PETROPHYSICS, VOL. 55, NO.

6 (DECEMBER 2014); PAGE 572586; 12 FIGURES; 2 TABLES

Experimental Study of the Effects of Wettability and Fluid Saturation on Nuclear

Magnetic Resonance and Dielectric Measurements in Limestone
Lalitha Venkataramanan1, Martin D. Hrlimann1, Jeffrey A. Tarvin1, Kamilla Fellah1, Diana Acero-Allard1
and Nikita V. Seleznev1

ABSTRACT
Results from experiments on three identical samples of
oolitic limestone show the systematic effects of wettability
and uid saturation on nuclear magnetic resonance (NMR)
and dielectric data in rocks partially saturated with brine
and crude oil. Mercury porosimetry and image analysis of
the samples indicate that the pore distribution is bimodal.
All samples are from the same outcrop rock and are
initially water-wet. They are systematically put through
the complete saturation cycle. Midway through the cycle,
the wettability of two of the samples is changed to mixedwet by aging the samples. NMR, resistivity and dielectric
measurements are performed at different stages of uid
saturation and wettability. Since the samples are identical

in their petrophysical properties, it is possible to relate the

differences between samples or different saturation stages
to differences in wettability and/or uid saturations. It is
observed that wettability has a signicant effect on NMR,
dielectric and resistivity data. The relative permeabilities
of the samples may also depend on wettability; this is
evidenced in the presence of a trapped water phase in the
mixed-wet samples. By helping improve our understanding
of the effects of wettability and uid saturations on NMR,
resistivity and dielectric data, we expect that this study
will be useful in exploring new avenues in the future, for
integrating these measurements.

INTRODUCTION

by measuring the complete capillary-pressure curve as

the sample goes through a complete saturation cycle. An
example of a typical saturation cycle undergone by a sample
is shown in Fig. 1 and consists of several spontaneous and
forced drainage and imbibition stages. These measurements
are time-consuming and involve the acquisition of capillary
pressure and uid saturations at different stages in the
saturation cycle. In general, the industry-accepted AmottHarvey and U.S. Bureau of Mines (USBM) wettability
indices are derived from these measurements (Abdallah
et al., 2007).
Many logging measurements are sensitive to wettability.
For example, formation resistivity, which has been the
cornerstone of logging measurements for decades, relies on
the presence of a continuous electrical path through the rock.
This continuous path is provided by the water phase. In an
oil-wet scenario or if water is trapped in pores, formation
resistivity is expected to be much larger than if the rock is
WW. This affects the saturation exponent, n, in Archies
equation that relates saturation and resistivity. In WW rocks,
this exponent is expected to be around 2. In MW and OW
rocks, it is expected to be much larger. Therefore, if n for

Wettability of a rock describes the preference of rock

grains to be in contact with one uid rather than another.
The constituents of the rock grains, brine chemistry and
oil composition play a role in governing rock wettability
(Buckley and Monsterleet, 1998). Most reservoirs are thought
to be water-wet prior to oil migration. Oil wettability affects
the relative permeability of oil and water and therefore plays
a critical role in primary and secondary recovery (Abdallah
et al., 2007).
In a porous medium partially saturated with oil and
water, water-wet (WW) and oil-wet (OW) rocks dene the
end members of a continuum, in which the surface prefers
contact with water and oil, respectively. In a conceptual
image of a WW rock, oil is considered to be in the center of
all pores. The reverse holds true for an OW rock, with water
at the center of pores. In a mixed-wet (MW) rock, some of
the surfaces of the pores have a preference for oil while other
parts of the surfaces and smaller pores are thought to have a
preference for water (Salathiel, 1973).
In a laboratory setting, core wettability is assessed

Manuscript received by the Editor June 13, 2012; revised manuscript received August 13, 2014.
1
Schlumberger Doll Research, One Hampshire Street, Cambridge, MA 02139, USA; Email: LVenkataramanan@slb.com;
hurlimann@slb.com; jtarvin@slb.com; kfellah@slb.com; DAcero-allard@slb.com; nseleznev@slb.com

572

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Experimental Study of the Effects of Wettability and Fluid Saturation on Nuclear Magnetic Resonance and Dielectric Measurements in Limestone

a MW formation is set to 2, a resistivity-based saturation

assessment may be inaccurate (Abdallah et al., 2007;
Abdelaal et al., 2013).
NMR measurements are sensitive to both oil and water
saturations and wettability (Zhang et al., 2000; Freedman
et al., 2002; Hrlimann et al., 2003; Freedman and Heaton,
2004; Looystijn and Hofman, 2006; Al-Muthana et al.,
2012). When the relaxation times of the two uids have
little or no overlap, the T1 or T2 distributions can be used
to quantify oil and water saturation. However, in partially
saturated rocks, the oil and water T2 distributions typically
overlap. In this case, the contrast in the molecular diffusion
in diffusion-relaxation (D - T2) map plays an important
role in quantifying the amount of oil and water in the
sample (Freedman et al., 2002; Hrlimann et al., 2003).
The underlying idea of qualitatively identifying the wetting
uid from NMR is straightforward: the nonwetting uid has
a relaxation rate similar to that of the bulk uid since it is
not in contact with the pore walls. The wetting uid has an
enhanced relaxation rate due to additional surface relaxation.
Therefore, if the bulk relaxation of both uids is known, the
wetting and nonwetting phases can be identied.
Dielectric measurements are also sensitive to uid
saturations and wettability (Abdallah et al., 2007; Ellis
and Singer, 2007). Since the dielectric constant of water
is an order of magnitude larger than that of hydrocarbons,
measurement of dielectric dispersion is useful for
quantifying water saturation in partially saturated rocks.
This involves measurement of the attenuation and phase of
an electromagnetic wave as it propagates through the rock.
In turn, these measurements are converted to permittivity
and conductivity. These measurements are made in the
laboratory at frequencies ranging from MHz to GHz.
The dispersion of permittivity and conductivity is
caused by many factors: ionic and molecular orientation
and interfacial polarization (Ellis and Singer, 2007). The
interfacial polarization, also referred to as the MaxwellWagner effect, is due to buildup of charges between
conductive brine and nonconductive grain. It is affected by
water salinity as well as pore and grain shape and orientation
in the rocks. In WW rocks, the interfacial polarization
between water and grain causes an increased permittivity.
On the other hand, in MW and OW rocks, the interfacial
polarization between water and grain is decreased because
water is not as much in contact with the grains. This leads
to decreased permittivity. The brine phase also does not
necessarily have a continuous, connected path across the
sample. Therefore, even when a WW and MW sample have
the same partial saturation of uids, a WW sample has a
higher permittivity and conductivity than a MW sample
in the frequency range of a few MHz to a few 100 MHz.

