem. Phys., Vol. 122, 74511, 2005. Trondheim, Norway in 2013. He has been
[7] Y. Jing, I. V. Timoshkin, M. P. Wilson, M. J. Given, S. J. Macgregor, T. employed by SINTEF Energy Research since
Wang, et al., "Dielectric properties of natural ester, synthetic ester midel 2013. His research interests are within electrical
7131 and mineral oil diala D," IEEE Trans. Dielectr. Electr. Insul., Vol. insulation materials, with a special focus on
21, pp. 644-652, 2014. conductivity and breakdown mechanisms.
[8] I. V. Timoshkin, R. A. Fouracre, M. J. Given, S. J. MacGregor, P.  
Mason, and R. Clephan, "Dielectric properties of Diala D, MIDEL 7131
and THESO insulating liquids," IEEE Conf. Electr. Insul. Dielectr.
Phenomena,(CEIDP) Quebec City, QC, pp. 622-625, 2008. Torbjørn A. Ve was born in Bergen, Norway in
[9] L. Onsager, "Deviations from Ohm's law in weak electrolytes," J. Chem. 1983. He received the M.Sc. degree from the
Phys., Vol. 2, pp. 599-615, 1934. Norwegian University of Technology and Science,
[10] R. Pethig and D. B. Kell, "The passive electrical properties of Trondheim, Norway in 2008. He started at
biological systems: Their significance in physiology, biophysics and SINTEF Energy Research in 2008, and is currently
biotechnology," Phys. Medicine and Biology, Vol. 32, pp. 933-970, employed there as a research scientist. His
1987. research interests include charge accumulation and
[11] A. K. Jonscher, Dielectric Relaxation in Solids: Chelsea Dielectrics transport in solid insulation materials, and liquid
Press Limited, 1983.   and gas absorption in polymer materials. 
[12] D. J. Griffiths, Introduction to Electrodynamics: Prentice Hall, 1999.   
[13] "MIDEL 7131 Technical Datasheet No 14, Thermal Properties."  
[14] C. G. Malmberg and A. A. Maryott, "Dielectric Constant of Water Øystein L. Hestad was born in Mo i Rana,
from 0 to 100 C," J. Research National Bureau of Standards, Vol. 56, Norway in 1978. He received the M.Sc. degree in
pp. 1-8, 1956. physics in 2003 and the Ph.D. degree in chemistry
[15] K. Wakino, "A new proposal on mixing rule of the dielectric constant in 2010, both at the Norwegian university of
of mixture," Ninth IEEE Int'l. Sympos. Applications Ferroelectrics science and technology (NTNU) in Trondheim.
(ISAF), pp. 33-38, 1994. Since 2003 he has worked with SINTEF Energy
[16] M. Jovalekic, D. Kolb, S. Tenbohlen, L. Bates, and R. Szewczyk, "A Research in Trondheim. His research interests
methodology for determining water saturation limits and moisture include prebreakdown and breakdown phenomena
equilibrium diagrams of alternative insulation systems," IEEE Int'l. in liquid and solid insulating materials.
Conf. Dielectr. Liquids, pp. 1-5, 2011.  
[17] R. Tobazeon, J. C. Filippini, and C. Marteau, "On the measurement of
the conductivity of highly insulating liquids," IEEE Trans. Dielectr.
Electr. Insul., Vol. 1, pp. 1000-1004, 1994.
[18] J. C. Filippini, R. Tobazéon, P. Guuinic, and O. Moreau, "The
spontaneous ionic purification phenomenon of transformer oil:
Presentation and consequences," J. Electrostatics, Vol. 67, pp. 737-740,
2009.
[19] D. Linhjell, L. Lundgaard, and U. Gäfvert, "Dielectric response of
mineral oil impregnated cellulose and the impact of aging," IEEE
Trans. Dielectr. Electr. Insul., Vol. 14, pp. 156-169, 2007.
[20] W. L. Marshall, "Electrical conductance of liquid and supercritical
water evaluated from 0 °C and 0.1 MPa to high temperatures and
pressures. Reduced-state relationships," J. Chem. Eng. Data, Vol. 32,
pp. 221-226, 1987.
[21] F. H. Stillinger, "Proton Transfer Reactions and Kinetics in Water,"
Theoretical Chem., Advances and Perspectives, Vol. 3, pp. 177-234,
1978.

Authorized licensed use limited to: UNIVERSIDAD MANUELA BELTRAN. Downloaded on May 04,2020 at 01:19:07 UTC from IEEE Xplore. Restrictions apply.