SPE 68779

A Comprehensive Study of the Relative Dielectric Permittivity in Porous Media

Ali A. Garrouch, SPE, Petroleum Engineering Department, Kuwait University

Copyright 2001, Society of Petroleum Engineers Inc.

Introduction
This paper was prepared for presentation at the SPE Western Regional Meeting held in
Bakersfield, California, 26–30 March 2001.
The use of resistivity and high-frequency dielectric logs
This paper was selected for presentation by an SPE Program Committee following review of
information contained in an abstract submitted by the author(s). Contents of the paper, as
helps in estimating reservoir hydrocarbon content. Thus,
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to careful interpretation of these logs is important. For fluid
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at saturated rocks the fluid-mineral interfaces give rise to large
SPE meetings are subject to publication review by Editorial Committees of the Society of dielectric permittivity. In the absence of an applied electric
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
for commercial purposes without the written consent of the Society of Petroleum Engineers is field, ions form a double layer at the mineral-water
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous interface. When an oscillating electric field is applied at low
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
frequencies, the ions polarize around the mineral grains.
This polarization gives rise to large dipoles (with charges
separated by a length scale on the order of the grain size),
Abstract and to large apparent relative dielectric permittivity (> 103).
This study investigated the effects of water saturation and As the frequency increases, ions have less time to travel
wettability on the dielectric permittivity experimentally, because of their finite velocities, and therefore polarize less.
using four-electrode impedance measurements, and Recently, Nguyen et al.1 measured the dielectric
theoretically, using models that account for the electrical permittivity of water-wet and oil-wet of acid-purified quartz
double layer polarization. sand in a frequency range of 300 KHz to 1.5 GHz. They
Complex impedance measurements, performed on observed a large difference in dielectric permittivity
Berea sandstone and on Ottawa-sand packs in the frequency between water-wet and oil-wet porous media. At low water
range 10 Hz to 1 MHz, indicated a linearly varying relative saturations, the dielectric permittivity of oil-wet sand was
dielectric permittivity with water saturations above 50%. found smaller than that of the water-wet one. At water
The rate of change of the relative dielectric permittivity saturations higher than 0.3, the dielectric permittivity of an
with saturation decreased as the frequency increased. oil-wet sand was found much larger than that of the water-
The relative dielectric permittivity of water-wet wet one. Knight and Abad2 measured relative dielectric
samples was higher than that of the oil-wet samples at all permittivity of hydrophobic and hydrophilic sandstones at 1
water saturations. The difference was more pronounced as MHz. They reported that hydrophilic sandstones had a
the saturation increased. The relative change was higher relative dielectric permittivity than the hydrophobic
approximately 60% at a water saturation of 100%. To ones, for the whole water saturation spectrum ranging from
confirm these experimental observations, this study 0 to 100%. Knight and Nur3 measured the relative dielectric
conducted simulations of rock wettability changes using a permittivity of eight sandstones at various water saturation
generalized Maxwell-Wagner model by varying the amount levels in the frequency range of 5 Hz to 4 MHz. They
of ionic surface charge of rocks. In general oil-wetting observed a power-law dependence of the relative dielectric
agents react with the formation matrix by connecting their
permittivity (χ) on the frequency (ω) :
positively charged tails to the negatively charged silica
surfaces, lowering the surface charge density. Simulations
showed that there was about an order of magnitude χ = β ω-α, (1)
difference in the relative dielectric permittivity as the rock
where β and α were empirical constants. They related the
surface charge changed by an order of magnitude. Both
power law exponent α to the water saturation and to the
simulations and experimental results showed a trend of
surface area to volume ratio of the pore space. Hoyer and
significant increase in the relative dielectric permittivity as
Rumble4 made complex impedance measurements on
the rock conditions changed from oil-wet to water-wet.
sandstone cores, and on clay-water suspensions in a
frequency range 10 Hz to 0.1 MHz using a four-electrode
bridge circuit. Their data showed that the relative dielectric
2 A. A. GARROUCH SPE 68779
9