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Many experimental papers in the past decade support this

observation (Bona et al., 1998; Capaccioli et al., 2000;
Bona et al., 2001, 2002). At high frequencies ( 1 GHz),
it is often thought that the interfacial polarization is
negligible. Therefore, the measurement at high frequencies
is not expected to be sensitive to rock texture and uid
conguration and is used to estimate water saturation.
It has long been recognized that the ow of oil through
partially saturated rock samples depends critically on the
geometrical conguration of oil and water phases within the
pore space. This geometrical conguration has often been
described by the concept of wettability, a quantity that is
difcult to measure experimentally. In the literature, there
have been many studies on the effect of wettability on NMR
data. There have also been other separate studies on the
effect of wettability on dielectric data (Knight and Endres,
1990; Knight and Abad, 1995; Li, 1999; Bona et al., 1998;
Nguyen et al., 1999; Capaccioli et al., 2000; Garrouch, 2000;
Araujo et al., 2001; Bona et al., 2001, 2002). However,
interpretation of wettability and uid saturations from NMR
and dielectric data can be ambiguous. Factors such as internal
gradients, high gas/oil ratios, and restricted diffusion affect
the quantitative interpretation of both water/oil saturation
and wettability from NMR data. If they are not taken into
account, interpretation can be misleading (Minh et al.,
2003). Similarly, differences in rock lithology, presence of
clay, rock heterogeneity, and the applicability of various
mixing laws to estimate Sw in a sample make dielectric
interpretation uncertain (Seleznev et al., 2004). In addition,
the extent of silanization, a process often used in laboratories
to make a sample MW, is often uncertain making dielectric
interpretation ambiguous (Bona et al., 2001).
Recently, there has been an effort to combine the
complementary nature of these two measurements to lower
the ambiguity in interpretation (Bachman et al., 2012;
Heaton et al., 2012). These studies are well motivated and
have been applied to a few eld datasets. Their applicability
can be further enhanced by more detailed laboratory studies
clearly showing the systematic effects of wettability and
uid saturation simultaneously on NMR and dielectric
data on rocks partially saturated with brine and crude oil.
These laboratory datasets can help improve our fundamental
understanding of the effects of wettability and uid
saturations on NMR and dielectric data and bring out the
value of an integrated analysis.
In this manuscript, we present an experimental study of
the effect of wettability and uid saturation on three identical
samples of the same lithology. All samples are from outcrop
and were initially WW. They were systematically put through
the complete saturation cycle, and the wettability of two of
the samples was changed to MW by aging the sample. NMR,

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Venkataramanan et al.

dielectric, and resistivity measurements were performed at

different stages of uid saturation and wettability. Analysis of
the NMR data clearly shows that aging the rock changes the
wettability. These changes are observed in the differences in
water-phase relaxivities of WW and MW samples, systematic
differences in oil and water T2 distributions, as well as the
amount of bound water between samples. The dielectric data
are also clearly sensitive to the oil water conguration in the
sample. The dispersion of permittivity and conductivity for a
WW sample is signicantly larger than for a MW sample. To
rst order, the data at ~ 1 GHz are apparently sensitive only
to the volume of water in the sample. These observations
are supported by analysis of resistivity measurements. In
addition, these changes in wettability of the samples are
clearly associated with modications to relative permeability.
This is evidenced by the presence of a trapped water phase
in the MW samples. By helping improve our understanding
of the effects of wettability and uid saturations on NMR
and dielectric data, we expect that this study will be useful
in exploring new avenues in the future, for integrating NMR,
resistivity, and dielectric measurements.
A detailed petrophysical study of the properties of the
rock, as well as uids, was made prior to the start of the
experiment. In addition to NMR, dielectric and resistivity
data, thin-section images of the sample were obtained using
confocal microscopy. Mercury-injection-capillary-pressure
(MICP) measurements were also made on an identical
cylindrical plug. All of these datasets were analyzed in
conjunction to provide an accurate picture of the pore
geometry and connectivity as well as the oil and water
conguration in the rock.
The paper is organized as follows. In the next section,
we describe the experimental procedure and provide
petrophysical information and bulk-uid properties. In the
following section, we describe the analysis of MICP, thin
section and NMR data to estimate uid saturations and
oil and water T2 distributions. The effect of wettability
on NMR, dielectric, resistivity and relative permeability
data is described in the next section. The value of an
integrated analysis involving NMR, dielectric and resistivity
measurements is discussed in the last section.
EXPERIMENTS
Petrophysical Information
Three identical samples of Edwards limestone,
labeled A, B and C were chosen for this study. The
petrophysical properties for this limestone are provided in
Table 1. Mineralogical analysis indicates that this limestone
is predominantly calcite, with 97.9% CaCO3, 1.2% MgCO3,
0.4% SiO2 and 0.2% clay. All samples are cylindrical and
about 1.5 in. in diameter and length. MICP measurements
574

were made on a separate but identical cylindrical plug.

