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S255S258
Ho-Soon Yang
Department of Physics, Pusan National University, Busan 609-735
Byung-Chun Choi
Department of Physics, Pukyong National University, Busan 608-737
Jeong-Bae Kim
School of Computer Aided Science, Inje University of Education, Kimhae 621-749
K. S. Hong
Busan Center, Korea Basic Science Institute, Busan 609-735
(Received 13 February 2005)
A cylindrical-shape sample cell was prepared to investigate the dependence of salt amounts in
a water-in-crude oil emulsion system by measuring the dielectric properties in the frequency range
from 102 Hz to 107 Hz with an impedance analyzer. High-sensitivity complex dielectric constant
measurements were obtained after calibration with several fluids having known dielectric constants.
From complex dielectric spectra, we observed two regions for frequency characteristics: conduction
relaxation in the low-frequency region due to diffusion by charge transport caused by impurities
such as resins and asphaltenes in the continuous phase, and the dielectric-relaxation mechanism in
the high-frequency region due to the modified Debye type where the relaxation time was in linear
proportion to the salt content in the disperse phase of the water-in-crude oil emulsion system.
PACS numbers: 77.22.-d, 77.84.Nh
Keywords: Water-oil emulsion, Dielectric constants, Dielectric relaxation, Emulsion stability
I. INTRODUCTION
The systems commonly called emulsions are complex
systems relevant to applications in the oil, food, or painting industries, and their properties are studied empirically in relation to various fields of science and engineering [1]. The behavior of emulsions depends on the nature
of the disperse phase [2], and the properties of obtained
emulsions strongly depend on the size of drops and their
concentration.
Dielectric spectroscopy is a powerful technique in analyzing heterogeneous systems of water-in-oil (W/O) and
oil-in-water (O/W) emulsions. The conductive and dielectric properties of emulsions have been extensively
studied theoretically and experimentally [16]. Dielectric relaxation was investigated in several materials recently [710], but this is not known in W/O and O/W
emulsions. We can divide an emulsion into continuous
E-mail:
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Dielectric constant (0 )
1.0005 0.0002
1.924 0.01
2.238 0.002
4.82 0.02
5.699 0.008
10.65 0.05
References
[12]
[13]
[14]
[15]
[14], [15]
[13], [14]
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() = +
(2)
+
1 + (ip )1p
() = +
Fig. 3. Schematic diagram of continuous and disperse
phases in salt-water/crude-oil emulsion system. S means salt,
white circles are water drops, and small black circles are impurities.
Figure 3 shows a schematic diagram of the salt-crudeoil/water emulsion system, where we can distinguish the
crude-oil region (continuous phase) and the salt-water
region (disperse phase). The continuous phase includes
conducting materials such as asphaltenes, resin, and nonconducting materials. Water holds salt (conducting material) in the disperse phase.
When we consider water only, as for Debye-type ideal
materials, the measured complex dielectric constant as a
function of angular frequency can be described by
() = +
s
,
1 + i
(1)
i
.
0
(3)
The first two terms on the right-hand side are the original
Cole-Cole model, which is dielectric relaxation caused by
dipole orientation polarization of polar molecules in the
frequency range 100 MHz 10 GHz. The third term
accounts for a low-frequency relaxation due to the interfacial polarization effect at the grain boundary. The last
term is purely empirical, and is the conductive loss in
the liquid, depending on the measurement cell, and is
the dc conductivity.
Figure 4 shows variations of the real (0 ) and imaginary
00
( ) parts of the dielectric constant versus frequency in
log-log scale for several salt contents. The real part 0
decreases slowly in the frequency range from 10 to 106 Hz
with salt content. The characteristic peak in the imaginary part 00 , which is shifted towards higher frequencies
when salt content increases, indicates the presence of a
relaxation process.
The values 0 and 00 decrease rapidly with frequency.
The absolute values of the slopes below 104 Hz are larger
than those above 104 Hz and seem to be independent of
the salt content. These two tendencies in frequency dependence suggest that two dispersion mechanisms are
involved in the dielectric-constant measurement. Therefore, the conductivity term in Eq. (3) should be improved, because the slopes of 0 and 00 at low frequency
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s
1 + (i )m
0
[1 + (i )n ].
0
ACKNOWLEDGMENTS
(4)
After evaluating all the frequency-dependent complexdielectric-constant data fitted with Eq. (4), we found
that the carrier polarization mechanism was weakly dispersive, while the interfacial polarization mechanism was
somewhat more dispersive. From the calculated values
of 1 and 2 in the emulsion system, we observed that
the relaxation time 1 was in linear proportion to salt
content while 2 was independent of the salt content in
the emulsion systems. These facts suggest that the highfrequency dielectric relaxation is not related to resins
and asphaltenes in the continuous phase, but is related
to the salt in the disperse phase. Since 1 and do not
depend on salt content, salt cannot move from disperse
phase to continuous phase and can be trapped strongly
to droplets. A dielectric response relation, which is considered as a generalization to the Cole-Cole dielectric expression, has been proposed. The influence of the chargecarrier contribution on the complex dielectric constant is
significant, as is demonstrated when both interfacial and
carrier polarization mechanisms are simultaneously considered.
IV. CONCLUSIONS
A cylindrical-shape sample cell was prepared to investigate the dependence of salt amounts in a waterin-crude-oil emulsion system by measuring the dielectric properties in the frequency range from 102 Hz to
107 Hz with an impedance analyzer. The characteristics of the measurement cell are optimized to give high
sensitivity. High-sensitivity complex-dielectric-constant
measurements were obtained after calibration with several fluids having known dielectric constants. From complex dielectric spectra, we observed two regions for frequency characteristics: conduction relaxation in the low-
This work was supported by Korea Science and Engineering Foundation Grant R05-2003-000-10451-0.
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