permittivity decreased by a factor of five when the radial stress of 500 psi and an axial stress of 250 psi were
frequency increased from 100 Hz to 1000 Hz for a 5% by applied. To make dry Berea samples and the sand packs
weight bentonite suspension. Hoyer and Rumble reported water-wet, the author treated these samples with NaOH
that in the frequency range investigated, relative dielectric solution (pH 11), flushed them with fresh water, and then
permittivity varied with water saturation as follows: heated them at 80 0C for 4 hours. To make these porous
media oil-wet, they were treated with a solution of Quilon-
C in isopropyl alcohol. Then they were heated at 80 0C for 4
hours. Quilon-C is a chemically reactive solution, provided
X = X 100 S wη (2) by Dupont, in which C14-C18 fatty acids are coordinated
with chromium. The Chromium bonds with negatively
where χ is the relative dielectric permittivity at 100% charged surfaces, such as silica, and forms an insoluble
100
water saturation (S ) and η is a constant approximately layer on the substrate surface. Quilon-C renders surfaces
w extremely hydrophobic over extended periods of time and is
equal to one. In their experiment, S varied from 0.3 to 1.0.
w a better agent than Dri-film, which is more water soluble
The objective of this paper is to examine both
and tends to be leached from the surface over time. Core
experimentally and theoretically the effects of wettability
samples and sand packs were vacuum saturated with a
and water saturation on the relative dielectric permittivity of
solution of 10 000 ppm NaCl brine, then flooded with n-
fully and partially-saturated porous media. Results of this
decane. This flooding sequence was repeated to check
study will put under scrutiny the various and sometimes
saturation hysteresis. The fluid displacement procedures are
conflicting conclusions reported in the literature regarding
detailed in Sharma et al.8 Brine saturations were established
the behavior of relative dielectric permittivity as a function
to within ± 1.0%. The circuit and the setup for making
of saturation, and wettability conditions. An advantage of
impedance measurements at different saturations is detailed
this study over previous ones, reported earlier, consists of
in Sharma et al.8 and in Garrouch.5 An LCR meter
conducting four-electrode impedance measurements instead
(HP4192A LF) was used to measure the gain in decibels (to
of the two-electrode measurements known to be plagued by
contact-electrode polarization.5 Another advantage consists within ± 0.1 dB) and the phase angle θ in degrees (to
of accounting for the electrical double layer polarization in within 0.5o). These two quantities are then converted into
modeling the dielectric behavior of porous media. impedance Z from which the resistance R and the reactance
Simulations of the dielectric dispersion in porous media X of the porous medium are calculated as follows:
is performed using a generalized Maxwell-Wagner complex
impedance model for shaly sands developed by Lima and R = Z cosθ , (3)
Sharma.6 In this analytical model, the grains are treated as and
charged insulating spheres surrounded by an electrical
double layer immersed in an electrolyte solution. The
X = Z sinθ . (4)
response of a sand particle to an oscillating electric field is
described by complex electrical properties that are The relative dielectric permittivity is based on a parallel
dependent on the particle surface charge, its dimension, and resistor-capacitor model and is given by
on the salinity of the electrolyte. Using the resultant
effective properties of a charged grain-water composite, ta C p
Lima and Sharma applied the Hanai-Bruggeman theory to X= (5)
derive the complex impedance of a shaly sand, fully
Aε o
saturated with brine, as a function of frequency. Garrouch In this notation, χ is the relative dielectric permittivity, ta is
and Sharma7 validated this model for shaly sandstone the sample thickness between the voltage measuring
porous media. A detailed description of this model is electrodes, A is the cross sectional area of rock sample, εo
provided in the same reference. is the permittivity of air, cp is the calculated capacitance of
The following paragraph presents a brief discussion of the rock assuming parallel resistor-capacitor model. The
the experimental procedures. This is followed by a latter is related to the angular frequency ω, the measured
discussion of the saturation and wettability effects on the series mode resistance Rs and capacitance cs of the rock by
relative dielectric permittivity.
Cs
Experimental Procedures Cp = (6)
ω Cs2 Rs2 + 1
2