Table 1Petrophysical Parameters of Edwards Limestone

Experimental Protocol
All samples followed the experimental protocol shown
in Fig. 1. Thin sections were prepared and examined using
confocal microscopy on a slice thickness of about 40 m.
As shown in Fig. 2, there is clear evidence of a two-pore
system: intergranular pores (radius 10 m) and micropores
(radius 1 m) in the grain caused by partial dissolution
of calcite. The microporosity is observed in thin, ring like
structures in the grain. Initially, all samples are completely
brine-saturated. As shown in Fig. 2, at this initial stage, the
three samples are similar, with almost identical NMR (T2)
and dielectric (permittivity and conductivity dispersion)
properties.
As shown in Fig. 1, the samples go through primary
drainage in which the wetting phase (water) is decreased
to irreducible saturation and is replaced by crude oil. Next,
Samples B and C are aged in an oven at 60C for about six
weeks. It is expected that aging the rock in crude oil for a
few weeks will modify its wettability: changing the sample
from a WW sample to a MW sample (Zhang et al., 2000).
Sample A continues to be WW whereas presumably, Samples
B and C are MW. Conclusive evidence for this change in
wettability and its effect on measurements is sought through
NMR and dielectric measurements that are performed at
each stage of the saturation cycle.
All three samples go through the next few stages
of the saturation cycle. Spontaneous imbibition of brine
was obtained by immersing all samples in brine. Forced
imbibition of brine refers to forced displacement of some
of the crude oil in the samples by centrifuging them in
brine. Spontaneous drainage of water was obtained by
immersing the samples in a bath containing crude oil. Next,
forced drainage (also called secondary forced drainage) was
obtained by centrifuging the partially saturated samples in
crude oil. In this paper, we have used the words drainage
and imbibition to describe the processes that increase oil
and water saturation, respectively. Strictly speaking, the
term drainage refers to the replacement of the wetting phase
by the nonwetting phase. Similarly, imbibition refers to the
replacement of the nonwetting phase by the wetting phase.
All the spontaneous displacements of uids were carried
out over six weeks. The forced displacement was carried
out over one week in the centrifuge at oil-water differential

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Experimental Study of the Effects of Wettability and Fluid Saturation on Nuclear Magnetic Resonance and Dielectric Measurements in Limestone

pressure of 40 to 80 psi. At the end of the saturation cycle,

the samples were placed in D2O for four months to enable
complete exchange of hydrogen and deuterium ions in the
water. It is expected that if water forms a continuous path in
the sample leading to the outside, all hydrogen ions will be
diluted by deuterium. Evidence of this exchange was sought
through NMR measurements.
The experimental data discussed in this paper were
acquired in a time frame spanning approximately 24
to 36 months. The dielectric measurement was made
using a reection probe of 2 cm diameter and spanned
frequencies ranging from 20 MHz to 1 GHz. The depthof-investigation in the sample is approximately 1 cm.
Resistivity measurements were obtained using both a twoand a four-terminal impedance analyzer at frequencies from
0.1 to 10,000 Hz. NMR experiments were performed using
a MARAN low-eld (2 MHz) hydrogen magnetic resonance
instrument. The T2 distributions were obtained using the
Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence with
an echo spacing of 200 sec and a delay time of 15 sec.
The T1 - T2 measurements were obtained using an inversionrecovery pulse sequence with 10 logarithmically spaced
wait times between a few milliseconds and 10 seconds. The
D - T2 maps were obtained using the diffusion editing pulse
sequence using pulse-free gradient method with stimulated
echo, with 10 to 15 gradients varying between 0 and 35 G/
cm.
Samples B and C experienced very similar saturation
cycles. The repeatability of measurements and analysis
on these two samples provides us an additional level of
condence in subsequent interpretation. At each stage and in
between measurements, the samples are stored in a storage
uid, which is either brine or crude oil. The storage uid was
chosen at each stage to reduce the probability of spontaneous
changes. One of the challenges is to reach a homogeneous
water saturation along the length of the sample in forced
imbibition or drainage stages. This is important since the
dielectric measurement is a local measurement and the
reection probe would provide different readings, depending
on the orientation of the sample. An attempt at achieving
uniform water saturation was made by ipping the sample
upside down in the middle of the centrifuge cycle. At the
end of each saturation stage, a prole of porosity along the
length of the sample was measured using NMR to verify a
homogeneous distribution of water.
Information on uids
The properties of the brine and crude oil used in this
setup are provided in Table 2. The brine was synthesized in
the laboratory. Before the start of the experiment, the heavy
North Sea dead crude oil used in this study was aged at 90C
for a few weeks. As shown by the gas chromatography in
Fig. 4a, this oil does not have any components lighter than

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decane. Previous studies indicate that oil composition,

specically the polar compounds in resins and asphaltenes,
is a key characteristic of wettability-altering crude oils
(Buckley and Monsterleet, 1998). Laboratory saturatesaromatics-resins-asphaltenes (SARA) analysis shows about
14 wt% of resins and asphaltenes, indicating that this oil is a
good candidate for this experiment. Figure 4b shows that the
crude oil has a range of components, resulting in a wide range
of T2 relaxations, with a maximum relaxation of 100 msec.
As expected from previous studies (Song et al., 2002), the
T1 - T2 map of the bulk oil shows a strong correlation with an
average T1 / T2 of 1.1. The D -T2 map of the crude oil in Fig.
4 indicates that the slope of the D -T2 line is slightly smaller
than that of conventional alkanes (Mutina and Hrlimann,
2008; Hrlimann et al., 2009). As will be discussed later, the
knowledge of the T2 distributions and D -T2 maps of the bulk
water and crude oil plays an important role in estimating
uid saturations and interpreting wettability. Further, the
100 msec upper limit of oil relaxation time is useful in
deriving an accurate lower limit of water saturation from
NMR measurements in partially saturated samples.

Fig. 1Diagram of the saturation cycle followed by Samples A, B, and C.

All samples are initially water-wet (WW). Midway through the saturation
cycle, the wettability of Samples B and C is changed to mixed-wet (MW)
by aging the samples. NMR, resistivity, and dielectric measurements are
performed at all stages of the saturation cycle.

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Venkataramanan et al.

Fig. 2Thin section of oolitic limestone showing pore distribution is

bimodal with intergranular pores (radius 10 m) and micropores
(radius 1 m) in the form of thin, ring-like structures in the grain.

Fig. 4Bulk-oil properties of crude oil used in this study. (a) Gas
chromatograph of oil shows no light ends. (b) T2 distribution of the crude
oil shows a wide distribution of T2 values with an upper limit of about 100
ms. (c) The D T2 plot shows a slightly smaller slope than expected from
the standard alkane line. (d) T1 T2 plot shows a strong correlation, with
an average T1 /T2 of 1.1.

Table 2Properties of Brine and Crude Oil at Room Temperature

DATA ANALYSIS
Fig. 3At the beginning of the saturation cycle, all samples have 100%
water and have identical NMR T2 and dielectric-dispersion properties.