The author performed measurements on fully and

partially saturated Berea cores (having 22% porosity) and The reactance X is defined as 1/ωCs.
Ottawa-sand packs (with porosity ranging from 28% to
35%) using a Hassler-type core-holder that houses 3-inch-
long core samples with 1.5-inch diameters.7 An effective
SPE 68779 A COMPREHENSIVE STUDY OF THE RELATIVE DIELECTRIC PERMITTIVITY IN POROUS MEDIA 3

Saturation Effects In this notation β1 is the surface counterion density

necessary to balance the immobile charges on the composite
As can be seen in Figures 1 and 2, the relative sphere of radius a; C1 is the bulk electrolyte cation
dielectric permittivity increases approximately linearly with
concentration; σ w is the complex electrolyte conductivity,
*
saturation for frequencies from 10 KHz to 1 MHz, for both
Ottawa-sand packs and Berea. Figure 3 also shows similar and Y is a complex parameter given by
trends for a 2% by weight bentonite-Ottawa sand mixture. It
is also possible to show theoretically the reason such a 1 + (1 − i) ωτ
Y= . (12)
linear relationship should be obtained. For a partially water
2 + 2(1 − i) ωτ − 2iωτ
saturated unconsolidated shaly sandstone, Lima and
Sharma6 deduced from Wagner’s theory the effective
* The variable τ is a characteristic relaxation time for the
complex conductivity σ o as double layer around the charged particle. It is related to the
diffusion coefficient D of the counterion in the double layer,
* * 2σ f* + σ *cs − 2φ (σ f* − σ cs
* ) and to the particle radius as follows :
σo = σ f * ) , (7) a2
2σ f* + σ *cs + φ (σ f* − σ cs τ= . (13)
2D
For situations where the Debye-Huckel length (κ-1)
In this notation, σ f is the composite fluid complex
*
becomes significant compared to the particle radius, this
*
conductivity, σ cs is the composite clay-sand grain characteristic relaxation time is given by:
* (a + κ −1 )2
complex conductivity, φ is the porosity, σ o is the effective τ= . (14)
complex conductivity of the shaly sand pack. Note that each D
of the complex conductivity functions above can be written Using the model presented by equations (7) through (14),
as the real and imaginary parts of the composite clay-sand
grain complex conductivity were calculated for a wide
range of fluid and clay-coated sand grain properties. As
σ *j = σ j − iωε j . (8) implied from Figure 4, the composite clay-sand grain
permittivity (εcs) is much greater than the water
Here j is a subscript and i is the imaginary number. In permittivity (εw) for a wide range of frequencies. For water
equation (7), the grain and its associated ionic double layer conductivities ranging from 0.002 to 2.0 S/m, εcs was at
are represented by an equivalent sphere which has an least one order of magnitude larger than the water
*
effective complex conductivity σ cs dependent on the permittivity (Figure 4). The composite fluid permittivity is
even smaller than the water permittivity.9 We may,
particle dimension, its surface charge density and the therefore, safely make a first approximation: (εcs>>εf). For
salinity. Thus for a sphere having a complex conductivity the range of fluid salinity used, it is intuitively obvious that
σ a* and coated with a uniform layer of clay with complex the fluid conductivity is much greater than the composite
clay-sand grain real conductivity. We may, therefore, make
conductivity σ c , the effective complex conductivity of a
*
a second approximation: ( σ f >> σ cs ). Using these two
grain and its associated double layer is expressed as approximations and inserting expressions for the effective
follows: complex conductivities similar to equation (8), into
2pσ c* + (3 − 2p)σ a* equation (7), the following expression is obtained:
σ cs
*
= σ c* . (9)
(3 − p)σ c* + pσ a* 2φσ f − iωε cs (3 − 2φ )
* *
σo = σ f . (15)
In this notation p is the volume fraction of the clay shell, σ f (3 − φ ) − iωφε cs
*
relative to the composite sphere volume, and σ c is given
By multiplying equation (15) by the conjugate of its
denominator and by separating the real and imaginary parts,
by the following expression for the effective permittivity as a
* δ σ* function of the fluid permittivity (εf) is obtained:
σc = 1 w , (10)
1 − δ 1Y
9ε (1− φ)σ 2 φ(3− 2φ)(2σf2 +ω2εcs 2)
where, εo = 2 cs 2 2f 2 2 + 2 2 f
ε ,
δ1 = β1/aC1. (11) σf (3 −φ ) +ω φ εcs σ f (3 −φ)2 + ω 2φ 2εcs
(16)
4 A. A. GARROUCH SPE 68779
9

In this notation, εo is the effective permittivity of the shaly early breakthrough in water flood projects. In the following
sand, εcs is the permittivity of the clay coated grain, σf is paragraph, the wettability factor is singled out for the
the composite fluid (oil and water) real conductivity, εf is purpose of studying its effect on the relative dielectric
the composite fluid (oil and water) permittivity, ω is the permittivity of both consolidated and unconsolidated porous
angular frequency. The linear dependence of permittivity on media.
water saturation is not obvious from equation (16), since The relative dielectric permittivity of water-wet
both the fluid conductivity (σf), and the fluid permittivity Ottawa-sand and Berea samples is found higher than that of
(εf) vary linearly with water saturation.9 This linear oil-wet samples at all water saturations (Figures 6a and 6b).
dependence is, however, more obvious for the special case The difference is more pronounced at water saturations near
2 unity. These results are consistent with Knight and Abad2
where (ωεcs)2φ<< σ f (3 − φ ) as suggested by Figure 5 report on the relative dielectric permittivity of hydrophobic
which is generated using the model presented by equations and hydrophilic sandstones. The reason for the observed
(7) through (14). For a composite fluid made of oil and differences between the water-wet and oil-wet relative
water, where both phases are continuous, the fluid dielectric permittivity is believed to be due to the
permittivity and conductivity are shown by Hasted (1973) neutralization of the negative surface charge on the mineral
to be related to the water permittivity (εw), the oil surfaces by the chromium ions in the Quilon-C solution. In
permittivity (εh), the water saturation (Sw), and the water the limit when the porous medium is fully saturated with
conductivity σw by oil, one expects the relative dielectric permittivity of the oil-
wet sample to be very close in value to that of the water-wet
εf = εw - εh Sw + εh , (17) sample. This is consistent with the trend observed in
and Figures 6a and 6b. The gap between water-wet and oil-wet
σ f = S wσ w . (18)
samples becomes narrower as the water saturation
decreases.
The wettability changes have been modeled by varying
Even though Figure 5 compares the term (ωεcs) with water the amount of ionic surface charge on the sand-grain
conductivity, this comparison remains valid vis-à-vis the surfaces. In general, oil wetting agents react with the
composite fluid conductivity for water saturations as low as formation matrix by connecting their positively charged
10% (equation (18)). For the special case where tails to the negatively charged silica surfaces, lowering the
2
(ωεcs)2φ<< σ f (3 − φ ) , substituting equations (17) and surface charge density. The wettability status of the
(18) in equation (16) leads to a linear dependence of the simulated samples is, therefore, suggested by the magnitude
effective permittivity of an unconsolidated shaly sand on of the surface charge; i.e., as indicated in Figure 7, the
the water saturation as follows: high-surface-charge sample is assumed to reflect the
behavior of a water-wet sample. The low-surface-charge
2φ(3− 2φ)(εw −εw) 9(1−φ)εcs+ 2φ(3−φ)εh) sample is assumed to reflect the behavior of a relatively oil-
εo = [ ]Sw + [ ]. wet sample. The effect of changing the surface charge
(3−φ)2 (3−φ)2 density on the relative dielectric permittivity is very
(19) significant at all frequencies in the range investigated
(Figure 7). The relative dielectric permittivity increased by
The decrease in the relative dielectric permittivity with about an order of magnitude as the surface charge density
increasing oil saturations is due to the replacement of increased by an order of magnitude. The simulated water-
polarizable ionic species by non-polarizable oil molecules. wet sample appears to have significantly higher relative
The additional interfacial charge contribution to the relative dielectric permittivity than the simulated oil-wet sample.
dielectric permittivity appears to be insignificant when This is in qualitative agreement with data presented in
compared to the replacement of polarizable ions by the non- Figures 6a and 6b.
polarizable oil molecules.
Summary
Effect of Wettability
This study used four-electrode complex impedance data
Wettability, which describes how immiscible fluids of porous media to investigate the behavior of relative
adhere to a reservoir rock, influences a variety of dielectric permittivity as a function of water saturation, and
parameters pertaining to oil flow. In oil-wet rocks, the fluid wettability conditions. The data of this study were measured at
distribution inside the pore space is opposite to the fluid elevated radial stress conditions of 500 psi and axial stress
distribution in water-wet rocks. In the former, oil occupies conditions of 250 psi, while varying the frequency from 10
the tiny pores and wets the surface of the large pores. This Hz to 1 MHz. Four-electrode measurements have been done in
fluid distribution causes the residual oil saturation to the past, but covered up to a frequency of 0.1 MHz, and were
increase, decreases the relative permeability to oil, induces done at ambient pressure conditions. For both oil-wet and
water-wet Berea and Ottawa-sand packs, the relative dielectric
SPE 68779 A COMPREHENSIVE STUDY OF THE RELATIVE DIELECTRIC PERMITTIVITY IN POROUS MEDIA 5