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Pore-Size Distribution from MICP Data

This measurement involves progressive injection of
mercury into a dry sample at steadily increasing pressures
(Jennings, 1987; Pittman, 1992). At incremental pressure
steps, pore throats of a particular size are invaded by mercury,
which enters pores with the largest throats rst. After pores

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Experimental Study of the Effects of Wettability and Fluid Saturation on Nuclear Magnetic Resonance and Dielectric Measurements in Limestone

with throats larger than a certain size are lled, the pressure
is increased to ll pores with smaller throats. The pressure
is increased in small increments up to a maximum pressure
of about 60,000 psi. Using the Laplace-Young equation, this
capillary pressure data can be converted into a pore-throat
distribution,

The total disconnected mercury saturation at the end of

the extrusion cycle is the sum of the disconnected mercury
saturation at any point and the disconnected saturation that
could arise from the connected phase from further extrusion,

(1)

From Eq. 3, with Si = 1, the variable C is calculated. Equations

2 and 4 lead to a quadratic equation of the form, aSdc2 + bSdc
+ k = 0, where

where Pc refers to capillary pressure, refers to surface

tension of mercury-air system (480 dynes/cm), refers to
the contact angle of mercury and air (usually 140), and r
refers to pore-throat radius.
In order to compare this pore-throat distribution with
NMR-estimated pore-body distribution, it is often assumed
that the pore-body/pore-throat ratio for this lithology is
known from the literature or available from image analysis.
Often, the extrusion (decreasing pressure) of mercury from
the sample is not measured. However, when it is available,
a self-consistent pore-body/pore-throat ratio can be obtained
from the measured hysteresis between the intrusion and
extrusion curves as follows (Ramakrishnan et al., 1998).
The intrusion curve is controlled by pore-throats whereas
the extrusion curve is controlled by pore radii, and their
connectivity. These curves, normalized to the total amount
of mercury in the sample at the end of the intrusion cycle, are
shown in Fig. 5a. An initial estimate of the pore-body/porethroat ratio is the ratio of radii for a given mercury-saturation
volume. For example, from Fig. 5a, at a saturation of 80%,
an approximate pore size is about 0.5 m with a throat size
of 0.2 m, resulting in a pore-body/pore-throat ratio of 2.5.
This ratio can further be averaged over all different mercury
saturations. This initial estimate can be further rened by
correcting the measured extrusion curve for trapped mercury
in the sample. At any point in the extrusion curve, the mercury
saturation in the sample is the sum of the disconnected and
connected network of mercury saturations
Simb = Sdc + Sc.

(2)

a=C

(5)

b = -C(Sres + Simb)

(6)

k = Simb[CSres - 1] + Sres.

(7)

The estimated connected and disconnected saturations

are shown in Fig. 5a. There is a fairly constant horizontal
shift between the intrusion and modied extrusion curve.
Therefore, a single pore-body/pore-throat ratio can be
assumed and obtained by computing a scaling factor that
best matches the measured intrusion and corrected extrusion
curves. In this scenario, this ratio was found to be 2.6.
Comparison of Pore Space from NMR T2 Distribution,
Image Analysis and MICP
A high-resolution image analysis of the thin section in
Fig. 2 yields a sample porosity of 26 p.u. The image was
analyzed using an automated petrographic-image-analysis
method that is based on the watershed algorithm (Roerdink
and Meijster, 2000). From this analysis, 70% of the porosity
is from pores with radii < 5 m and 30% from pores with
radii > 5 m. The pore-body/pore-throat ratio is estimated to
be 2.77. This is in agreement with analysis of MICP data.
A pore-size distribution can be obtained from a fully watersaturated NMR T2 distribution as follows.
(8)

At the end of the intrusion cycle, the amount of mercury

saturation in the sample, Si, is unity. At the end of the extrusion
cycle, there is a residual disconnected network of mercury in
the sample, denoted by Sres. With knowledge of the initial and
nal saturations and using Lands equation, which relates
the residual to initial saturation (Ramakrishnan and Wasan,
1986), the amount of connected and disconnected saturations
at any point in the extrusion curve can be computed:
(3)

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(4)

where is the relaxivity, is the ratio of area to volume

of a pore, and T2,B is the relaxation of the bulk water. For
spherical pores with radius TTTTTTTherefore, the NMR T2
distribution can be converted to a pore-size r distribution
by suitable choice of relaxivity . Figure 5b compares the
pore-size distribution from the mercury-extrusion data (with
a pore-body/pore-throat ratio of 2.6) with NMR pore-size
distribution. A relaxivity of around 6.6 m/sec was chosen
to optimize the MICP and NMR comparison. As will be
presented later in Figs. 8a and 8c, this relaxivity value is

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Venkataramanan et al.

in reasonable agreement with the relaxivity of 8 m/sec

obtained from D T2 plots. The microporosity (pores size
< 5 m) from mercury and T2 distribution is about 60% and
consistent with image analysis.
Analysis of NMR D T2 Data to Estimate Water
Saturation and Oil and Water T2 Distributions
Figure 6 illustrates the method used in this study to
estimate saturations and oil and water T2 distributions from
D T2 and T2 distribution of partially saturated sample.
In the literature, the diffusion-coefcient-logarithmicmean (DCLM) technique is often used to separate out the
contributions of oil and water in this regime. This method
involves computing the logarithmic-mean diffusion
coefcient as a function of relaxation time in D T2 plots.
The relative differences between the logarithmic-mean
diffusion coefcient and expected diffusion coefcients of
restricted water and bulk oil are used to estimate water and
oil saturations (Zielinski et al., 2010). This DCLM method
is not directly applicable on our laboratory data for the
following reasons. First, the porosity sensitivity is different
at different regions of the D T2 domain and is dependent
on the different T1/T2 ratios of the two uids. Second, the
heavy oil used in this study has a viscosity of 100 cp at
room temperature. Consequently, a signicant part of the T2
distribution is below the resolution limit of 10 msec on the
D T2 map. Lastly, this method does not take into account a
priori knowledge of the bulk relaxation of oil.
To address these issues, we modify the DCLM method
as follows and demonstrate it on the D T2 map of the partial
mixture of oil and water shown in Fig. 6a. The DCLM line
is superimposed in red on this D T2 map. First, as shown
in Fig. 6b, this oil has a an relaxation time upper limit of
100 msec. Therefore, any signature in the D T2 map greater
than 100 msec corresponds to the water phase. Both oil and
restricted water contribute to the map between 10 msec (the
resolution of the D T2 map) and 100 msec. The DCLM
technique can be used in this regime to estimate water
saturation, Sw(T2), as a function of relaxation time, as shown
in Fig. 6b. For example, at 10 msec, the water saturation is
about 80%. Therefore, at 10 msec, a rst-order estimate of
the water and oil T2 distributions are 0.8f(T2) and 0.2f(T2),
respectively. Initial estimates of water and oil T2 distributions
between 10 and 100 msec are computed from f(T2) as Sw(T2)
f(T2), and (1 Sw(T2))f(T2), respectively, and are shown in
Figs. 6c and 6d, respectively. This method is carried out at
all relaxation times larger than 10 and 100 msec.
From this initial estimate of water and oil T2 distributions,
a more rened estimate of the T2 distributions and net uid
saturations in the sample is computed as follows. The ratio
of the maximum amplitude of the initial oil T2 distribution to

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the maximum amplitude of the bulk-oil T2 distribution is a

reasonable approximation to oil saturation So in the sample.
The reasoning behind this is as follows: if the sample is WW,
oil is expected to relax at its bulk relaxation. In this case,
the oil T2 distribution is expected to be a scaled version of
the bulk-oil distribution. The scaling factor is proportional
to net oil saturation in the sample, So. On the other hand, if
the sample is MW, the oil T2 distribution will shift to shorter
relaxation times due to enhanced surface relaxation. Despite
the shift, the maximum amplitude of the resulting oil T2
distribution is scaled by So to the maximum amplitude of the
bulk oil T2 distribution. The amount of the T2 shift is due to
additional surface relaxation and, when added to the known
bulk relaxation of oil, can be used to compute the entire
oil T2 distribution as shown in Fig. 6e. The magnetization
data from the predicted oil T2 distribution is subtracted from
the measured CPMG data of the sample to estimate the
magnetization data of the water phase. The corresponding T2
distribution of water is shown in blue in 6e.

Fig. 5(a) Plot showing a pore-body/pore-throat ratio of 2.6 obtained

from measured intrusion and corrected extrusion curves using the
method described in section Data Analysis and Ramakrishnan
et al. (1998). (b) Using this pore-body/pore-throat ratio, the pore-size
distribution obtained from the mercury-intrusion curve is found to match
well with the NMR pore-size distribution obtained with a relaxivity of 6.6
m/s in Eq. 8.

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Experimental Study of the Effects of Wettability and Fluid Saturation on Nuclear Magnetic Resonance and Dielectric Measurements in Limestone

Fig. 6Method to estimate oil and water saturations and T2 distributions.

(a) D T2 plot of Sample A in spontaneous drainage showing the
presence of water in small pores and a mixture of oil and water in large
pores. (b) Water saturation estimated from DCLM method on the D
T2 map. (c and d) Initial estimates of water and oil T2 distributions.
From comparison of this oil T2 distribution to the bulk oil, the estimated
oil saturation is about 0.68. (e) Final estimates of water and oil T2
distributions.

Fig. 7Effect of wettability is observed in T2 distributions at different

stages of the saturation cycle. In Samples B and C, water in larger pores
shows a clear shift toward the bulk relaxation of water in the later stages
of the saturation cycle. This shift implies decreased surface relaxation of
water, implying that Samples B and C are MW. This shift is not observed
in Sample A since it is WW.

EFFECT OF WETTABILITY ON NMR AND

DIELECTRIC DATA

remain WW while the intergranular pores are dalmatian-wet

or MW.

Effect of Wettability on T2 Distributions Obtained from

CPMG Data
The T2 distributions of bulk oil, WW and MW samples in
different stages of partial saturation in the three samples are
shown in Figs. 7ac. The peak in the T2 distribution around
250 msec corresponds to water in the larger pores. This peak
does not shift signicantly for WW Sample A as it goes
through the saturation cycle. On the other hand, for Samples
B and C, this T2 peak shows a clear shift toward the bulk
relaxation of water of 2.2 sec. This shift implies decreased
surface relaxation of water, implying that Samples B and
C are MW. This difference in wettability was supported by
resistivity measurements obtained during spontaneous- and
forced-imbibition stages. These measurements show that
after aging Samples B and C have 1 to 3 orders of magnitude
lower resistivity compared to Sample A. It is possible to
explain these T2 distributions and resistivity measurements
by hypothesizing that the micropores in Samples B and C

Effect of Wettability on Water-Phase Relaxivity

Zielinski et al., (2013) have also proposed that, while
comparing samples of the same lithology, a difference in
wettability can be inferred from observing differences in
relaxivity of the water phase in large pores (Zielinski et al.,
2013). The D T2 plots of Samples A and B when they are
fully water saturated and in spontaneous drainage are shown
in Fig. 8.
Diffusion-restricted water lines corresponding to
relaxivities of 2 and 8 m/s are superimposed on all the D
T2 plots (Zielinski et al., 2010). The line corresponding
to a = 8 m/s passes through the center of the water peak
for both stages in Sample A and the fully water-saturated
stage in Sample B. This implies that relaxivity (and therefore
wettability) is similar for the fully water-saturated stages in
Samples A and B. Further, since = 8 m/s passes through
both stages of Sample A, we infer that wettability is identical
between these two stages. On the other hand, when Sample

December 2014

PETROPHYSICS

579

Venkataramanan et al.

B in secondary spontaneous drainage, the line corresponding

to = 2 m/s passes through the center of its water peak.
This decrease in relaxivity occurs because only a fraction of
the grain surface is in contact with water. This decrease is
yet another clear indication that Sample B has changed from
being WW in the fully water-saturated stage to MW in the
drainage phase. This conclusion was supported by resistivity
data that showed that the DC conductivity of Sample A is two
orders of magnitude higher than Sample B in the drainage
phase.

Fig. 8Effect of MW behavior is observed in the decrease in waterphase relaxivity in MW samples in D T2 maps. It is seen that = 8 m/s
ts Samples A and B when they are water saturated and ts Sample A
when it is in spontaneous drainage. On the other hand, the relaxivity
drops to = 2 m/s in Sample B when it is in spontaneous drainage.
This decrease is another indication that only a fraction of the grain
surface is in contact with water in (d).