permittivity varied linearly with water saturation above 50%. Nomenclature

The rate of change of the relative dielectric permittivity with
saturation varied with frequency. A the cross sectional area of rock sample
Water-wet porous media systematically displayed higher a particle radius
relative dielectric permittivity than oil-wet porous media. This c empirical constant
study asserted even further these conclusions by using a cs the measured series mode capacitance
Generalized Maxwell-Wagner model to simulate the C1 the bulk electrolyte cation concentration
experimentally observed behavior of the relative dielectric cp the capacitance of the rock assuming parallel
permittivity. The advantage of this model over the commonly resistor-capacitor model
used mixing formulas consisted of accounting for the effects D diffusion coefficient of the counterion in the
of the electrical double layer polarization, thereby allowing double layer
adequate modeling of the dielectric dispersion of shaly sands. f the frequency in Hz
As a consequence, the study helped in clearing previously p the volume fraction of the clay shell, relative to the
reported conflicting conclusions in the literature regarding the composite sphere volume
effects of wettability and saturation on the relative dielectric R rock resistance
permittivity. Rs the measured series mode resistance
S water saturation
w
References ta the sample thickness between the voltage
measuring electrodes
1. Nguyen, B., Bruining, J., Slob, E.C., “Effects of X rock reactance
wettability on dielectric properties of porous Y a complex parameter given by equation (19)
media,” paper SPE 56507 presented at the 1999 z the valence of the ion
SPE Annual Technical Conference and Exhibition, Z complex impedance
Houston, TX, October 3-6.
2. Knight, R. J., and Abad, A., “Rock/water Greek Letters
interaction in dielectric properties: Experiments
with hydrophobic sandstones,” Geophysics (1995) α empirical constant
60, 431-436. β empirical constant
3. Knight, R. J., and Nur, A., “The dielectric constant
β1 the surface counterion density
of sandstones, 60 KHz to 4 MHz,” Geophysics
εh the permittivity of hydrocarbon
(1987) 52, 644-654.
εo the permittivity of air
4. Hoyer, W.A., and Rumble, R.C., “Dielectric
εf the composite fluid (oil and water) permittivity
constant of rocks as a petrophysical parameter,”
εcs the permittivity of the composite clay-sand grain
paper O, presented at the 17th SPWLA Annual
Logging (1976), 25 p. εw the permittivity of water
5. Garrouch, A.A., “A systematic study revealing φ porous medium porosity
resistivity dispersion in porous media,” The Log η empirical constant
Analyst (1999) 40, 271-279. σf real composite fluid (oil and water) conductivity
6. Lima, O.A.L., and Sharma, M.M., “A generalized σ a* sphere complex conductivity
Maxwell-Wagner theory for membrane
polarization in shaly sands,” Geophysics (1992) σ c* uniform layer of clay complex conductivity
57, 431-440.
7. Garrouch, A.A., and Sharma, M.M., “The σ f* composite fluid complex conductivity,
influence of clay content, stress, and wettability on σ cs
*
composite clay-sand grain complex conductivity
the dielectric properties of Brine-saturated rocks,”
Geophysics (1994) 59, 909-917. σ cs the real part of the composite clay-sand grain
8. Sharma, M.M., Garrouch, A.A., and Dunlap, H.F., complex conductivity
*
“Effects of wettability, pore geometry, and stress σw complex electrolyte conductivity
on electrical conduction in fluid-saturated rocks,” *
The Log Analyst (1991) 32, 511-526. σo effective complex conductivity of the shaly sand
9. Hasted, J. B.: Aqueous dielectrics: Chapman and θ phase angle measured in degrees
Hall (1973). χ relative dielectric permittivity
χ relative dielectric permittivity at 100% water
100
saturation
ω angular frequency
6 A. A. GARROUCH SPE 68779
9