Effect of Wettability on Oil and Water T2 Distributions

Obtained from D T2 Maps
It is instructive to compare the T2 distributions of oil
and water for the same sample at almost the same partial
saturations but with different wettability. Oil and water T2
distributions for Sample B in primary drainage are shown in
Fig. 9a. At this stage, the sample is WW and we observe oil
relaxing at its bulk-relaxation rate. According to conventional
wisdom, the bound water is expected to be in the small pores
and lining the pore walls of the larger pores.
Figure 9b shows the same sample after its wettability
has changed to MW and the sample is in spontaneous
secondary drainage. We observe that some water is bound
(short T2). There is also some water lling some of the

580

larger pores (long T2). Comparing this to the T2 distribution

in Fig. 7b when the sample is completely lled with water,
we see that relaxation time of water in some of the large
pores in secondary drainage is closer to its bulk relaxation.
This implies that water is relaxing at the bulk rate in either
some of the larger pores or part of some of the larger pores.
Therefore, water in these pores exhibits MW behavior. The
amount of bound water (T2 < 100 msec) in Fig. 9a is about
18% whereas that in Fig. 9b is about 12%, indicating that
when the sample is in MW state, the amount of water in
small pores or bound to the larger pores is lower than when
the sample is WW.
Comparing oil T2 distributions in Figs. 9a and 9b, we
observe that the oil T2 distribution has moved to shorter
relaxation times. This implies that oil is experiencing an
additional surface relaxation in addition to the bulk relaxation.
It is interesting that there happens to be an almost identical
volume of water ~ 18 to 19% in both stages in the sample.
However, the relative geometrical arrangement of oil and
water are different in the two stages. The measured NMR
data are sensitive to the different geometrical congurations.
To delineate the effects of primary and secondary
drainage and wettability, a comparison between data from
Samples A and B in forced primary and secondary drainage
would be very instructive. Unfortunately, Sample A was
accidentally completely desaturated in the centrifuge during
secondary forced drainage. Therefore, the effect of primary
and secondary drainage on WW Sample A could not be
studied.
Effect of Wettability on Dielectric Data
The different oil and water conguration is also seen
to affect the dielectric dispersion in Figs. 9c and 9d. When
the sample is WW, permittivity and conductivity are higher
than when it is MW. As expected, this difference is larger
at lower frequencies. When water adheres to pore walls,
there is a buildup of charge at the interface between water
and grain. At low frequencies the electric eld changes
slowly enough that the ions can follow the variations and
develop maximum polarization. At high frequencies, there
is not enough time for the charge to buildup and the effect
is reduced. On the other hand, since oil is nonpolar, there is
little or no charge buildup in the interface between oil and
grain when oil is in contact with the grain surface. Thus, the
measured dispersion of permittivity for Sample B when it
is MW is smaller than that when it is WW. We note that at
about 1 GHz, the dielectric properties are only sensitive to
the amount of water in the sample and the measurements
are almost identical. Similarly, due to the presence of fewer
continuous conductive pathways across the sample, the
conductivity of Sample B in MW stage at all the measured

PETROPHYSICS

December 2014

Experimental Study of the Effects of Wettability and Fluid Saturation on Nuclear Magnetic Resonance and Dielectric Measurements in Limestone

frequencies is smaller than when it is in the WW stage. An

independent measurement of resistivity also shows that DC
conductivity, DC, of Sample B in the WW stage is larger
than in the MW stage.
This observation is also shown in Fig. 10 where we
compare oil and water T2 distributions when the three
samples are in spontaneous drainage. All samples have about
30% water. In MW Samples B and C, water in large pores
is not completely in contact with the surface. We deduce
this from two observations. First, in comparison to WW
Sample A, water T2 in larger pores has a longer relaxation
time. However, it is not relaxing at the bulk rate of 2.2 sec,
which implies that some of the water in larger pores is still in
contact with the pore walls. Second, in comparison to Sample
A, oil in Samples B and C have a slightly shorter relaxation
time. This implies that some of the oil is adhering to the
pore walls. The repeatability of T2 distributions in Samples
B and C provides additional condence in this conclusion.
Thus, although all samples happen to have almost identical
lithology and water and oil saturation, the conguration of
oil and water in the rock is different between Sample A and
Samples B and C, giving rise to different NMR oil and water
T2 distributions.
The corresponding dielectric-dispersion curves are
shown in Figs. 10d and 10e. All samples are observed to have
similar permittivities and conductivities at 1 GHz. Using
the complex refractive index (CRI) model, this translates to
about 30% water saturation in all samples (Seleznev et al.,
2004). As expected, WW Sample A has higher permittivity
and conductivity than MW Samples B and C over the
frequency range of measurement. It is also reassuring to
see repeatability of dielectric measurements in Samples B
and C which have gone through identical workows. An
independent measurement of resistivity also conrms that
the DC conductivity of WW Sample A is larger than MW
Samples B and C.
Effect of Wettability on Water- and Oil-Phase Saturation
and Connectivity
At the end of the secondary forced drainage phase,
Sample B was placed in an Amott cell with D2O for four
months. NMR data before and after exchange with D2O are
shown in Fig. 11. The concentration of deuterium in the
Amott cell was many orders of magnitude larger than the
concentration of hydrogen ions in the water phase in the
sample. Therefore, if water in the pores of the rock formed
a continuous connected path to the outside of the sample,
most of the hydrogen in the water phase in the rock will be
diluted by deuterium. The time for this dilution or exchange
is determined by restricted diffusion of hydrogen ions.
Four months is a sufcient time period to see a complete

December 2014

Fig. 9The effect of wettability on the same sample results in different

oil and water congurations and is observed in NMR, dielectric and
resistivity data. Sample B is WW in primary drainage and MW in
secondary forced drainage. Water saturation in both stages is about
18%. (a) In primary drainage, water is bound to pore walls. Oil is relaxing
at its bulk rate. (b) In secondary drainage, there is less bound water.
There is more water relaxing closer to its bulk relaxation, implying less
surface relaxation compared to (a). (c and d) Dielectric dispersion
curves and DC conductivity for Sample B are larger when it is WW than
when it is MW.

Fig. 10Samples A (WW) and B, C (MW) show different NMR, dielectric

and resistivity properties in spontaneous drainage due to differences
in wettability. (a, b, c) Water present in the larger pores in Samples B
and C undergoes less surface relaxation, resulting in longer relaxation
times than in WW sample A. Similarly, oil (green) in Samples B and
C undergoes more surface relaxation, resulting in shorter relaxation
than in Sample A. (d and e) Even though all samples have similar water
saturations, the geometrical congurations of the water and oil in the
samples are different and affect dielectric dispersion.

PETROPHYSICS

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Venkataramanan et al.

exchange of ions, even with a tortuosity of 100. Since

deuteriums nuclear-spin properties differs from that of light
hydrogen, deuterium is not seen by an NMR instrument
tuned to light-hydrogen and will therefore not appear in the
NMR T2 distribution. In Fig. 11, we observe that only a small
volume of water in the larger pores has exchanged with D2O.
This implies that some of the water is trapped in the pores
and disconnected from the outside. Further supporting and
independent evidence for this conclusion was provided by
the resistivity measurement. As shown in Fig. 10e, the DC
conductivity when it is WW in primary drainage is larger
than DC conductivity when it is MW and in secondary
drainage. Since water saturation in the sample is around
20% in both stages, water in the secondary forced drainage
must be trapped in pores and not contributing to the DC
conductivity. This conclusion is also consistent with other
observations in the literature on the effect of rock wettability
on oil and water phase connectivity and has implications
in the relative permeabilities of the two phases and the oil
recovery factor (Abdallah et al., 2007).

Fig. 11Even after a time period of four months, we observe that only
a small volume of water in the larger pores has exchanged with D2O.
This implies that some of the water in the larger pores is trapped and
disconnected from the outside and cannot be exchanged by diffusion.

INTEGRATION OF NMR AND DIELECTRIC DATA

Downhole NMR and the new-generation multifrequency
dielectric tools have similar depths of investigation and
are sensitive to about 1 to 4 in. into the formation. Since
the measurement volumes of both measurements are
commensurate and the measurements and are both sensitive
to wettability and uid saturation, it is natural to try to
develop an integrated analysis (Bachman et al., 2012; Heaton
et al., 2012).
The use of diffusion-relaxation maps is a signicant
step forward in uid characterization and quantication

582

of saturations (Hrlimann and Venkataramanan, 2002).

Interpretation of these maps is relatively straightforward
when the uids have large diffusion and/or relaxation contrast
and obey standard correlations. When the D - T2 maps do not
resolve into separate peaks for the different phases, one of
the standard methods of estimating saturations is the use of
the DCLM method. Since it is necessary to partition merged
peaks into separate uid contributions, the DCLM method
results in a redistribution of amplitude at each relaxation
time onto oil and water model response lines. It is a very
pragmatic approach. However, this method does have its
limitations. For example, the results are sometimes affected
by choice of inversion parameters, such as the minimum
value of the diffusion coefcient used for inversion. In
addition, factors such as internal gradients, high gas/oil
ratios as well as restricted diffusion affect the quantitative
interpretation of uid saturations and wettability from NMR
data. If they are not taken into account, the interpretation can
be misleading (Minh et al., 2003). Therefore, these effects
need to be recognized and accounted for.
We expect that this study will be useful in exploring new
avenues, in the future, for integrating NMR and dielectric
measurements. To date, several specic approaches show
promise. An independent estimate of water saturation
(such as from dielectric measurement) can be helpful in
inverting and interpreting the NMR data. For example, in
heavy oils, the relaxation time of oil is expected to be much
shorter than that of water. In this case, a T2 cutoff can be
derived so that water saturation from NMR is constrained
to match that from dielectric data. Bulk-oil properties such
as viscosity are then estimated, assuming the rock is WW
(Bachman et al., 2012). More recently, Heaton et al. (2012)
suggest an elegant workow to integrate NMR and dielectric
data in a Monte Carlo framework. Given water saturation
from dielectric measurement and its associated uncertainty,
this workow attempts to provide realistic uncertainties
in heavy-oil viscosity. In our laboratory study, as shown
in Fig. 10 when the samples are in spontaneous drainage,
the amount of water in the samples, as determined from
dielectric measurements using the CRI model, is about 30%.
Application of the DCLM technique to D T2 maps below
100 msec, combined with the knowledge that any relaxation
above 100 msec corresponds to the water phase, provides a
comparable estimate of water saturation in the three samples.
Water saturation from both measurements on all samples and
at all stages are compared in Fig. 12 and shows reasonable
agreement, providing us an additional level of condence in
the interpretation of NMR data.
Figure 9 clearly demonstrates the value of NMR data in
interpreting dielectric data. Consider a scenario, where the
dielectric measurements in Figs. 9c and 9d are measured at

PETROPHYSICS

December 2014

Experimental Study of the Effects of Wettability and Fluid Saturation on Nuclear Magnetic Resonance and Dielectric Measurements in Limestone

two successive depths downhole. Since, both datasets are

almost identical at 1 GHz, both depths would be interpreted
to have about 20% water. However, several factors such as
differences in lithology, aspect ratio of the grains, and the
amount of clay can be proposed to explain the differences
between the datasets at lower frequencies. The NMR data
in Figs. 9a and 9b highlight that the conguration of oil and
water in the two rocks are different and leads to different
signatures in dielectric-dispersion.
Figure 10 also highlights the same point. In carbonates,
with increasing depth, the reservoir can transition in depth
from an OW to a MW and a WW reservoir (Minh et al., 2003).
Thus, it is possible to consider a scenario where Samples A,
B and C correspond to different depths in a reservoir. Again,
the value of NMR data is the ability to clearly identify that
wettability of Sample A is different from Samples B and
C. This helps reduce the ambiguity in the interpretation of
dielectric dispersion data.

Fig. 12Water saturation Sw obtained from NMR compares well with

water saturation obtained from dielectric data at 1 GHz using the CRI
method.