20000

10 KHz
0.1MHz
DIELECTRIC CONSTANT 1 MHZ

10000

0
0.5 0.6 0.7 0.8 0.9 1.0
WATER SATURATION
Figure 1: Dielectric constant versus water saturation at multiple frequencies for
water-wet Ottawa sand pack saturated with n-decane and NaCl brine.

5000

10 KHz
4000 0.1MHz
1MHz
DIELECTRIC CONSTANT

3000

2000

1000

0
0.5 0.6 0.7 0.8 0.9 1.0

WATER SATURATION

Figure 2: Dielectric constant versus water saturation at multiple frequencies

for water-wet Berea saturated with n-decane and 10 000 ppm NaCl brine.
SPE 68779 A COMPREHENSIVE STUDY OF THE RELATIVE DIELECTRIC PERMITTIVITY IN POROUS MEDIA 7

30000

10 KHz
0.1 MHz
1 MHz
DIELECTRIC CONSTANT

20000

10000

0
0.5 0.6 0.7 0.8 0.9 1.0
WATER SATURATION
Figure 3: Dielectric constant versus water saturation for 2% by weight
bentonite-Ottawa sand pack saturated with n-decane and 10 000 ppm
NaCl brine at different frequencies.

1000

100
PERMITTIVITY (nF/m)

10

water permittivity
composite clay-grain permittivity
1

.1
10 0 10 5 10 6

FREQUENCY (HZ)

Figure 4: Comparing the permittivity of a single charged wet sphere to water

Particle radius = 9 E-7 m. Surface charge density = 1.2 E18 ions/m^2. Water
conductivity = 0.024 S/m.
8 A. A. GARROUCH SPE 68779
9

10 -1

10 -2
Water conductivity (S/m)

ω∗ε cs

10 -3

10 -4

10 -5 Charge density = 1.2 E18 ions/m 2

Particle radius = 9 E-7 m

10 -6
10 0 10 5 10 6
FREQUENCY (Hz)

Figure 5: Comparing the water conductivity to the product of the angular frequen
by the dielectric permittivity of a single charged spherical wet grain.
SPE 68779 A COMPREHENSIVE STUDY OF THE RELATIVE DIELECTRIC PERMITTIVITY IN POROUS MEDIA 9

300

oil-wet at 1MHz
water-wet at 1 MHz
DIELECTRIC CONSTANT

200

100

0
0.5 0.6 0.7 0.8 0.9 1.0
WATER SATURATION
Figure 6a: Comparing the dielectric constant-saturation profiles for water-wet and oil-wet
Berea saturated with n-decane and 10 000 ppm NaCl brine at a frequency of 1 MHz.

1000
water-wet at 1 MHz
oil-wet at 1 MHz
800
DIELECTRIC CONSTANT

600

400

200

0
0.5 0.6 0.7 0.8 0.9 1.0
BRINE SATURATION
Figure 6b: Comparing the dielectric constant-saturation profiles for water-wet and oil-wet
ottawa sand packs saturated with n-decane/10 000 ppm NaCl brine at a frequency of 1 MHz.
10 A. A. GARROUCH SPE 68779
9

100000

10000
DIELECTRIC CONSTANT

.45 E20 ions/m^2

.45 E19 ions/m^2

1000

Porosity = 20%
100 Clay particle radius = .1 E-6 m
Clay percentage = 12%

10
10 1 10 5 10 6
FREQUENCY (Hz)
Figure 7: Dielectric constant versus frequency profile for a simulated sandstone
20 000 ppm NaCl brine using the Lima-Sharma model for various surface charge dens