SUMMARY
The geometrical conguration of water and oil in
the pore space has been described in the literature by the
concept of wettability. It is measured in the laboratory
using the Amott-Harvey and USBM indices. Both of these
measurements are time-consuming and difcult to measure
experimentally. NMR and dielectric measurements may
potentially be able to give a more direct measurement of
the conguration of the uid phases. In this paper, we have
presented an experimental study of the effect of wettability
and uid saturation simultaneously on NMR and dielectric
data. Thin sections of the studied oolitic limestone indicate
that the pore distribution is bimodal. Intergranular pores

December 2014

have radii of nearly 10 m and intragranular pores have radii

around 1 m. Using a method described in Ramakrishnan
et al. (1998), we show that MICP extrusion and intrusion
data can be used to estimate a pore-body/pore-throat ratio of
2.6 and can be converted into a pore-size distribution. This
pore-size distribution is consistent with that obtained from
NMR.
We have shown that prior knowledge of bulk T2
relaxation of oil and brine can be used to provide reliable
lower limits of water saturation. The D T2 maps provide an
additional dimension to further resolve the T2 distributions
of oil and water. Together with knowledge of bulk-relaxation
properties, they can be used to estimate uid saturations and
understand changes in wettability between samples. Changes
in wettability are evidenced in the following differences
between WW and MW samples: water-phase relaxivities, oil
and water T2 distributions and the amount of bound water.
The measured dielectric data are clearly sensitive
to the oil and water conguration in the sample. In these
samples, the effect of interfacial polarization is small, at
1 GHz. Therefore, to rst order, the data at this frequency
are seemingly sensitive only to the volume of water in the
sample. However, at lower frequencies, between a few
MHz and a few 100 MHz, the dispersion of permittivity and
conductivity for a WW sample is signicantly larger than for
a MW sample.
Since downhole NMR and dielectric tools have similar
depths of investigation and are both sensitive to wettability
and uid saturation, it is natural to try and develop an
integrated analysis. By helping improve our understanding
of the effects of wettability and uid saturations on NMR,
resistivity and dielectric data, we expect that this study
will be useful in exploring new avenues in the future, for
integrating these measurements.
ACKNOWLEDGEMENTS
This work was made possible due to data patiently
acquired over a period of a few years in Schlumberger
Doll Research (SDR) in Cambridge, Massachusetts, by
many colleagues: Abigail Matteson, Lisa Meeks, Kyle
Blake, Benjamin Costanza, Andrew Caston, Tim Simes and
Jeffrey Crank. NMR properties of bulk oil were measured
by Philip Singer in Schlumberger Reservoir Laboratories
in Houston. SARA analysis on the oil was performed by
OilPhase, Houston. Kate Washburn was responsible for
providing us access to this crude oil. We are grateful to T.S.
Ramakrishnan for discussions on many issues, including
MICP, wettability and relative permeability. We are also
grateful to our managers Tarek M. Habashy, Ridvan Akkurt
and Smaine Zeroug for patiently supporting this work. The
authors wish to acknowledge Thomas Neville for initiating
this laboratory study at SDR.

PETROPHYSICS

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Venkataramanan et al.

NOMENCLATURE
A
D
f(T2)
Pc
r

dc
Sc
Sdc
Si
Simb
Sres
So
Sw

T1
T2
T2,B
V

= area of a pore, m2
= diffusion coefcient,
= T2 distribution
= capillary pressure, psi
= pore-throat radius, m
= relaxivity, m/s
= surface tension of mercury-air system, N/m
= DC conductivity of partially saturated rock, S/m
= connected mercury saturation
= disconnected mercury saturation
= mercury saturation at the end of intrusion cycle
= mercury saturation in the extrusion cycle
= residual amount of mercury
= oil saturation in core
= water saturation in core
= contact angle of mercury and air
= longitudinal relaxation time, sec
= transverse relaxation time, sec
= transverse relaxation time of bulk uid, sec
= volume of a pore, m3
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Sayed, R.H., and Abdelaal, A.F., 2010, Restricted Diffusion
Effects in Saturation Estimates from 2D Diffusion-Relaxation
NMR Maps, paper SPE-134841, presented at the SPE Annual
Technical Conference and Exhbition, Florence, Italy, 1922,
September.

December 2014

ABOUT THE AUTHORS

Lalitha Venkataramanan is a Scientic
Advisor and Program Manager of
Measurement Interpretation program
in Schlumberger Doll Research,
Boston. Her current interests include
mathematical modeling and inversion,
optimization, probability and stochastic
processes. Trained as an Electrical Engineer, she obtained
her M.S and PhD degrees from Yale University in 1998.
Martin Hrlimann is a Scientic Advisor
working in the research laboratory of
Schlumberger in Cambridge, USA. He
obtained a Dipl. Natw. degree from the
Swiss Federal Institute of Technology in
Zrich, Switzerland, and a Ph.D. degree
in Physics from the University of British
Columbia in Vancouver, Canada. After spending two years
at the University of California in Berkeley as a postdoctoral
fellow, he joined Schlumberger Doll research in 1992.
His work has focused on the development of new NMR
techniques for the study of porous media and complex uids
with particular emphasis on well logging applications. He is
a fellow of the American Physical Society and was awarded
the Christiaan Huygens Medal by the European Geosciences
Union in 2011.
Jeffrey Tarvin earned an AB degree in
Physics at Thomas More College and
a PhD in condensed matter physics
at MIT. He studied the dynamic
properties of condensed matter at
Brookhaven National Laboratory and
high temperature plasma physics at
KMS Fusion. He developed oil-well
instrumentation and interpretation at Schlumberger for more
than 20 years. He is now an independent consultant at Tarvin
Professional Services.

PETROPHYSICS

Kamilla Fellah is a research engineer

at Schlumberger-Doll Research. She
works in the dielectric spectroscopy
and low eld NMR labs. She has a
M.S. in geology from Washington
State University and a B.A. in geology
from the College of Wooster.

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Venkataramanan et al.

Diana Acero-Allard is a graduate of

Geology and holds an MSc degree
in Geophysics from the Universidad
Nacional de Colombia, Bogota.
She works in acquisition and image
processing using Laser Scanning
Confocal Microscopy. She has
developed workows to acquire
Middle East microporous carbonates 2D and 3D images and
process those to quantify microporosities and synthetic core
analysis. She also has analyzed images from sandstones and
mudstones reservoirs in the United States.
Nikita V. Seleznev is a Petrophysics
program manager and principal
research scientist at SchlumbergerDoll Research (SDR), Boston,
Massachusetts, USA. He conducts
research in dielectric and resistivity
logging tools and techniques,
petrophysics of conventional and unconventional reservoirs.
He has been developing interpretation products that directly
measure water volume and rock textural information for
the Dielectric Scanner tool. He joined Schlumberger in
1998 as a Wireline eld engineer. Nikita obtained as PhD in
petrophysics from the Delft University of Technology, The
Netherlands.

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PETROPHYSICS

December 2014